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  • General Chemistry  (10,264)
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  • 1995-1999  (9,359)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2147-2156 
    ISSN: 1434-1948
    Keywords: Tetrapodal pentadentate ligand ; Ligand periphery ; Polydentate amine complex ; Nickel ; Podand ; Schiff base ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrapodal pentaamine ligand 2,6-bis(1′,3′-diamino-2′-methylprop-2′-yl)pyridine (1), which contains four equivalent primary amino groups, can be derivatised partly or completely by Schiff base condensation with suitable carbonyl compounds. The new ligands thus obtained are mononucleating, as shown by the X-ray crystal structures of their respective nickel(II) complexes. Reaction of 1 with 1 equiv. of salicylaldehyde and subsequent reduction allows the selective modification of one of the four sidearms. The resulting ligand 2 is hexadentate and uninegative in its nickel(II) complex {[(2)Ni]PF6} (3) with both the secondary amine and the phenoxide functionalities coordinated to the metal centre. The unreduced Schiff base form of the ligand, 4, does not form a complex with nickel(II) as readily, and only a small quantity of the mixed salt {[(4)Ni][(1)Ni(H2O)](Br)2(PF6)} (5)has been obtained. While the overall coordination of 4 resembles that of 2, there is considerably more strain in the appended chelate ring, due to the presence of the C=N double bond. Modification of one arm in 1 can also be achieved by condensation with 1 equiv. of acetylacetone, to give the new ligand 6 which, likewise, is hexadentate in its NiII complex {[(6)Ni](PF6)2} (7). In this case, however, the N/O-functional sidearm is not deprotonated. Rather, it is coordinated as the keto-imine tautomer, making 7 a rare example of a metal complex containing this structural fragment. Two-fold functionalisation of 1 is observed upon reaction with acetone, regardless of whether the ketone is present in stoichiometric amounts or in excess, to give the pentadentate ligand 8with two diagonally juxtaposed isopropylidene-imine units. The complex isolated with this ligand {[(8)Ni](PF6)2} (9) contains pentacoordinate NiII, the sixth coordination site being blocked by the rigidly positioned isopropylidene groups. When reacted with 4 equiv. of trans-cinnamaldehyde, all the primary amino groups in 1 condense to give the four-fold Schiff base 10, which acts as a pentadentate podand towards nickel(II). In this complex, {[(10)Ni(OH2)]Br2} (11), an aqua ligand completes the coordination octahedron. All ligands are stable towards hydrolysis when coordinated to the metal, despite the presence of alkyl-imine groups in some cases.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2157-2166 
    ISSN: 1434-1948
    Keywords: Septadentate N5S2-ligand ; Dinuclear complexes ; Nickel ; Reactivity ; Redox chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination chemistry of a series of dinickel complexes of the new septadentate amine-thiolate ligand N,N′-bis[2-thio-3-aminomethyl-5-tert-butylbenzyl]diethylenetriamine, H29, has been investigated in the context of ligand binding and oxidation state changes. The complexes [Ni2(9)(L)][ClO4]2 (10), [Ni2(9)(Cl)][Cl] (11), [Ni2(9)(L)][BPh4]2 (12), and [Ni2(9)(NCS)][OH·OH2] (13) have central N2Ni(μ-SR)2NiN′3L cores [L = labile solvent molecule (10, 12), Cl- (11), and NCS- (13)] composed of dithiolate bridged planar NiN2S2 and six-coordinate NiN′3S2L units. This is demonstrated for 11 and 13 by crystal structure determinations and for 10 and 12 by UV/Vis spectroscopy and room temperature magnetic susceptibility measurements. Complexes 10, 11, or 12 readily add other co-ligands at the NiN′3S2L fragment by substitution of the solvent molecule L (10, 12) or the chloride substituent (11). The overall structure of the parent complexes is not affected by the substitution reactions. An electrochemical study has shown that complex 10 undergoes two successive one-electron oxidations at +0.88 and +0.41 V vs SCE. The oxidized species are not thermally stable, but electronic absorption spectra and EPR spectra are indicative of the presence of NiIII species.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2167-2172 
    ISSN: 1434-1948
    Keywords: Macrocyclic compounds ; Amine-Thiolate Donors ; Polynuclear Complexes ; Nickel ; Condensation reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel route to macrocyclic amine-thiophenolate ligands is described. The new, air-stable thiophenolate precursor 1,2-bis(4-tert-butyl-2,6-diformyl-phenylsulfanyl)ethane (4) is readily condensed with two equivalents of 1,2-ethanediamine or 1,3-propanediamine under medium to high dilution conditions to give 2 × 4 condensation products. The smaller 1 × 2 macrocyclic compounds are not produced under these conditions. Subsequent reduction with NaBH4 (reduction of imine groups) and Na/NH3 (reductive cleavage of aryl-alkylsulfides) provides the 36- and 40-membered amine-thiophenolate ligands H46a and H46b. The macrocyclic compounds are versatile ligands for the preparation of polynuclear transition metal complexes. With divalent nickel H46a forms the di- and tetranuclear complexes [Ni2(6a)] (7) and [Ni4(6a)][ClO4]4 (8). Reaction of 8 with four equivalents of NH4SCN yields the novel isothiocyanate complex [Ni4II(6a)(NCS)4]·10MeCN (9). The structure consists of well-separated molecules of the tetranuclear complex [NiII4(6a)(NCS)4] (Ci symmetry). Two symmetry-related binuclear [N2Ni(μ2-SR)2NiN4] fragments composed of thiolate-bridged distorted planar {N2S2Ni}- and distorted cis-octahedral {(SCN)2N2S2Ni} units reside within the cavity of the macrocycle. The intramolecular distance between the two binuclear units is 6.144(1) Å.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2173-2185 
    ISSN: 1434-1948
    Keywords: EPR spectroscopy ; Metallocenylboranes ; Organovanadium radicals ; Redox chemistry (CV) ; X-ray diffraction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The paramagnetic complexes di(mesityl)([5]trovacenyl)borane (5·), (mesityl)di([5]trovacenyl)borane (6··), and tri([5]trovacenyl)borane (7···) were prepared from [5]trovacenyllithium, (η5-C7H7)V(η5-C5H4Li), and (Mes)2BF, (Mes)BF2, and BF3, respectively. The propeller-shaped species 5·, 6··, and 7··· were subjected to X-ray diffraction with the aim of possibly correlating the twist angles with intramolecular intermetallic communication. Cyclic voltammetry points to successive vanadium-centered oxidation processes and boron-centered reduction, a small redox splitting δE1/2[(2+/+), (+/0)] being observed for 6··. According to EPR spectroscopy, performed in fluid solution, the exchange interaction J in the diradical 6·· approaches the fast-exchange region and is attenuated significantly by quaternization at boron in [6··-nBu]-. Although EPR spectroscopy of the triradical 7··· also indicates an extensive exchange interaction, the exchange parameters, derived from spectral simulation, follow the gradation J(7···) ≈ 1/3 J(6··). The magnetic susceptibility of 6·· and 7··· follows the same trend. As expected, compound 7··· exhibits spin frustration because it contains three antiferromagnetically coupled S = 1/2 systems that are arranged in an equilateral triangle.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2187-2199 
    ISSN: 1434-1948
    Keywords: Ansa compounds ; Cp-derived chelate ligands ; Neopentane chemistry ; Spiro compounds ; Tripodal ligands ; Cyclopentadienyl compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The neopentane-derived functionalized oxetane O(CH2)2C(CH3)(CH2OMs), 1, reacts with indenyllithium (LiInd) or fluorenyllithium (LiFlu) to produce the derivatives O(CH2)2C(CH3)(CH2R) (R = indenyl, fluorenyl), 2. The oxetane ring of 2 undergoes nucleophilic ring-opening by reaction with LiPR′2 to give the chiral chelate ligands (HOCH2)(CH3)C(CH2R)(CH2PR′2) (R = indenyl, fluorenyl), 5. Nucleophilic ring-opening by LiInd or LiFlu is possible too, resulting in the functionalized ansa-Cp ligands (HOCH2)(CH3)C(CH2R)(CH2R′) (R, R′ = indenyl, fluorenyl), 12. Electrophilic ring-opening of 2 with HBr to give (HOCH2)(CH3)C(CH2R)(CH2Br) (R = indenyl, fluorenyl), 3, is also possible. The alcohol function of 3 may be activated directly, whereas activation of this group in 5 is only possible after BH3 protection of the phosphane function. The mesylates (MsOCH2)(CH3)C(CH2R)(CH2Br) (R = indenyl, fluorenyl), 4, undergo, under basic conditions, spiro cyclization to produce spirocyclobutane derivatives 9 with the α-carbons of the five-membered cycles acting as the spiro centres. Substitution of the mesylate group of 4 by PR2 nucleophiles is therefore not possible. Ansa-Cp derivative (MsOCH2)(CH3)C(CH2Ind)(CH2Flu), 12c also reacts with LiPPh2 with spiro cyclization to produce 9d, instead of giving the substitution product. Tripodal ligands (CH3)C(CH2R)(CHPPh2)2 (R = indenyl, fluorenyl), 11, are accessible by the reaction of (MsOCH2)(CH3)C(CH2PPh2)2 with LiInd or LiFlu. All compounds are fully characterized by the usual spectroscopic and analytical techniques including single-crystal X-ray analyses in several cases.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2201-2207 
    ISSN: 1434-1948
    Keywords: Carboxylate syn-anti ; N-centered tripodal ligand ; Manganese ; Imidazole ; Helicoïdal inorganic chiral chain ; Magnetism ; π-π interaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of an infinite inorganic chain consisting of MnII and an N-centered tripodal ligand N,N-(2-pyridylmethyl)[(1-methylimidazol-2-yl)-methyl]glycinate is presented. It exhibits a chiral helical structure with a pitch of two monomeric units (each monomeric unit containing one Mn atom). Each manganese is connected to its neighbor through a carboxylate bridge in a syn-anti geometry. Around each manganese center, two carboxylates bind in a cis geometry. This peculiar bridging geometry (syn-anticis) provides a broken-line chain, running in a zig-zag manner along the b axis of the P21 space group. The magnetic properties have been investigated. They show a pseudo-2D magnetic structure, with one major pathway along the chain and an inter-chain minor one. The intrachain coupling is a weak antiferromagnetic interaction (J/k = -0.25). This low value is entirely consistent with the geometry of the bridge. The interchain coupling is a weaker antiferromagnetic coupling (J′/k = -0.11) and could be mediated through π-π interactions between pyridine and imidazole from two adjacent helixes.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2221-2231 
    ISSN: 1434-1948
    Keywords: Calixarenes ; Inclusion compounds ; Imido Complexes ; Molybdenum ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses, spectroscopic properties, molecular structures, and bonding of novel calix[4]arene imido compounds are described. Treatment of M(NtBu)2(NHtBu)2Ia (M = Mo), Ib (M = W) or M(NMes)2Cl2(dme) IIa (M = Mo), IIb (M = W) (Mes = 2,4,6-Me3-C6H2) with p-tBu-calix[4]arene LH4 affords calix[4]arene metal complexes LM(NR) 1a, b (M = Mo, W; R = tBu) and 2a, b (M = Mo, W; R = Mes). Analytical and spectroscopic data are consistent with monomeric structures for 1 and 2, retaining a local C4v symmetry for the calix[4]arene metal fragment. These complexes are well-suited to bind small molecules like acetonitrile, tBu-isonitrile, or water within their macrocyclic pockets. The spectroscopic data of some inclusion compounds and the crystal structures of LMo(NtBu)(NCMe) 1a(NCMe), LW(NtBu)(OH2) 1b(OH2), LW(NtBu)(CNtBu) 1b(CNt Bu), LMo(NMes)(NCMe) 2a(NCMe), and LW(NMes)(NCMe) 2b(NCMe) are reported. All complexes contain a group VI metal imido [M=NR] moiety mounted on the phenoxide rim of the calix[4]arene ligand as well as an incorporated guest molecule within the cavity. Some insights into the structures of complexes of the type L′W(NR′) (L′ = p-H-calix[4]arene; R′ = H, Me) and into bonding in these compounds are provided by density functional theory, applying the B-P86 density functional and an all SVP basis set within the RI-J-DFT approximation. At least one π bond is of importance for calix[4]arene-metal bonding in these compounds. The metal-imido bond can be described as a triple bond. A geometrically optimized minimum structure of L′W(NMe) 4 shows a calix[4]arene ligand only slightly distorted from a local C4v symmetry and an almost linear tungsten-imido moiety.
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  • 8
    ISSN: 1434-1948
    Keywords: Arsonium salts ; Superacidic systems ; Structure elicidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of trimethylarsane in the superacidic systems hydrogen/fluoride antimony pentafluoride and hydrogen fluoride/arsenic pentafluoride leads to trimethylarsonium fluorometallates. These salts are stable up to 60 °C and 5 °C, respectively. Structures were successfully elucidated in the cases of trimethylarsonium undecafluorodiarsenate and trimethylarsonium hexafluoroantimonate. (CH3)3AsH+As2F11- crystallizes in the monoclinic space group P21/n with four formula units per unit cell with the dimensions a = 7.362(1), b = 12.589(1), c = 13.598(1) Å and β = 95.37(1)°. (CH3)3AsH+SbF6- crystallizes in the monoclinic space group P21/m with four formula units per unit cell with the dimensions a = 8.313(1), b = 8.855(1), c = 13.285(1) Å and β = 94.358(1)°.
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  • 9
    ISSN: 1434-1948
    Keywords: Molybdenum ; μ-Oxo ; Conformational equilibrium ; X-ray diffraction ; NMR spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new thiocyanatomolybdenum(VI) dioxo-μ-oxo complex dimer bearing a 4,4′-di-tert-butyl-2,2′-bipyridine ligand (2) is shown to exist in the crystal cell unit as a meso (Mo-O-Mo angle of 180°) and d,l, pair (Mo-O-Mo angle of 155.7°). These conformers are in equilibrium in solution and have been observed clearly by 1H NMR spectroscopy.
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  • 10
    ISSN: 1434-1948
    Keywords: Macrocycles ; Lithium ; Fluorescence ; Cryptands ; Coordination ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three aza-cages with the anthracene-containing photoactive groups L1, L2, and L3 have been synthesized. All compounds are able to selectively encapsulate a lithium ion and solid complexes have been isolated. The formation equilibria have been investigated by UV/Vis and 1H, 13C and 7Li NMR spectroscopic techniques. The fluorescence emission of both free ligands and lithium complexes have been investigated. Results indicate that the CHEF (chelation enhancement of the fluorescence) effect obtained by lithium coordination exits although lower than that occurring upon full protonation.
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  • 11
    ISSN: 1434-1948
    Keywords: Copper ; Trinuclear complexes ; Formamidines ; Magnetism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three new copper(II) linear trinuclear compounds are reported, all of which were synthesized in-situ, with the general formula [Cu3(L)4](CF3SO3)2(Y)x, where L is the dehydronated ligand: N,N′-bis(pyridine-2-yl)formamidine (abbreviated as Hpdf), N,N′-bis(pyrimidine-2-yl)formamidine (abbreviated as Hpmf) and N,N′-bis(5-methylpyridine-2-yl)formamidine (abbreviated as Hmpdf), Y = EtOH or H2O and x = 0.5-1.5. The compounds were characterized by X-ray diffraction, IR, LF, and EPR spectroscopy and by magnetic susceptibility down to 4 K. The structure of the compound [Cu3(pmf)4](CF3SO3)2(H2O)1/2 was determined by X-ray crystallography; it was found to crystallise in the triclinic space group P-1 with a = 8.529(5), b = 15.760(5), c = 19.639(5) Å, α = 101.793(5), β = 101.263(5), γ = 102.389(5)°, Z = 2. The structure [Cu-Cu-Cu angle 174.96(11)°] consists of four nearly flat molecules of the ligand, which contribute to the propeller-type structure around the Cu-Cu-Cu axis. A strong antiferromagnetic interaction between the CuII ions is observed with calculated J values, based on the Hamiltonian H = -2J(S1·S2 + S2·S3) - 2J′·S1·S3, of -174(1) cm-1, -120(1) cm-1, and -167(1) cm-1 for the compounds studied with L = pdf, pmf, and mpdf, respectively. These values are in agreement with an S = 1/2 ground state below temperatures of 120-160 K.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2277-2281 
    ISSN: 1434-1948
    Keywords: Boron ; Iron ; Nickel ; Carbyne complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The μ3-boryloxycarbyne complexes [{Fe(CO)3}3{μ3-COBCl{NtBu(SiMe3)}}2] (1) and [{(η5-C5H5)Ni}3{μ3-COBX(NR2)}μ3-CO] (2a: NR2 = NtBu(SiMe3), × = Cl; 2b: NR2 = N(SiMe3)2, × = Cl; 2c: NR2 = NMe2, × = BNMe2Cl) were obtained by reaction of the anionic complexes K2[{Fe(CO)3}3{μ3-CO}2] and K[{(η5-C5H5)Ni(CO)] with the corresponding chloroboranes Cl2BNR2 {NR2 = NtBu(SiMe3), N(SiMe3)2}, or 1,2-dichlorodiboranes(4) B2(NMe2)2Cl2, respectively. The products are formed by a nucleophilic attack of the CO oxygen atom at the boron centres with subsequent salt elimination. All compounds were characterized by IR and multinuclear NMR spectroscopy, and the structures of 1 and 2c in the solid state were determined by single-crystal X-ray diffraction studies.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1271-1279 
    ISSN: 1434-1948
    Keywords: Chirality ; Dinuclear complexes ; Rhodium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dinuclear and polynuclear metal complexes with octahedral centers coordinated to di- or polydentate ligands are often obtained as complicated mixtures of various stereoisomers. Stereospecific synthesis of such species is therefore of high current interest. Chiral derivatives of pyridine can be used for this purpose. Dinuclear μ-chloro-bridged RhIII complexes with two didentate, cyclometalated thienylpyridine-type ligands at each metal center are formed stereoselectively when pinene groups are fused to the pyridine rings. The two octahedral RhIII centers have homochiral configurations, ΔΔ and ΛΛ. The heterochiral diastereomer ΔΛ is not observed. With (8R,10R)-2-(2′-thienyl)-4,5-pinenopyridine [Hth4,5-(R,R)ppy] the ΔΔ to ΛΛ ratio is 9:1 when the separation eluent contains NaCl. Modeling the ΛΛ and the ΔΛ isomers of the dinuclear species shows crowding of the pinene groups in both cases; however, the strain can be released by relatively small distortions only in the case of the ΛΛ isomer. NO3- cleaves the dichloro bridge, yielding the mononuclear species Δ[Rh(L2)2(NO3)] (2) in a completely stereoselective manner when NaCl is replaced by KNO3 in the eluent mixture. The molecular structure has been determined by X-ray structure analysis for both the ΔΔ and the mononuclear complex Δ[Rh(L2)2(NO3)] (2) in order to confirm the configuration at the metal center. 1H-NMR, 13C-NMR and CD spectra were measured and the latter shows that the CD activity is solely due to the chirality at the metal center.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1281-1289 
    ISSN: 1434-1948
    Keywords: Phosphaalkynes ; Dimerization mechanism ; Diphosphacyclobutenes ; Density functional theory ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimerization of phosphaalkynes (R-C≡P, R = H, Me, tBu) without and with the presence of transition metal fragments, including CpCo (Cp = cyclopentadienyl) and COT-Ti (COT = cyclooctatetraene), has been probed using density functional theory calculations (B3LYP with different basis sets). MP2 and CCSD(T) calculations were also performed for the [H2C2P2] systems. In an attempt to address the exciting controversy and uncertainty about phosphaalkyne dimerization, a number of dimer formation mechanisms proposed in the literature have been examined. Some new and plausible intermediates have also been identified.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1315-1324 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; EHMO ; Vinylidene complexes ; Cobalt ; Rhodium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transformation of acetylene into vinylidene, as promoted by the metal fragment [(pp3)Co]+ [pp3 = P(CH2CH2PPh2)3], is unimolecular and features the hydride-acetylide species as an intermediate. The paper describes a detailed ab initio study of the reaction, in particular with regard to the step involving 1,3-H shift. The best computational results are obtained by mimicking the pp3 ligand with actual ethylenic chains rather than with single PH3 molecules. The keypoints along the two-step reaction path (π-acetylene, hydride-acetylide, and vinylidene complexes, as well as intermediate transition states) have been optimized for CoI and RhI derivatives at the MP2 level. For the fragment [(pp3)Co]+, the barrier associated with transformation of the hydride-acetylide intermediate to vinylidene (20.6 kcal/mol) is easier to surmount compared to that for reversion to the reactants (28.6 kcal/mol). The situation is reversed for the analogous RhI system, with the initial π-acetylene adduct being slightly more stable. Although higher in energy, the hydride-acetylide species is the experimentally detected product of the reaction of acetylene with the fragment [(pp3)Rh]+. The salient chemical aspects of the 1,3-H shift are discussed in terms of perturbation theory arguments. Parallel EHMO calculations, which have provided a relatively good consistency with the ab initio results, allow the proposal of an orbital rationale for the mode of migration of the hydride ligand along the substantially linear Co-Cα-Cβ grouping.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1335-1342 
    ISSN: 1434-1948
    Keywords: Photolysis ; Alkynes ; Matrix isolation ; DFT ; Oxygenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photolytically-induced reactions of chromyl chloride with acetylene and but-2-yne (dimethylacetylene) in low-temperature argon matrices yield end-on ketene and dimethylketene complexes of O=CrCl2, respectively. The product formation probably results from an electrophilic attack of a Cr=O linkage on the C≡C triple bonds, leading to radical-like transition states or intermediates, which subsequently rearrange through 1,2-H or 1,2-methyl shifts. Consequently, allene is attacked at its central carbon and the allyl radical thus generated undergoes subsequent ring-closure to give a cyclopropanone complex of O=CrCl2.
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  • 17
    ISSN: 1434-1948
    Keywords: Copper chelates ; EPR spectroscopy ; Electronic structure ; Schiff base ligands ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of tetrahedrally distorted copper(II) complexes with thiolate and imine coordination were synthesized. Schiff bases derived from 4-benzoyl-3-methyl-1-phenyl-2-pyrazoline-5-thione and various diamines were used as tetradentate ligands to obtain tetrahedrally distorted metal chelates with [CuN2S2] complex units. Crystal structures of the complexes 1, 2, 5 and 6 and of ligand H25 have been determined by means of single-crystal X-ray structure analysis. The structure data show a strong influence of the diamine building blocks on the tetrahedral distortion of the copper(II) complexes. Results of Extended Hückel LCAO calculations correlate strongly with structural, electrochemical, UV/Vis- and EPR-spectroscopic features obtained experimentally. The calculations confirm for the whole complex series a strong delocalization of the frontier orbitals. The highest fully occupied molecular orbital shows a weak contribution, resulting from thiolate donor atoms, whereas the antibonding singly occupied molecular orbitals (SOMOs) are distributed between the copper(II) centre (ca. 35-40%) and the N2S2 donor set. The SOMO energy significantly lowers with increasing tetrahedral distortion of the coordination sphere. The influence of the tetrahedral distortion of copper(II) complexes on redox potentials, UV/Vis and EPR spectra is discussed.
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  • 18
    ISSN: 1434-1948
    Keywords: Half-sandwich complexes ; Molybdenum ; Optically active complexes ; Rhenium ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of (η5-PinCp*)Re(CO)3 [PinCp* = tetramethyl(pinanyl)cyclopentadienyl] is described. Successive substitution of two CO ligands by NO+ and PPh3 generates a 1:1 diastereomeric mixture of chiral-at-metal [(SRe)/(RRe)-(PinCp*)Re(CO)(NO)(PPh3)]BF4. The diastereomers are converted with sodium methoxide into the derivative “esters” (SRe)/(RRe)-(PinCp*)Re(COOCH3)(NO)(PPh3), and then with (+)-(R)-(1-naphthylethyl)amine to the “amides” (SRe)/(RRe)-(PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7] [(SRe)/(RRe) = 1:1]. Fractional crystallisation separates the (SRe) isomer with an optical purity of 〉 98%. The latter compound has been characterized by X-ray structure analysis. By treating the (SRe)-amide with CF3CO2H and NaBF4, (SRe)-(PinCp*)Re(CH3)(NO)(PPh3) can be generated. Protolysis of this compound with HBF4/Et2O in CD2Cl2 at -78 °C leads to the solvent-stabilized complex (SRe)-[(PinCp*)Re(NO)(PPh3)(ClCD2Cl)]+BF4-. The thermal and configurational stability of this chiral Lewis acid is investigated at various temperatures. The syntheses of [PinCp*RhCl2]2, PinCp*TiCl3 and PinCp*M(CO)2(NO) (M = Mo, W) are also described. Starting with PinCp*M(CO)2(NO), the relatively stable 16-VE complexes PinCp*MCl2(NO) and PinCp*W(CH2SiMe3)2(NO) are synthesized.
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  • 19
    ISSN: 1434-1948
    Keywords: 2,2′-Bipyridines ; Chelate complexes ; Hydrogen bonding ; π-π stacking ; Crystal structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new synthetic route for the synthesis of 5,5′-diamino-2,2-bipyridine (5) based on the coupling of 2-chloro-5-aminopyridine in the presence of NiCl2 × 6 H2O/PPh3/Zn in dimethylformamide is described. The reactions of the potentially ambidentate ligand 5 with salts of the transition metals Mn, Fe, Ni, Cu, Zn, Ag, and Cd gave a variety of 13 metal-ligand complexes depending on the anion, the crystallization conditions and the metal-to-ligand ratio. The complexes obtained were characterized by thermal analyses, NMR including 113Cd-NMR, IR, and for the iron complex 57Fe-Mößbauer spectroscopy. The structure of eight of the compounds was elucidated by X-ray crystallography. All of these metal complexes show a bipyridine-metal coordination. The amino functionality was never involved in metal coordination. The intermolecular arrangement is dictated by hydrogen bonding from the amino functionality and by π-π stacking of the bipyridine rings.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/99078_s.pdf or from the author.
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  • 20
    ISSN: 1434-1948
    Keywords: Iron(III) ; Peroxo Complexes ; Kinetics ; Hydrogen Peroxide ; Catalase ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new diiron complex [Fe2(tbpo){O2As(CH3)2}(CH3O)(CH3OH)](ClO4)3 · 5 CH3OH · 2 H2O (1) containing a (μ-alkoxo)(μ-dimethylarsinato)diiron(III) core was synthesized using the heptadentate ligand N,N,N′,N′-Tetrakis(2-benzimidazolylmethyl)-1,3-diamino-2-propanol (Htbpo). The complex was characterized structurally by X-ray crystallography. 1reproduces the coordination mode and the stoichiometry of the proposed purple acid phosphatase-arsenate inhibitor complex. More importantly, 1 is a good functional model for the activation of small molecules, since the solvent molecule in the coordination sphere of each iron ion can be substituted very easily by a small substrate molecule. This is confirmed by the comparatively high pH-dependent catalase-like activity of 1. In order to study the influence of the cacodylate bridge on the formation of the metastable adduct with hydrogen peroxide, the analogous hydroxo-bridged complex [Fe2(tbpo)(OH)(NO3)2](NO3)2 · CH3OH · 2 H2O (2) was employed. The reactions of 1and 2 with H2O2 were studied as a function of [H2O2], pH, temperature, and pressure, and the kinetic results including the activation parameters are reported. In the case of compound 2 the reaction proceeds in one step, and the observed first order rate constant, kobs, shows a linear dependence on the hydrogen peroxide concentration with a zero intercept. For complex 1 the kinetic traces could be fitted to two exponential functions. One of the observed pseudo-first-order rate constants, kobs1, exhibits a linear dependence on the hydrogen peroxide concentration with a zero intercept, whereas the other rate constant, kobs2, was independent of the hydrogen peroxide concentration. A mechanistic interpretation is presented.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/99068_s.pdf or from the author.
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  • 21
    ISSN: 1434-1948
    Keywords: Ruthenium ; Coordination chemistry ; Paramagnetic complexes ; Magnetic properties ; Ion exchange ; Antitumor agents ; Colon tumors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Indazolium trans-tetrachlorobis(indazole)ruthenate(III) exhibits excellent results against different tumor models in vitro and in vivo. To improve the water solubility necessary for the introduction of this tumor-inhibiting compound into clinical trials, we synthesized the corresponding sodium salt in a two-step ion exchange via the tetramethylammonium salt. The sodium salt shows a 35-fold higher solubility in water relative to the indazolium salt. We also synthesized the n-butylammonium, n-octylammonium, and tetraphenylphosphonium salts, all of which showed improved solubility in organic solvents. The X-ray crystal structure of the latter could be solved, proving the trans configuration of the complex anion. In spite of the paramagnetic RuIII center an assignement of the coordinated indazole protons could be made with the help of a COSY experiment.
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  • 22
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2355-2368 
    ISSN: 1434-1948
    Keywords: Phosphane complexes ; Lithium ; Aminophosphanes ; Hydrazides ; (N-lithioamino)diorganophosphanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Butyllithium (nBuLi) deprotonates Ph2P-NHtBu in ether to give (Ph2P-NLitBu)2·OEt2. There is no Li···P interaction in this molecule. Three compounds of the type R′P(NLiR)2 have been obtained by lithiation of R′P(NHR)2, isolated as [BuP(NLitBu)2·OEt2]2, [PhP(NLiPh)2·OEt2]2 and [PhP(NLiPh)2]2. Reaction of nBuLi with MeP(NHiPr)2 in hexane/THF leads to [MeP{N(Li)iPr]2·THF}4 with an asymmetric cluster structure comprising one LiP3, three LiPN2, three LiP2N and one LiN3 cluster units. The molecular structures of these compounds as determined by X-ray structure analysis show that they are best depicted as N-lithioaminophosphanes and not as the isomeric P-lithioiminophosphoranes.
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  • 23
    ISSN: 1434-1948
    Keywords: Alkylation ; Carbonyl complexes ; Lewis acids ; Phosphaalkenes ; Protonation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the carbonyl-functionalized phosphaalkenes RC(O)P=C(NMe2)2 [R = tBu (2a), Ph (2b)] with protic acids and alkylating reagents occurred at the two-coordinate phosphorus atom to give the phosphanyl-substituted carbocations 3a,b and 4a,b. In contrast, treatment with Me3SiOSO2CF3 resulted in attack at the oxygen atom by the silyl group, and the formation of [RC(OSiMe3)=PC(NMe2)2]SO3CF3 (5a,b). Similarly, the Lewis acids B(C6F5)3, Al(tBu)2Cl and AlMe3 were ligated to the oxygen atom of the carbonyl group. Two equivalents of GaMe3 were added to the oxygen and phosphorus atom of the phosphaalkene to yield the thermolabile complexes [RC(OGaMe3)=P(GaMe3)C(NMe2)2] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)4], [Fe2(CO)9] or [{(Z)-cyclooctene}Cr(CO)5] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)P{M(CO)n}C(NMe2)2] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical transformations reported here underline the versatile chemistry of phosphaalkenes and emphasize a relationship between carbonyl-functionalized phosphaalkenes and the well-investigated class of phosphorus ylides. X-ray structures of compounds 6b, 7b*, 10a, 11a and 12a are reported.
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  • 24
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2127-2134 
    ISSN: 1434-1948
    Keywords: Gallium ; Azides ; Chemical vapour deposition ; Gallium nitride ; Single source precursors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, properties and X-ray single crystal structure analysis of the intramolecularly adduct-stabilised organogallium bisazide (N3)2Ga[(CH2)3NMe2] (1), the mono azide (N3)Ga[(CH2)3NMe2]2 (2) and the trialkylamine adducts of triazidogallium of the type (N3)3Ga(NR3) (3a-d; R = alkyl) are reported. An unusual isomer 1b of compound 1 is described, which was obtained by slow cooling of the analytically pure neat liquid compound 1 to 0 °C. The new and unusual structure 1b can be regarded as a weak associate of dimers linked together by head-to-tail azide bridges. In contrast, compounds 2 and 3a-b (R = CH3, C2H5) are monomeric in the solid state. The suitability of the volatile compounds 1 and 2 as single source precursors to grow GaN thin films by chemical vapour deposition is compared, showing that preferentially oriented crystalline films can be obtained from compound 2 on sapphire substrates at 600-700 °C in vacuo (0.1 Pa). However the films have a grey rather than a transparent appearance, which is presumably due to N-deficiency owing to the lower N-content of the single molecule precursor 2 relative to 1.
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  • 25
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2135-2145 
    ISSN: 1434-1948
    Keywords: Density functional calculations ; Epoxidation ; Peroxo complexes ; Titanium ; Transition states ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epoxidation of olefins by TiIV peroxo and hydroperoxo (alkylperoxo) complexes was investigated using a hybrid DFT method (B3LYP). Reaction energies and activation barriers for direct oxygen transfer to ethylene as a model olefin were computed for various model complexes to compare the epoxidation activity of Ti(η2-O2) and TiOOR (R = H, CH3) moieties. The activity of complexes with a Ti(O2) peroxo group is shown to be essentially quenched when the coordination sphere of the complex is saturated by strongly basic (σ-donor) ligands. In contrast, the activity of a TiOOH functional group depends only weakly on the saturation of the coordination sphere of the Ti center. Substitution of methyl for hydrogen in a TiOOH group is found to slightly increase the activation barrier of epoxidation. The computational results give preference to reaction paths that involve TiOOR species. The factors governing the activity of Ti(O2) and TiOOR groups, in particular the effects of donor ligands, are discussed on the basis of a molecular orbital analysis.
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  • 26
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2289-2294 
    ISSN: 1434-1948
    Keywords: Intercalations ; Vanadyl phosphate ; Ethanol ; Hydration ; Kinetics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The course of the replacement of ethanol by water molecules in the VOPO4·2C2H5OH intercalate, and of water by ethanol in VOPO4·2H2O has been studied by X-ray diffraction and infrared and Raman spectroscopy. Formation of mixed phase VOPO4·C2H5OH·H2O was not observed. The shape of the kinetics curves indicates a transition of at least one reaction zone through the crystal. A delay in formation of the product in comparison with the decrease in the amount of starting material can be explained by the existence of non-diffracting advancing phase boundary. In a VOPO4/ethanol/water system, VOPO4·2C2H5OH is formed as the only product when the system contained more than 96 vol% of ethanol, whereas in the system with less than 94 vol% of ethanol only VOPO4·2H2O is present.
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  • 27
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2295-2299 
    ISSN: 1434-1948
    Keywords: Lewis acids ; Bismuth ; Aluminum ; Phosphorus ; Tin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dilithium salts of N-methyl-N′,N′′-bis(diisopropyl)- and -(trimethylsilyl)-diethylenetriamine 1a,b react with SnCl2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl3 to give the bismuth chloride 5 (90% yield). Derivatives 2b and 5 have a symmetrical bicyclic structure and are monomeric both in solution and in the solid state. When 2b is treated with BiCl3 or PCl3, an oxidation reaction leads to the hypercoordinated tin(IV) dichloride 3 (58% yield), or a transmetallation gives rise to the oniophosphane 4 (95% yield), respectively. Transmetalation reactions also occurred when 5 was treated with AlCl3, GaCl3 or SnCl2 affording the corresponding aluminum chloride 6 (81% yield), gallium chloride 7 (38% yield) or tin dichloride 3 (38% yield). The observed reactivity for 2 and 5 is compared to that reported for Veith's stannylene or bismuth chloride.
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  • 28
    ISSN: 1434-1948
    Keywords: Ruthenium ; Triazole ; Titanium ; Electron Transfer ; Sensitizers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexes [Ru(dcb)2(L)] {L = 3-(2-hydroxyphenyl)-5-(pyridin-2-yl)-1,2,4-triazole (2-ppt), 3-(4-hydroxyphenyl)-5-(pyridin-2-yl)-1,2,4-triazole (4-ppt), 3,5-bis(pyrazin-2-yl)-1,2,4-triazole (bpzt), 3-(2-hydroxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole (2-ppzt) and dcb = 4,4′-(CO2H)2-2,2′-bipyridine} have been synthesized, spectroscopically characterized and anchored to nanocrystalline TiO2 electrodes for the conversion of light into electricity in regenerative solar cells. The different efficiencies observed have been rationalized on the basis of an analytical expression relating the incident photon-to-current conversion efficiency (IPCE) to the kinetic parameters of the relevant electron transfer processes involved in the solar cell.
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  • 29
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1295-1299 
    ISSN: 1434-1948
    Keywords: Solid-state chemistry ; Structure elucidation ; Reactive flux syntheses ; Oxysulfides ; Niobium chalcogenides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new compounds K4Nb2S10O and Rb4Nb2S10O have been synthesized by the reaction of potassium or rubidium alkaline polychalcogenides with NbO2, Nb2O5, or mixtures of Nb and NbO. Their structures consist of discrete [Nb2Q11]4- anions (Q = O, S) built up of two face-sharing pentagonal bipyramids, which are connected via the alkali metal cations.
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  • 30
    ISSN: 1434-1948
    Keywords: Pyrazolato ligands ; Rhenium ; Group-11 metals ; Heterometallic complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By treating [(CO)3Re(Hpz)2(pz)] (Hpz = pyrazole) with [Cu(CH3CN)4]BF4, AgNO3, or [Au(tht)Cl] (tht = tetrahydrothiophene) in acetonitrile in the presence of Et3N, the corresponding trinuclear complexes {(CO)3Re(pz)3[M(CH3CN)]2} (1a-c) have been obtained. Treatment of complexes 1a-c with cyclohexyl isocyanide (c-C6H11NC) afforded the derivatives {(CO)3Re(pz)3[M(c-C6H11NC)]2} (2a-c). Complexes 2a-c have been characterized in solution by 1H-NMR spectroscopy and in the solid state by single-crystal X-ray diffraction analysis.
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  • 31
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1309-1313 
    ISSN: 1434-1948
    Keywords: Phthalocyanines ; Rhenium ; Nitrido(octa-n-alkylphthalocyaninato)rhenium compounds ; Nucleophilic additions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of nitrido(tetra-tert-butylphthalocyaninato)rhenium (1) with boron tribromide leading to (tBu4Pc)ReNBBr3 (4) and with acetone to give the imido complex (tBu4Pc)Re[NC(CH3)2CH2C(O)CH3]OH (2b) and its μ-oxo dimer 3 are reported. Starting from the corresponding 4,5-di-n-alkylphthalonitriles and ammonium perrhenate four soluble nitrido(octa-n-alkylphthalocyaninato)rhenium complexes 5-8 were synthesized. Nitrido(octa-n-pentylphthalocyaninato)rhenium (6) was treated with boron tribromide to afford [(C5H11)8Pc]ReNBBr3 (9).
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  • 32
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1325-1333 
    ISSN: 1434-1948
    Keywords: Platinum ; Palladium ; Platinum blues ; Naphthyridine complexes ; Trinuclear complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: All three dinuclear complexes [Pd2(donp)2(bpy)2] (1) (H2donp = 1,8-naphthyridin-2,7-dione), [Pd2(H2nonp)2(bpy)2](ClO4)2 (2), and [Pt2(H2nonp)2(bpy)2](PF6)2 (3) (H3nonp = 7-amino-1,8-naphthyridin-2-one) exhibit the μ-1ĸN1:2ĸN8 bridging mode for their head/tail orientated naphthyridine ligands. Whereas 1 and 3 may be prepared by direct reaction of the dinucleating ligand with [MCl2(bpy)], formation of competing tripalladium(II) complexes must be avoided for 2 by employment of the precursor H2acnonp (7-acetamido-1,8-naphthyridin-2-one), which affords [H2nonp]- on cleavage of its original acetyl group. A mixture of the head/tail (4a) and head/head (4b) isomers of [Pd3(Hnonp)2(bpy)3](ClO4)2 is obtained when H3nonp is treated with [PdCl2(bpy)] and LiOH at room temperature for 2 d, followed by precipitation with LiClO4. Contrastingly exclusive formation of 4a is observed upon refluxing this reaction mixture for 3 d in aqueous solution. The [Hnonp]2- ligands exhibit a μ3-1ĸN1:2ĸN8:3ĸN7 bridging mode that leads to short Pd···Pd interactions of 2.781(2) and 2.775(2) Å. Similar metal-metal distances of 2.771(3) and 2.816(3) Å are observed in head/head-[Pt3(acnonp)(Hnonp)(bpy)3]Cl2 (5). An in situ 2e--oxidation (Ag+/Ag) of the [Pt3]6+ core in triplatinum(II) species such as 5 formed by the reaction of [PtCl2(bpy)] with H2acnonp allows the isolation of diamagnetic dark-brown head/head-[Pt3(Hnonp)2(NO3)(bpy)3](ClO4)2(NO3) (6) with an average oxidation state of Pt (2.67+). The Pt-Pt distances of 2.723(2) and 2.670(2) Å are markedly shorter than in 5.
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  • 33
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1343-1350 
    ISSN: 1434-1948
    Keywords: Indium ; O ligands ; N ligands ; C ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New heteroleptic indium compounds have been synthesized starting from indium(III) halides and hexamethyldisilazyllithium to form MeXInN(SiMe3)2 [X = Cl (1), Br (2)], and then subsequent alcoholysis to afford the molecules [ClMeIn(OtBu)]2 (3), [BrMeIn(OtBu)]2 (4), {ClMeIn[O(C6H4)OMe]}2 (5), {[(SiMe3)2N]MeIn(OtBu)}2 (6) and [MeIn(OtBu)2]2 (7). The molecular structures of molecules 3-7 have been obtained by single crystal X-ray diffraction studies. The structures of the compounds 3-7 are almost identical: 3-5 crystallize in the monoclinic crystal system with two dimeric molecules per unit cell in the space group P21/c, 6 crystallizes in the monoclinic space group C2/c with four molecules per unit cell, and compound 7 crystallizes in the triclinic crystal system with one dimeric molecule per unit cell in the space group P-1. The central centrosymmetric In2O2 ring, common to all the compounds, is achieved by two bridging oxygen atoms. Due to the additional coordination by an oxygen atom of the methoxy group, the coordination number of the metal center rises from 4 to “4+1” if the OtBu ligand (compounds 3, 4, 6, and 7) is exchanged for a methoxyphenol ligand (compound 5). In addition to the In2O2 ring the compound 5 possesses two annealed five-membered InO2C2 rings. The common indium methyl group of all compounds, which is transfered by an original route from the silicon to the indium atom, is used to compare structural and spectroscopic properties of the molecules, as there is a correlation between the In-C bond length and the chemical shift of the methyl group which depends on the ligand system used.
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  • 34
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1359-1366 
    ISSN: 1434-1948
    Keywords: Selenium ; Fluorine ; Multinuclear NMR ; Raman spectroscopy ; X-ray crystallography ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of perfluoroaryllithium RC6F4Li, where R = F or 4-CF3C6F4O, respectively, with selenium gives the known diselanes (RC6F4Se)2 (1a, 1b). Redox reactions of 1 with hydrogen peroxide result in the formation of the seleninic acids RC6F4SeOOH which crystallize as hydrates (2a, 2b); with mercury give the bis(arylseleno)mercuries (RC6F4Se)2Hg (3a, 3b); with sulfuryl chloride or bromine give the selenenyl chlorides (4a, 4b) or selenenyl bromides (5a, 5b). Selenenyl chlorides (4a, 4b) react with a variety of trimethylsilyl reagents Me3SiX (X = Br, CN, NMe2, NEt2) to form 5a, 5b; selenocyanates RC6F4SeCN (6a, 6b); selenenyl amides RC6F4SeNMe2 (7a, 7b) and RC6F4SeNEt2 (8a, 8b). A new synthetic route to diorgano selanes is developed by reaction of 4a, 4b with perfluoroaryllithium to give the symmetric (RC6F4)2Se (9a, 9b). All derivatives are thoroughly characterized and in addition the molecular structures of 2a, 6a, and 9a are established by X-ray crystallography.
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  • 35
    ISSN: 1434-1948
    Keywords: Metallomesogens ; Nickel ; Salicylidenediamines ; Azo compounds ; (E)/(Z) photoisomerization ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bis[4-(n-CmH2m+1O)-5-(p-C14H29C6H4N=N)]-substituted N,N′-salicylidenediamines H2[LN(m,14)] (N = 1: 1,2-diaminoethane; N = 2: 1,3-diaminopropane; N = 3: 1,3-diamino-2,2-dimethylpropane; m = 6 or 18) have been synthesized. Both the N = 2 and 3 series of compounds display a smectic C (SmC) mesophase, with clearing points well below 100 °C. By treating the H2[LN(m,14)] ligands with an NiII salt, liquid crystalline mononuclear complexes with “unconventional” (lateral-tailed) molecular shape form. These Ni[LN(m,14)] complexes, showing nematic and smectic disordered phases, are stable over a quite large temperature range and have been characterized by different spectroscopic techniques. The newly synthesized mesogens exhibit lower transition temperatures and higher thermal stability than homologous complexes Ni[LN(14)] with a “conventional” rod-like molecular geometry.
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  • 36
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1467-1477 
    ISSN: 1434-1948
    Keywords: Oxidations ; Tertiary alcohol ; Porphyrins ; Neophyl rearrangement ; Cleavage reactions ; β-Scission ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of 4-(1-hydroxy-1-phenylethyl)benzoic acid HPEBA with a water-soluble metalloporphyrin as catalyst and KHSO5 as oxygen atom donor gives the major products, acetophenone AC and acetylbenzoic acid ABA, by a Caliph-CAr bond cleavage, but a minor product, benzoyloxybenzoic acid BOBA, requires the insertion of an oxygen atom to form the ester. This compound becomes the main oxidation product on increasing the amount of acetonitrile in the reaction medium, and its formation is oxygen-dependent. The conversion is drastically lowered by using D2O instead of H2O, suggesting that an alkoxyl radical is formed in the rate-determining step. Labeling experiments using 18O2 or H218O under different reaction conditions show that the carbonyl oxygen atoms of AC and ABA originate either from substrate, water or dioxygen. However, the carbonyl oxygen atom in the ester group of BOBA originates from dioxygen while the other oxygen atom of the ester remains unlabeled. These results can be explained by an O-neophyl rearrangement of the initial alkoxyl radical to afford a carbon-based radical which then reacts with dioxygen or MnIV-OH/water. In a competitive reaction pathway, direct β-scission of the alkoxyl radical leads to unlabeled products. The oxidation of other tertiary diaryl alcohols is also discussed.
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  • 37
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1489-1495 
    ISSN: 1434-1948
    Keywords: Peroxo complexes ; Vanadium ; Mass spectrometry ; 51V-NMR spectroscopy ; Vanadium dependent bromoperoxidases ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ESI mass spectrometry and 51V-NMR spectroscopy have been used to study the reactions occurring between bisperoxo vanadates and a number of histidine and histidine-like ligands, in aqueous alcoholic solutions. Coordination of one and two molecules of ligand is observed with all the compounds investigated affording [VO5L]- and [VO52L]-, respectively. Characterization of these species has been achieved by MSn experiments, which have allowed specific fragmentations of the peroxidic moiety to be distinguished. In particular, with [VO52L]-, two distinct modes of decomposition were observed, depending on the presence in the ligand of a free carboxylic function. - Possible biochemical implications related to vanadium haloperoxidase enzymes are discussed.
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  • 38
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1479-1488 
    ISSN: 1434-1948
    Keywords: Phosphorus heterocycles ; Cations ; Tungsten complexes ; Coordination modes ; Phosphaalkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1,1,3-tris(diisopropylamino)diphosphirenium salt 1 reacts with lithium aluminium hydride leading to the P-hydrogeno-C-phosphinophosphaalkenes 2, which on treatment with a catalytic amount of BF3·OEt2 afford the 1,3-bis(diisopropylamino)-1H-diphosphirene 3. The corresponding η1-coordinated 1H-diphosphirene 6 can be prepared by treatment of 2 or 3 with one equivalent of [W(CO)5(thf)]. Alternatively, the diphosphirenium salt 1 reacts with an excess of [W(CO)5(thf)], affording the corresponding η1-coordinated diphosphirenium salt complex 4, which is converted into the P-hydrogenophosphaalkene complex 5 with lithium aluminium hydride. The dinuclear tungsten complexes 7 and 8 are obtained by treatment of the free 1H-diphosphirene 3 with two equivalents of [W(CO)5(thf)] or one equivalent of [W(CO)4(thf)2], respectively. Compound 6 reacts with two equivalents of hydrogen chloride, giving the 1-chloro-3-diisopropylamino-1H-diphosphirene 9, which can be subsequently converted into the 1-diisopropylamino-, 1-azido, or 1-phenyl-3-diisopropylamino-1H-diphosphirenes 6, 10 and 11 by nucleophilic substitution with diisopropylamine, azidotrimethylsilane or sodium tetraphenylborate, respectively. The [η2-(3-diisopropylaminodiphosphirenylium salt)·W(CO)5] complexes 12a-c can be prepared by reaction of 9 with silver trifluoromethanesulfonate, aluminium or gallium trichloride or, alternatively, by treatment of 6 with two equivalents of trifluoromethanesulfonic acid. Reaction of 12a with diisopropylamine, water, bis(triphenylphosphoranylidene)ammonium chloride or tetrabutylammonium fluoride gives the corresponding 1H-diphosphirene complexes 6, 13, 9, or 14, respectively. Compound 12a also reacts with one or two equivalents of [W(CO)5(thf)], leading to the di- and tri-nuclear complexes 15and 16, respectively.
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  • 39
    ISSN: 1434-1948
    Keywords: Phosphane ligands ; 31P-NMR spectrometry ; Substituent increments ; Electronic and steric properties ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses and spectroscopic parameters of the new tertiary phosphane ligands (p-MeOC6H4)(o-MeOC6H4)2P (1), (p-MeOC6H4)(o-MeSC6H4)2P (2), (p-MeSC6H4)(o-MeSC6H4)2P (3), (p-MeSC6H4)(o-MeOC6H4)2P (4), (p-MeOC6H4)(o-NC5H4)2P (5), and (p-MeSC6H4)(o-NC5H4)2P (6) are reported. Single-crystal X-ray structures of all the compounds (1-6) have been determined. The dependence of the 31P-NMR chemical shifts on the substituent groups of the phosphanes is discussed.
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  • 40
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1373-1379 
    ISSN: 1434-1948
    Keywords: Sodium bis(borane)dimethylamide solvates ; X-ray structure ; Reduction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of sodium metal with dimethylamine-borane in THF yields Na[(H3B)2NMe2] (1) which can be isolated as {Na[(H3B)2NMe2]}5·THF or as Na[(H3B)2NMe2]·15-crown-5 (2) and Na[(H3B)2NMe2]·benzo-15-crown-5 (3) after addition of the appropriate crown ether to the THF solution of 1. Reaction of 1 with ZrCl4 yields Me2HN-BH2-NMe2-BH3 (4), the structure of which has been determined. In THF solution, 1 reduces aldehydes, ketones, acyl chlorides, and esters to the corresponding alcohols. It also reacts slowly with nitriles and allylbenzene. Compound (1)5·THF crystallizes in an extended three-dimensional lattice, in which the Na atoms are coordinated by 6-9 hydridic H atoms, while 3 is a molecular compound in the solid state. Only one hydrogen atom of each BH3 group coordinates to the sodium center. On the other hand, 4 forms dimeric associates in the solid state through N-H···H-B interactions.
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  • 41
    ISSN: 1434-1948
    Keywords: Haloalkyl complexes ; Five-coordinate platinum complexes ; Alkene complexes ; Olefin halogenation ; Oxidative addition ; Platinum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five-coordinate complexes [PtX2(olefin)(2,9-Me2-phen)] (1; 2,9-Me2-phen = 2,9-dimethyl-1,10-phenanthroline; olefin = ethene denoted by a, propene by b, 1-butene by c; × = Cl denoted by x, Br by y) undergo photoactivated reactions with Cl2 and Br2 to give the (β-haloalkyl)platinum(IV) complexes [Pt(CH2CHRX)(2,9-Me2-phen)X3] (2). Bromination of the chloro species 1ax leads to the formation of the PtIV species 2axy containing the bromide, the bromoalkyl, and the phenanthroline ligands in the equatorial plane and two chloride ions in axial positions. The iodo complexes 1(a-c)z are not oxidized by iodine even under UV irradiation but react readily with Cl2 or Br2 to give 2(a-c)x and 2(a-c)y. The structure of 2ay, the first structurally characterized (β-haloalkyl)platinum complex, has been determined by X-ray diffraction methods. The stereochemistry of the (β-haloalkyl)platinum(IV) complexes is in accord with a simultaneous addition of two halogen atoms to the coordinated olefin and to the metal center.
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  • 42
    ISSN: 1434-1948
    Keywords: Phosphanes ; Disilanes ; Disilanylamines ; Germanes ; Stannanes ; Stannanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of dialkyl(trimethylsilyl)phosphanes RR′PSiMe3 (1:R, R′ = tBu; 3: R, R′ = iPr; 5: R = iPr, R′ = tBu) with Si2Cl6 provide stable trichlorosilylphosphanes RR′PSiCl3 (2, 4, 6); the reactions of silyl- and stannylamines of iPr2NMMe3 (M = Si: 11; M = Sn: 12) with Si2Cl6, however, provide the stable pentachlorodisilanylamine iPr2NSi2Cl5 (13). Heating of 1 with the technical mixture Me2(Cl)SiSiCl2Me/(MeCl2Si)2 yields the stable silylphosphane tBu2PSiMe2Cl (8) and the disilanylphosphane tBu2PSi(Me)(Cl)Si(Me)Cl2 (9). Methylation of 9 with MeLi gave tBu2PSi2Me510, which was isolated in a pure state. Reactions of tBu(iPr)PSiMe3 (5) and of organometal phosphanes tBu(iPr)PMR3 (14: M = Ge, R = Me; 17a-c: M = Sn; R = Me, Et, nBu) with Si2Cl6 were monitored by 31P, 29Si, and 119Sn NMR. - In the first step of these reactions, new tBu(iPr)PSi2Cl5 (7) is formed. 7 is accompanied by increasing amounts of tBu(iPr)PSiCl3 (6) and Me3GeSiCl3 (15)/(Me3Ge)2Si(SiCl3)2 (16) or traces of compounds R3SnSiCl3 (19a-c) that decompose providing (R3Sn)2Si(SiCl3)2 (18a-c) and nBu3SnSi(SiCl3)3 (20c). Subsequently, compounds 19a-c decompose providing increasing amounts of 18a-c. Stannylphosphane 17bis also cleaved by SiCl4 leading to 6 with liberation of Et3SnCl, whereas 17bis formedfrom the reaction of 5 with Et3SnCl under liberation of Me3SiCl. The suggestion of an extra stabilisation of P-Si bonds of trichlorosilylphosphanes was subjected to direct evidence through the structure determination of the trichlorosilylphosphane tBu2PSiCl3 (2) in the gas phase by electron diffraction. This crowded molecule has a “normal” P-Si bond length of 225.0(12) pm; its C1 symmetric conformation with both tBu groups and the SiCl3 group twisted about 17° from the perfectly staggered positions, and with each of the three groups tilted about 6° away from each other, allows to reduce steric strain.
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  • 43
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1421-1428 
    ISSN: 1434-1948
    Keywords: Grid complexes ; Self-assembly ; Co ; Zn ; Coordination chemistry ; Bis(tridentate) ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tretrametallic [2 × 2] grid-type complexes 1-4 are formed by self-assembly of the bis(tridentate) ligands 5 and 6 with ZnII and CoII cations. They have been characterized by spectroscopic studies in solution as well as by crystal structure determination. The substituents in the central pyrimidine ring play an important role in terms of geometry and physical properties of the complexes. They induce an orthogonal orientation of the ligand in the complexes which is critical for the formation of ordered monolayers and extended self-organized arrays of grids. The physical properties of the complexes such as metal-metal interaction and π-π* stacking between the ligands may be modulated by changing these substituents.
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  • 44
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1429-1433 
    ISSN: 1434-1948
    Keywords: Antitumor drugs ; Platinum ; DNA ; Dendrimers ; L1210 Mouse leukemia ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterisation of the first generation of a poly(propyleneimine) dendrimer DAB(PA)4, substituted with four trans-diamminechloroplatinum moieties is reported. The compound DAB(PA-tPt-Cl)4 was designed to overcome two problems often associated with cisplatin resistance in cancer cells: (i) deactivation of the platinum species by intracellular thiolates and (ii) improved repair of crosslinks with DNA. The four-armed molecule can be expected to form crosslinks with DNA that are very different from the adducts formed by cisplatin. Also, the tetranuclear compound has four leaving groups, while cisplatin has only two. Therefore, DAB(PA-tPt-Cl)4 would be less susceptible towards inactivation by reaction with intracellular thiolates. A reaction with an excess of the model nucleobase guanosine 5′-monophosphate (GMP) confirmed that the tetranuclear compound is capable of binding a maximum of four nucleobases. Therefore, the inactivation of one or two arms would still leave the molecule with enough reactivity to form crosslinks with DNA. Cytotoxicity tests were performed on two mouse leukemia L1210 cell lines, both sensitive and resistant towards cisplatin, and in seven human tumor cell lines. In all cell lines, the tetranuclear compound showed a low cytotoxicity. It is suggested that the low activity is related to the structure of the compound. Probably the high charge (+6) at physiological pH and its branched structure hamper the molecule in crossing the cell membranes.
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  • 45
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1453-1459 
    ISSN: 1434-1948
    Keywords: Group-5 bent metallocene cation complexes ; (Butadiene)tantalocene cation ; (s-trans-η4-Butadiene)metal complex ; Ethene polymerization ; Metallocenes ; Homogeneous catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Butadiene)TaCp*Cl2 (6) was treated with CpNa to yield (η2-butadiene)TaCp*CpCl (7). Subsequent reaction with [Cp2ZrCH3+][CH3B(C6F5)3-] resulted in transfer of the chloride ligand from tantalum to zirconium with formation of the [(s-trans-η4-butadiene)TaCp*Cp]+ cation [8, with CH3B(C6F5)3- anion]. Complex 8 was characterized spectroscopically and by an X-ray crystal structure analysis. The group-5 [(s-trans-η4-C4H6)TaCp*Cp]+ bent metallocene cation complex 8 reacts with ketones (acetone, adamantanone) to yield the corresponding seven-membered 2-tantalatetrahydrooxepine cation complexes (9, 10). 1-Cyanoadamantane reacts with 8 to yield the 2-tantala-3,6-dihydro-2H-azepine cation system 11. Activation of 8 with methylalumoxane gives an active ethene polymerization catalyst.
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  • 46
    ISSN: 1434-1948
    Keywords: Metallacycles ; Solid-state structures ; Heterocycles ; Oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct oxidation of PhC(O)NHPPh2, H2NC(S)NHPPh2, (C5H4N)C(S)NHPPh2 with O2, S8, or Se gives [PhC(O)NHP(O)Ph2] (1), [H2NC(S)NHP(S)Ph2] (2), [H2NC(O)NHP-(S)Ph2] (3), [PhC(O)NHP(S)Ph2] (4), [(C5H4N)C(S)NHP(S)Ph2] (5), and [H2NC(S)NHP(Se)Ph2] (6). Deprotonation of 1, 2, 4-6 with potassium tert-butoxide gives K[PhC(O)NP(O)Ph2] (7), K[H2NC(S)NP(S)Ph2] (8), K[PhC(O)NP(S)Ph2] (9), K[(C5H4N)C(S)NP(S)Ph2] (10), and K[H2NC(S)NP(Se)Ph2] (11). Reaction of 4with KOBu and [Cu(Ph3P)2][NO3] gives [Cu(Ph3P)(PhC(O)NP(S)Ph2)] (12) which is the first crystallographically characterised example of a non-ionic six-membered “true” heterocycle (i.e. a ring in which every heterocatom is different). 9 and 10 were treated with [PdCl2(COD)] to give [Pd{PhC(O)NP(S)Ph2}2] (13) and [Pd{(C5H4N)C(O)NP(S)Ph2}2] (14), respectively The anion of 8 coordinates to zinc forming [Zn{H2NC(S)NP(S)Ph2}2] (15). Treatment of 2 or 8 with [PtCl2(COD)] gives [Pt{H2NC(S)NP(S)Ph2}{H2NC(S)NHP(S)Ph2}]+Cl- (16) and [Pt{H2NC(S)NP(S)Ph2}2] (17), respectively. The X-ray structures of 12, 15-17are reported.
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  • 47
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1523-1529 
    ISSN: 1434-1948
    Keywords: Boron ; Iron ; Ruthenium ; Boryl Complexes ; Borylene Complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactivity of aminodihaloboranes R2NBX2 (R = Me, SiMe3; × = Cl, Br) towards transition metal complexes of the type Na[(η5-C5R′5)M(CO)2)] (M = Fe, Ru; R′ = H, Me) was investigated. In the case of Me2NBBr2 and M = Fe the borylcomplexes [(η5-C5R′5)(CO)2Fe{BBr(NMe2)}] (C5R′5 = C5H59a; C5R′5 = C5H4Me 9b; C5R′5 = C5Me510) were obtained. The compounds 9aand 9bwere formed together with the corresponding bridged borylene complexes [μ-BNMe2(μ-CO){(η5-C5R′5)Fe(CO)}2] (C5R′5 = C5H511a; C5R′5 = C5H4Me 11b) in a 1:1 ratio, the latter, however, could be isolated from these mixtures as pure materials. In addition the novel boryl and borylene ruthenium complexes [(η5-C5H5)(CO)2Ru{BX(NMe2)}] (X = Cl 12a; × = Br 12b), [(η5-C5H5)(CO)2Ru{BCl{NSiMe3{BClN(SiMe3)2}}}] (13) and [μ-BN(SiMe3)2(μ-CO){(η5-C5H5)Ru(CO)}2] (14) were obtained by similar methods. All compounds were characterized by multinuclear NMR and IR spectroscopy. The structure of 13 in the solid state was determined by a single-crystal X-ray diffraction study.
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  • 48
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1531-1535 
    ISSN: 1434-1948
    Keywords: SiCl4 Combustion ; OSiCl2 ; Matrix isolation ; Thermodynamic data ; DFT calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the technical important combustion of SiCl4 with oxygen [SiCl4(g) + O2(g) = SiO2(s) + 2·Cl2(g)] many intermediates have been detected in the past. However, the presence of the primary species O=SiCl2 has been discussed controversially until today. With the help of matrix isolation technique we have now been successful to monitor O=SiCl2 via its IR spectrum. With the help of quantum chemical calculations the thermodynamic data have been calculated first. On this basis it was possible to find the optimal conditions to trap OSiCl2 from the high-temperature equilibrium. Furthermore it could be shown via IR spectroscopy and quantum chemical calculations, that the radical OSiCl does not play a significant role within this combustion process.
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  • 49
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1545-1550 
    ISSN: 1434-1948
    Keywords: Phosphates ; Structure ; IR spectroscopy ; Raman spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The low-temperature form of K3Sm(PO4)2 crystallizes in the monoclinic system [a = 7.4347(5) Å, b = 5.6270(5) Å, c = 9.4919(5) Å, β = 90.870(6)°, Z = 2, space group P21/m]. The structure has been determined using 1263 independent reflections (R = 0.045, Rw = 0.11) and is found to be of the glaserite type. The Raman and infrared spectra have been investigated: they are consistent with the proposed space group and an assignment of the observed frequencies is given.
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  • 50
    ISSN: 1434-1948
    Keywords: Palladium ; Phosphane ligands ; Bite angle ; Allylic alkylation ; Molecular modelling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The natural bite angle of bidentate phosphane ligands influences the isomer distribution (syn and anti) in (1-methylallyl)(bisphosphane)Pd OTf complexes. It was found (31P- and 1H-NMR studies) that the syn/anti ratio changes from 12 (dppp) to 1.3 (sixantphos). Molecular orbital calculations [PM3(tm) level] indicate that for ligands inducing a large bite angle, the phenyl rings of the ligand embrace the allyl moiety, thus influencing the syn/anti ratio. This bite-angle effect on the syn/anti ratio is transferred to the regioselectivity in stoichiometric allylic alkylation. Ligands inducing large bite angles direct the regioselectivity towards the formation of the branched product 2. Catalytic alkylation of (E)-2-butenyl acetate showed that for ligands with a small bite angle the regioselectivity of the catalytic and stoichiometric alkylation are in good agreement. This correspondence is worse for ligands with a larger bite angle, which is rationalised in terms of the relative rates of syn/anti isomerisation and alkylation. The ligand with the largest bite angle (sixantphos) gives the most active catalytic species.
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  • 51
    ISSN: 1434-1948
    Keywords: Metal string complexes ; Multicentered metal-metal multiple bond ; Quadruple bonds ; Metal-metal interactions ; Chromium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The linear pentanuclear chromium complexes [CrII5(μ5-tpda)4Cl2] (1), [CrII5(μ5-tpda)4(NCS)2] (2), [CrIIICrII4(μ5-tpda)4F2](BF4) (3), and [CrIIICrII4(μ5-tpda)4F(OTf)](OTf) (4), with four all-syn tri(α-pyridyl)diamido dianion (tpda2-) ligands, have been prepared and structurally characterized. Compounds 1 and 2 possess a delocalized Cr(II)-Cr(II)-Cr(II)-Cr(II)-Cr(II) five-centred metal-metal bond of order 1.5. In both 1 and 2 two values for CrII-CrII bond lengths are found both; the outer ones connected with axial ligands are 2.284(1) and 2.285(2) Å, and the inner ones are 2.2405(8) and 2.246(1) Å, for 1 and 2, respectively. When compound 1 reacts with 2 equiv. of AgBF4 or Ag(OTf), a oxidation reaction takes place and one of the terminal chromium(II) ions is oxidized to produce [CrIIICrII4(μ5-tpda)4F2]BF4 (3) or [CrIIICrII4(μ5-tpda)4F(OTf)](OTf) (4). Two short Cr-Cr distances [1.969(2) and 2.138(2) Å for 3, 1.846(1) and 1.922(1) Å for 4] are found, with the presence of two quadruple bonds among four adjacent CrII ions. The fifth CrIII ion, which is separated from the neighboring CrII ion by 2.487(2) Å for 3 and 2.610(1) Å for 4, is simply a square pyramidal unit with no metal-metal bonding interaction.
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  • 52
    ISSN: 1434-1948
    Keywords: Aluminium ; Amides ; Calcium ; Metallacycles ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of calcium bis[bis(trimethylsilyl)amide] with two equivalents of tris(trimethylsilylmethyl)alane yields (Me3SiCH2)2Al-N(SiMe3)2 (1) and the dimer [(Me3Si)2N-Ca(μ-CH2SiMe3)2Al(CH2SiMe3)2]2 (2). The five-coordinate bridging carbon atoms show Ca-C bond lengths of 264 and 268 pm. A similar reaction with calcium bis[bis(trimethylsilyl)phosphanide] gives the dimer [(Me3SiCH2)2Al-P(SiMe3)2]2 (3) with crystallographic C2 symmetry. A calcium-containing species is not isolable, however, in the presence of DME - ether cleavage reactions and the formation of the centrosymmetric dimer [(Me3SiCH2)2Al-OCH2CH2OMe]2 (4) are observed. The central moiety is an Al2O2 cycle with fivefold coordinated aluminium centers.
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  • 53
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2215-2220 
    ISSN: 1434-1948
    Keywords: Magnesium ; Metalation ; Phosphorus ; Polyhedra ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnesiation of triisopropylsilylphosphane with dibutylmagnesium in toluene yields the octanuclear complex [Mg8(PSiiPr3)6{P(H)SiiPr3}4] (1) which consists of MgPSiiPr3 units forming a hexagonal Mg6P6 prism, with two opposite Mg2P2 moieties capped by additional Mg[P(H)SiiPr3]2 groups. If a small amount of THF is present during the metalation reaction [(THF)4Mg6(PSiiPr3)6] (2) also containing a hexagonal Mg6P6 prism can be isolated. The magnesiation of H2P-SiiPr3 in tetrahydrofuran leads to the formation of the tetrameric complex [(THF)MgPSiiPr3]4(3) with a slightly distorted Mg4P4 cubane-like structure.The structures depend strongly on the steric strain caused by the trialkylsilyl substituents and the neutral coligands at the magnesium center. The highest steric strain, which is induced by coordination to every magnesium atom, leads to the smallest MgnPn polyhedron - the central Mg4P4 heterocubane moiety. In compounds 1 and 2 the hexagonal Mg6P6 prism is formed, however, with reduced steric strain as observed for 2 where the Mg-P bond lengths become more similar.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2233-2241 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Heterocycles ; Phosphinines ; Gold ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination behaviour of 2,6-disilyl-substituted phosphinines towards gold(I) has been examined. The reaction of the bis(trimethylsilyl)phosphinine 1 with [AuCl(SMe2)] gives the corresponding AuCl derivative 2. X-ray crystal structure analysis reveals that the aromaticity of the phosphinine ring is slightly reduced as a result of the poor π-back bonding ability of the AuCl fragment. The same phenomenon is observed in the cationic complex [Au(1)2][GaCl4] (3) which was readily prepared by reaction of two equivalents of 1 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. Reaction of 2,6-bis(phenylethynyldimethylsilyl)phosphinine (4) with the same precursor leads similarly to the complex [AuCl(4)] (5). Interestingly, this complex dimerizes upon crystallization to give the bis(phosphabarrelene) complex 6, also structurally characterized. The formation of 6 results from a [4 + 2] cycloaddition between one alkynyl group of each phosphinine with the other phosphinine subunit. The formation of the cationic complex [Au(4)][GaCl4] (8) occurs under classical conditions but it disproportionates to give the cationic complex [Au(4)2][GaCl4] (9) and colloidal gold deposition. The formation of 9 has been ascertained by treating 8 with one equivalent of ligand 4. Additionally, 9 can also be obtained in a straightforward fashion by treating two equivalents of 4 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. The structure of 9 has been elucidated. Despite a particular arrangement of the alkyne groups which encapsulate the gold coordination sphere, no gold-alkyne interactions are visible.
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  • 55
    ISSN: 1434-1948
    Keywords: Metallaoxirane ; HBR2 addition ; (Formaldehyde)zirconocene ; (Butadiene)zirconocene ; Heterocycles ; Boron ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (η2-Formaldehyde)zirconocene dimer (8) cleanly adds one or two molar equivalents of the borane HB(C6F5)2 by insertion of the H-[B] unit into the zirconium-carbon bond of the metallaoxirane moieties to form the mono- and bis-insertion products 16 and 17, respectively. These systems contain five-membered heterocyclic rings that are built up by connecting five different elements, namely H, B, C, O, and Zr. The bis(borane) insertion product 17 was characterized by an X-ray crystal structure analysis. (Butadiene)zirconocene reacts with HB(C6F5)2 in a similar way by insertion of the H-[B] unit into the (butadiene)C4-Zr linkage to form the metallacycle 18.
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  • 56
    ISSN: 1434-1948
    Keywords: N-ligands ; Yttrium ; Samarium ; Ring-opening polymerization ; Lactones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of one equivalent of dilithiated O(SiMe2-Ap-H)2 [Ap-H = -N(2-amino-4-methylpyridine)] (1), generated in situ, with LnCl3 (Ln = Y, Sm) in THF affords O(SiMe2-Ap)2YCl(THF)2 (2) or O(SiMe2-Ap)2SmCl(THF)3 (3). In contrast, the reaction of one or two equivalents of dilithiated 1, again generated in situ, with LaBr3 in THF affords O(SiMe2-Ap)2)2LaLi(THF)3 (4). An X-ray structural analysis of 2 and 3 reveal the O(SiMe2-Ap)2- ligand to bind in a planar tetradentate manner. Equivalent Sm-N distances in 3 indicate a delocalized binding mode. Compound 2 reacts with Bu4NBH4, NaBH4 or LiCH(SiMe3)2 to give the corresponding “ate” complexes O(SiMe2-Ap)2Y(BH4)Cl(THF) Bu4N (5), O(SiMe2-Ap)2Y(BH4)2Na(THF)2 (6) and O(SiMe2-Ap)2Y(CH(TMS)2)2Li(THF)3 (7), respectively. The steric demand of the O(SiMe2-Ap)2- ligand is not large enough to stabilize monoalkyl or monoborohydride complexes. Complex 4 has been used as an initiator for the ring-opening polymerization of ε-caprolactone or δ-valerolactone. In both cases an almost linear relation between the monomer-to-initiator ratio and the molecular weight of the obtained polyester is observed. By conducting the polymerization in neat ε-caprolactone at room temperature a solid polyester block is formed after 3 min (300000 g·mol-1, Mw/Mn 2.3).
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2301-2307 
    ISSN: 1434-1948
    Keywords: Multiple bonds ; Silicon ; Silylene ; Cycloadditions ; Insertions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Di-tert-butylsilylene, generated by photolysis of hexa-tert-butylcyclotrisilane 1 or 1,1-di-tert-butyl-trans-2,3-dimethyl-silirane (2), reacts with the 1,3-diyne (tBu-C≡C-)29 to furnish the dialkynylsilane 11 via the isolable alkynylsilirene 10. Photolysis of excess 1 in the presence of 9 furnishes the C-C linked 2,2′-disilirene 12 which, upon prolonged irradiation, rearranges to the 2,5-disilabicyclo[2.2.0]hexa-1(6),3-diene (13). Treatment of 9 with diarylsilylenes, formed by irradiation of hexamethyl-2,2-dimesityltrisilane (3) or hexamethyl-2,2-bis(2,4,6-triisopropylphenyl)trisilane (4), gives the corresponding alkynylsilirenes 14 and 15, respectively. Photolysis of 1 or 2 in the presence of (Me3Si-C≡C-)216 yields the dialkynylsilane 17 which, on further reaction with 2, yields the 2,5-disilabicyclo[2.2.0]hexa-1(6),3-diene (18). Irradiation of 3 in the presence of 16 affords the cis- and trans-isomeric 1,3-dimethylene-2,4-disila-cyclobutane derivatives cis-21 and trans-21, presumably via a 1-silaallene intermediate. The structures of 12, 15, 18, cis-21, and trans-21 have been determined by X-ray crystallography.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2319-2325 
    ISSN: 1434-1948
    Keywords: Dichloroanilines ; Propanil ; Iron(III) tetrasulfonatophthalocyanine ; Oxidations ; Catalysts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We investigated the degradation of polychlorinated pollutants, such as dichloroanilines and related anilides, catalyzed by iron(III) tetrasulfonatophthalocyanine (FePcS) with potassium monopersulfate or hydrogen peroxide as oxidant. The reaction is influenced by the positions of the two chloro-substituents and by the nature of the oxidant. The FePcS-catalyzed oxidation of 3,5-dichloroaniline with potassium monopersulfate leads to the formation of more biodegradable products (carboxylic acids) and to potentially toxic dimers (azo and azoxy compounds). The oxidation of 3,4-dichloroaniline by FePcS/H2O2 converts this pollutant into coupling products. The formation of dimers in the catalytic oxidation of dichloroanilines can be avoided by acylation of the amine function.
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  • 59
    ISSN: 1434-1948
    Keywords: Asymmetric catalysis ; Transfer hydrogenation ; Ruthenium ; Amino alcohol ligands ; X-ray structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nature of ruthenium-amino alcohol precursors in the catalytic cycle of asymmetric hydrogen transfer reactions was studied using two C2-symmetrical tetradentate ligands (1 and 2) that were synthesised from (nor)ephedrine. The structure of the catalyst precursor was examined through catalysis and NMR experiments. It was shown that the active catalyst contains one ligand per metal, which coordinates in a didentate N,O fashion (9). In addition, a RuIICl2 complex, in which N,N′-bis(2-hydroxy-1-methyl-2-phenylethyl)-1,2-diaminoethane (1) coordinates through two nitrogen atoms, was structurally characterised by X-ray diffraction (8). - Based on the results of this study a series of new amino alcohol ligands was synthesised from easily available starting materials. Optimisation of the amino alcohol ligand structure resulted in the most effective chiral amino alcohol ligand (5) so far that is capable of reducing acetophenone at 0 °C with up to 97% ee in the RuII-catalysed transfer hydrogenation.
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  • 60
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2327-2333 
    ISSN: 1434-1948
    Keywords: Heterocycles ; Organo-phosphorus compounds ; Dithiadiphosphetane disulfides ; Phosphonates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New salts of thionated (naphthalene-1,8-diyl)bis(phosphonic) acid monoanhydrides [PPh4+]2[C10H6PS2(μ-S)PS22-] (2) and [K+]2[C10H6PS2(μ-S)POS2-]·H2O (3) both containing the C3P2S ring, were prepared in high yields by the reaction of 2,4-(naphthalene-1,8-diyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (1) with NaHS and PPh4Cl, or KOH, respectively, in water. The derivative 3, containing a P=O terminal bond as well as P-S-P bridge, undergoes, in acid conditions, a rearrangement reaction leading to the O,S-symmetrically substituted derivative [K+]2[C10H6PS2(μ-O)PS22-] (4) containing a C3P2O heterocycle. Dipotassium salt 4 was converted into the bis(tetraphenylphosphonium) salt 5 by the treating with PPh4Cl. Hydrolysis of [PyH+][C10H6P(S)(NHMe)(μ-S)PS22-] (15) led to [CH3NH3+][PyH+][C10H6POS(μ-O)POS2-]·1.5 Py (6). New compounds were characterised by 31P{1H}-, 1H- and 13C{1H}-NMR, FT-IR, ES-MS and in the cases 2-6 by X-ray structure determination. The 31P{1H}-NMR spectra of these mixed O,S-derivatives are briefly discussed.
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2343-2346 
    ISSN: 1434-1948
    Keywords: Chromium ; Cyanides ; Density-functional calculation ; Electronic structure ; Spin state ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The steric and electronic factors responsible for the reactivity differences between CN and Cl complexes of CpCrIII were examined by DFT/B3LYP computational techniques. The energy difference between quadruplet and doublet [CpCr(CN)2(PH3)], ΔED-Q, was calculated to be 21.2 kcal mol-1 with the LanL2DZ basis set. Although the high-spin configuration is still the ground state for the cyanide complex, the energy gap is 8.7 kcal mol-1 less than that found for the corresponding chloride species. The difference between quadruplet [CpCr(CN)2(PH3)] and doublet [CpCr(CN)2(PH3)2] less free PH3, ΔECr-P, is also smaller than for the Cl system. The components of ΔECr-P for CN and Cl were analyzed by calculating energies at fixed geometries in both spin states, which indicated that the influence of the cyanide group on the pairing energy was more important than changes in Cr-PH3 bond strength or steric effects.
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  • 62
    ISSN: 1434-1948
    Keywords: Cyclopropanation ; Copper ; N ligands ; Macrocycles ; Supported catalysts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CuI and CuII complexes of cyclic and open-chain polyaza compounds have been tested as catalysts in the benchmark cyclopropanation reaction of styrene with ethyl diazoacetate. In general, only small amounts of copper are needed to promote the reaction. The catalytic activity depends on the structure of the ligand, e.g. amine-amides are more efficient than polyamines, and on the oxidation state of copper, CuII being more active than CuI. Given that CuI is the active species, these changes of behavior must be related to the stabilities of the complexes. The nature of the counterion also has a noticeable influence on the catalytic activity, the role of which is discussed. XAS measurements suggest the formation of oligomeric species. Some of the chiral ligands lead to small enantiomeric excesses. Open-chain ligands can easily be supported on organic polymers and their complexes can be used as catalysts. Furthermore, cyclic and acyclic complexes can be supported on clays by cation exchange and the solids obtained tend to promote the reaction with a decrease in the trans/cis ratio.
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  • 63
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    Berichte der deutschen chemischen Gesellschaft 2000 (1999), S. 455-461 
    ISSN: 1434-1948
    Keywords: Aluminium ; Gallium ; Indium ; Azide ; Rietveld ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new tetraazido complexes of aluminium, gallium, and indium [thf2Na][thf2Al(N3)4] (1), [py2Na][py2In(N3)4] (2), and Na[Ga(N3)4] (3) have been synthesized from MCl3 and NaN3 by salt metatheses and characterized by X-ray diffraction analysis. In compounds 1 and 2, the Group 13 metal atom and the sodium atom are each hexacoordinated by four azido groups and two additional solvent molecules. The azido groups act as μ(1,3)-bridging ligands between the Group 13 metal and sodium, thereby forming network structures. In contrast, complex 3 is solvent-free and exhibits a tetracoordinated gallium centre and a heptacoordinated sodium atom. The structure of 3 has also been investigated by means of X-ray powder data and the Rietveld method and the results are compared with the single-crystal data.
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  • 64
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1259-1269 
    ISSN: 1434-1948
    Keywords: Metal dithiolenes ; Charge-transfer complexes ; Azo compounds ; Electrical conductivity ; High-resolution X-ray powder diffractometry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Combination of the planar redox-active ions [ML2]2- (L = mnt2- = maleonitrile-1,2- dithiolate; M = Ni (1), Pd (2), Pt (3); dmit2- = 2-thioxo-1,3-dithiol-4,5-dithiolate: M = Ni (4), Pd (5) and trans-4,4′-azobis(1-methyl-pyridinium), (a2+) affords 1:1 ion pairs exhibiting partial and complete electron transfer as evidenced by UV-Vis and EPR spectra. Replacement of planar a2+ by a non-planar dipyridinium ketone b2+ leads to the complexes 1b and 4b. 1a, 2a, and 3a are predominantly composed of dications and dianions while 4a, 5a, and 4b are rare examples of ion pairs consisting of two radical ions. Single crystal X-ray structural analyses was performed on 4a, a(PF6)2, and a(MeSO4)2 while the structure of 1a was resolved by powder X-ray diffractometry. The latter consists of mixed stacks of planar dianions and dications forming a slipped arrangement with the centers of the two ions displaced relative to each other by 250 pm. The short interplanar distances of 340 pm are in agreement with the presence of a weak charge-transfer interaction as indicated by the corresponding absorption band at about 1400 nm. A mean reorganization energy of 0.85 ±0.04 eV is calculated from the Hush equation for complexes 1a, 2a, and 3a. No ion pair charge-transfer band is observable for 4a, 5a, and 4b. Surprisingly, in the solid state structure of 4a the [Ni(dmit)2]- monoanions do not form segregated columns as found in the many ion pairs with redox inert counterions, but prefer a mixed stack arrangement as observed also for 1a.The specific electrical conductivity of pressed powder pellets of complexes exhibiting a charge-transfer band is in the range of 2 × 10-7 to 1 × 10-5 Ω-1cm-1, increasing with increasing driving force of electron transfer in accordance with previous results. Different to that, the conductivity of the other complexes does not depend on driving force and is much higher (2 × 10-4 to 4 × 10-4 Ω-1cm-1).
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  • 65
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1291-1293 
    ISSN: 1434-1948
    Keywords: Aluminum ; Lead ; O ligands ; Alkoxy carboxylates ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel heterometallic aggregate Pb2Al5(μ3-O)(μ4-O)(μ-OiPr)9(OiPr)3(μ-OAc)3 obtained from the interaction of Pb(OAc)2 and Al(O-iPr)3 is the first structurally characterized example based on lead and aluminum. This compound has been isolated in high yield and examined by 1H-, 13C-, and 27Al NMR, and in the solid state by X-ray crystallography.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1405-1407 
    ISSN: 1434-1948
    Keywords: Agostic interactions ; Samarium ; Silylamide ; Transsilylamination ; Trinuclear complex ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sm[N(SiMe3)2]2(thf)2 reacts with 1,1,3,3-tetramethyldisilazane by a transsilylamination reaction to form the hexane-soluble Sm[N(SiHMe2)2]2(thf)x in high yield. An X-ray diffraction study reveals a novel trinuclear complex of composition Sm{[μ-N(SiHMe2)2]2Sm[N(SiHMe2)2](thf)}2 featuring a bent array of metal centers. Multiple metal···SiH β-agostic interactions sterically and electronically saturate the samarium(II) centers implying a new coordination mode of the bridging amide ligands.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1409-1414 
    ISSN: 1434-1948
    Keywords: Ruthenium complexes ; Luminescence ; Bridging ligands ; Terpyridine ligands ; Polynuclear metal complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption spectra and the luminescence properties of three dinuclear RuII complexes and one trinuclear RuII complex have been investigated. All the complexes have rack-type structures. The dinuclear complexes 1, 2, and 3 incorporate a bis-tridentate bridging ligand made up of a pyrimidine and four pyridine moieties, as well as two 2,2′:6′,2′-terpyridyl (tpy) ligands. The trinuclear complex 4 incorporates a tris-tridentate bridging ligand made up of two pyrimidine and five pyridine moieties, as well as three tpy ligands. The absorption spectra of the complexes show a large number of ligand-centered (LC) and metal-to-ligand charge-transfer (MLCT) bands. All the complexes exhibit emission from a triplet MLCT state, with maxima in the spectral range 840-950 nm (lifetimes between 40 and 80 ns) at 298 K in fluid solution, and in the spectral range 760-810 nm (lifetimes between 2 and 3 μs) at 77 K in rigid matrices. A fine tuning of the absorption and luminescence properties of complexes 1-3can be achieved by changing the substituents on the pyrimidine ring of the bridging ligand. Efficient energy transfer within the rack structure 4 occurs from the (upper-lying) central metal-based chromophore to the (lower-lying) peripheral ones.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1415-1420 
    ISSN: 1434-1948
    Keywords: Combinatorial chemistry ; Molecular recognition ; Functionalized bipyridine metal complexes ; Janus molecules ; Hydrogen bonding ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The functionalized ligands 1 and 2 bearing hydrogen-bonding recognition groups have been synthesized. Their assembly by metal ions such as CuI and PdII having different coordination geometries generates different receptor architectures for the binding of suitable substrates. Addition of the complementary bis(imide) Janus molecules (4-7) to [1a, 2a, CuTf] or to [1b, 2b, Pd(BF4)2] mixtures leads to a moderate selective increase of the fraction of the [(1a)2Cu]+ or [(1b)2Pd]2+ complex depending on the Janus substrate used. Largest enhancements are observed for those Janus substrates that may be expected to display highest geometrical complementarity with the two complexes. These results represent a process directed by target binding based on dynamic combinatorial chemistry.
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  • 69
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1435-1443 
    ISSN: 1434-1948
    Keywords: Captopril ; Cysteine ; Rhenium ; S ligands ; Thioaldehydes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral racemic rhenium thioaldehyde complexes [CpRe(NO)(PPh3)(η2-S=CHR)]PF6 (2a-g) bearing functionalized aliphatic groups R [R = CH2Ph (a), COOEt (b), CH2COOMe (c), CH2C(O)NHCH2Ph (d), (R)-CH(NC8H4O2)COOMe (e), (S,S)-CH(Me)C(O)NC4H7COOMe (f), C4H3O (g)] have been obtained by hydride abstraction from the corresponding thiolate complexes [CpRe(NO)(PPh3)(SCH2R)] (1a-g). With the exception of 2b, only single stereoisomers with like configurations at rhenium and the thioaldehyde carbon atom were obtained. In some cases, the corresponding sulfinate complexes [CpRe(NO)(PPh3)(SO2CH2R)] (3d-f) were formed as by-products. The analogous toluenesulfinate complex [CpRe(NO)(PPh3){SO2(4-C6H4CH3)}] (3a) has been prepared from [CpRe(NO)(PPh3)(THF)]BF4 (8), and the structure of 3e has been determined by X-ray crystallography. The use of phosphorus ligands other than PPh3 was briefly explored with the synthesis of [CpRe(NO)(PR′3)(η2-S=CHR)]PF6 (5a-d) [R′ = OPh, R = Ph (a), 4-C6H4Cl (b), R′ = iPr, R = Ph (c), H (d)]. Nucleophilic addition of NaSMe to [CpRe(NO)(PPh3){η2-S=CH(4-C6H4OMe)}]PF6 (5e) gave the dithioacetal complex [CpRe(NO)(PPh3){SCH(SMe)(4-C6H4OMe)}] (9) in high yield and with low diastereoselectivity. Diels-Alder additions of 5a, e with 2,3-dimethylbutadiene and 2,3-dimethoxy-butadiene gave complexes of cyclic thioethers (10a-c). From the relative rates of reaction (5a 〉〉 5e) and the low diastereoselectivity, it was concluded that the cycloadditions as well as the nucleophilic addition proceed via the linkage isomers [CpRe(NO)(PR′3)(η1-S=CHR)]PF6.
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  • 70
    ISSN: 1434-1948
    Keywords: Diene complexes ; η3-Cyclooctatetraene metal complex ; B(C6F5)3 addition ; Tantalum ; Bicyclo[5.1.0]octadienyl metal complex ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The [(η4-diene)(η5-RCp)TaCl2] complexes 6a-e (diene = butadiene, isoprene or 2,3-dimethylbutadiene; RCp = pentamethylcyclopentadienyl, methylcyclopentadienyl or cyclopentadienyl) react with cyclooctatetraene dianion (employed as [(cot)Li2]) to yield the (η4-diene)(η3-cyclooctatetraene)(η5-RCp)tantalum complexes 7. The η3-cot coordination was confirmed by an X-ray crystal structure analysis of the compound [(supine-s-cis-η4-C4H6)(η3-cot)(η5-Cp*)Ta] 7a. In solution, the cot ligand of all the complexes 7 is fluxional. Two isomers [supine and proneorientation of the (diene)CpTa subunit] were found for the (η4-butadiene)(η3-cot)CpTa system (7e/7e′ = 95:5). Complex 7e cleanly adds the organometallic Lewis acid B(C6F5)3 to yield the betaine system [(η4-C4H6){C8H8B(C6F5)3}Cp*Ta] 8, which contains a substituted bicyclo[5.1.0]octadienyl ligand.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1557-1562 
    ISSN: 1434-1948
    Keywords: Calixarenes ; Macrocycles ; Silver ; Radiotracer technique ; Metal-ion extraction ; Radiochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calixareneglycine ester acetamides 4a-c have been synthesized from calixareneacetyl chlorides 5a-c and glycine ethyl ester (6). Their ion-binding properties have been investigated by liquid-liquid extraction with radiotracer techniques. The experiments reveal a moderate affinity towards silver(I) ions, which increases with calixarene ring size.
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  • 72
    ISSN: 1434-1948
    Keywords: Functionalized Cp ligand ; ĸ2O,O′-Chelate ; Carboxamido-substituted cyclopentadienides ; Zirconium complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of sodium cyclopentadienide with two molar equivalents of tert-butyl isocyanate yields sodium 1,2-bis(N-tert-butylcarbamoyl)cyclopentadienide (6). The [C5H3(1,2-CONHCMe3)2]Na reagent 6 adds to Cp2Zr(CH3)Cl (8) to yield Cp2Zr(CH3)[C5H3(CONHCMe3)2] (9). In 9 the C5H3(CONHCMe3)2 ligand is bonded to zirconium through one of its carboxamido-oxygen atoms (ĸO-coordination). Treatment of 6 with CpZrCl3(THF)2 yields CpZrCl2[C5H3(CONHCMe3)2](THF) 11. In 11 the 1,2-bis(N-tert-butylcarbamoyl)cyclopentadienide moiety serves as a Cs-symmetric chelate ligand, binding to zirconium through both carbamoyl oxygens (ĸ2O,O′-coordination). The same seven-membered metallacyclic structural type is found in the reaction products of 6 with ZrCl4(THF)2 in 1:1 and 2:1 molar ratios. The former yields the distorted octahedral complex ZrCl3[C5H3(CONHCMe3)2](THF) (12), the latter gives the chiral octahedral system ZrCl2[C5H3(CONHCMe3)2]2 (13). In solution, complex 13 undergoes a thermally induced enantiomerization process (Λ → Δ interconversion), for which a Gibbs activation energy of ΔG
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  • 73
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 35-39 
    ISSN: 1434-1948
    Keywords: Fluorescent sensors ; Molecular recognition ; Charge transfer excited states ; Metal complexes ; pH Sensors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fluorescent emission of the N,N-dimethylaniline fragment of the tetramine system 3varies with pH, displaying a maximum of the fluorescent intensity, IF, at pH = 5. Binding of transition metals (CuII, NiII) induces fluorescence quenching and modifies the IF vs. pH profile, giving rise to an OFF-ON-OFF type of sensor. The [ZnII(3)]2+complex recognises carboxylate anions, both aliphatic and aromatic. Recognition is signalled via fluorescence quenching only for aromatic carboxylates.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 27-33 
    ISSN: 1434-1948
    Keywords: 103Rh NMR ; Rhodium complexes ; Nitrogen ligands ; Chemical-shift computation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study electronic and steric effects on δ(103Rh), the103Rh-NMR spectra of a series of [Rh(cod)L2] complexes (with L = nitrogen, oxygen, or chloride) have been measured by gradient-enhanced HMQC (1H,103Rh) NMR spectroscopy. Density functional computations of representative examples have been performed at the GIAO-B3LYP level of theory. The obtained experimental values of 103Rh shifts fit the generally observed trend of coordinating ligands in the first coordination sphere of the metal: P 〈 N 〈 O. Calculated 103Rh shifts agreed to within 8 % with experimental values. The computational results indicate that the Rh-N bond distance has a larger influence on the chemical shift than the N-Rh-N angle.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 21-26 
    ISSN: 1434-1948
    Keywords: Silicon ; Silanes, sterically congested ; Tris(trimethylsilyl)silanes ; (Chloromethylene)ammonium chlorides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(trimethylsilyl)silyllithium (1) reacts with dialkyl(chloromethylene)ammonium chlorides (molar ratio 2:1) to give the (dialkylamino)bis(hypersilyl)methanes [(Me3Si)3Si]2CHNR2 (5a-c; a: R = Me, b: R = Et, c: R2 = [CH2]5). Due to the extreme bulkiness of the hemispherical (Me3Si)3Si substituents, the structures of these geminal bis(hypersilyl) derivatives are characterized by tremendous distortions of their molecular skeletons. This was confirmed by X-ray structural analyses of 5a and 5c, which revealed considerable elongations of the central Si-C bonds (5a: 2.01 and 1.95 Å; 5c: 1.99 and 1.97 Å) and an extreme widening of the Si-C-Si angles at the central sp3-carbon atoms (5a: 132.6°; 5c: 128.7°). By concentrated sulfuric acid, 5a is converted to give, after hydrolysis, the silanol (Me3Si)2Si(OH)-CH2Si(SiMe3)3 (13). The formation of 13 is discussed as proceeding through the transient silene (Me3Si)2Si=CHSi(SiMe3)3 (11), generated by a formal (dimethylamino)trimethylsilane elimination from 5a according to an acid-induced sila Peterson mechanism.
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  • 76
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 41-49 
    ISSN: 1434-1948
    Keywords: Phosphorus heterocycles ; Aromaticity ; Phosphenium cations ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aromatic stabilization of cyclic phosphenium cations (general type C2N2P+) was studied by experimental methods (synthesis, multinuclear NMR, single crystal X-ray crystallography) and quantum chemical calculations (ab initio methods). The structures of the 1,3,2-diazaphosphole derivatives [(tBuN-CH=CH-NtBu)P+]Cl- (1), (tBuN-CH2-CH2-NtBu)P-Cl (2), [(tBuN-CH=CH-NtBu)P]+PF6- (3) and [(tBuN-CH2-CH2-NtBu)]P+PF6- (4) were examined by single crystal X-ray diffraction. The chloro phosphane [(tBuN-CH=CH-NtBu)P]+Cl- (1) has an ionic P-Cl bond and contains an aromatically stabilized phosphenium cation [shortest distance P···Cl = 275.9(2) pm], while the CC-saturated compound (tBuN-CH2-CH2-NtBu)P-Cl (2) is covalent. The two chloro-phosphanes 1 and 2 differ sharply in their volatility and solubility in organic solvents. Compound 2 is soluble in hydrocarbons and sublimes readily at 90 °C/0.1 Torr but 1 is insoluble in hexanes and not volatile below 180 °C/0.1 Torr. The degree of aromatic stabilization in the phosphenium cation 1 was investigated by ab initio methods. For the model cations [RN-CH2-CH2-NR]P+ and [(RN-CH=CH-NR)P]+, thermochemical stabilization energies of 25.8 kcal · mol-1 (R = H) and 28.1 kcal · mol-1 (R = Me) were obtained from isodesmic hydrogenation reactions at the RHF/MP2/6-31G*//RHF/6-31G* level.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 67-68 
    ISSN: 1434-1948
    Keywords: Hydroformylations ; Rare gas ; Homogeneous catalysis ; Carbonylcobalt compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of cobalt-catalyzed hydroformylation of cyclohexene to cyclohexanecarboxaldehyde is significantly reduced when xenon is added to the reaction mixture at a concentration similar to that of the olefin. No significant effect is produced by helium or neon under similar conditions. These experiments suggest competitive coordination of xenon to the catalytically active cobalt species.
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  • 78
    ISSN: 1434-1948
    Keywords: Zirconium arsenate ; Crystal structure ; Amine intercalation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystalline structure of γ-Zr(AsO4)(H2AsO4) × 2 H2O (γ-ZrAs) has been refined by the Rietveld method. It has a monoclinic P21 layered structure built up from AsO4 tetrahedra and ZrO6 octahedra stacked along the 001 direction. The cell parameters are: a = 5.5752(6) Å, b = 6.8290(7) Å, c = 12.110(1) Å, and β = 103.03(1)°. The layered nature of γ-ZrAs is confirmed by the intercalation of n-alkylamines (CH3[CH2]nNH2; n = 0-5) as well as of cyclic amines (benzylamine, cyclohexylamine, piperidine, and pyridine). Among the linear amines, only with methyl-, ethyl-, and hexylamine is the maximum incorporation attained. With the cyclic amines, except in the case of pyridine, pure new phases are obtained, with the highest degree of intercalation being one mol of amine per mol of γ-ZrAs.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 51-59 
    ISSN: 1434-1948
    Keywords: Asymmetric catalysis ; Allylic alkylation ; 1-Methyl-5-(1′-methylpent-2′-ynyl)barbituric acid ; Palladium catalysts ; Chiral phosphane imine ligands ; Methohexital ; Anesthetic dose ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Allylation of 1-methyl-5-(1′-methylpent-2′-ynyl)barbituric acid (MBS) with allyl acetate using in situ catalysts of palladium(II) acetylacetonate and chiral phosphane imine ligands resulted in the enantioselective formation of 5-allyl-1-methyl-5-(1′-methylpent-2′-ynyl)barbituric acid (Methohexital), an important anesthetic drug. Both, MBS and Methohexital contain two stereogenic carbon atoms. In MBS, the asymmetric centre in the barbiturate system is labile due to enolization. The asymmetric centre in the hexyne side chain is stable and racemic. The two asymmetric centres of Methohexital are stable and give rise to four stereoisomers, two diastereomeric racemates. An analysis of the isomers of MBS and Methohexital was established on the basis of 1H NMR and, in particular, GC including a base-line separation of the four stereoisomers of Methohexital. The stereoselectivity of the allylation is difficult to control, because the new quaternary asymmetric centre in the barbiturate ring of Methohexital is formed within the nucleophile, attacking the η3-allyl ligand of the catalyst from the side opposite to the palladium atom. Classical optically active ligands, such as diop or norphos, give only 2-6 % ee. Chiral phosphane imine ligands are a successful class of compounds, synthesized by Schiff base condensation of (2-formylphenyl)diphenylphosphane with optically active primary amines. The most efficient ligands have a hydroxymethyl and a bulky alkyl substituent at the asymmetric centre in the imine part, e.g. the L-iso-leucinol and the L-tert-leucinol derivatives 5 and 7. In the Pd-catalyzed allylation of MBS a kinetic resolution and the effect of the enantioselective catalyst interplay, the contributions of which are separated. For MBS the best stereoselectivity factor of the kinetic resolution s = kR/kS was 2.6 and 83 % “ee” were achieved. The corresponding values for Methohexital were s = 3.5 and 80 % ee in the α-dl pair. For 10 mixtures of Methohexital stereoisomers the anesthetic doses for rats were determined. With 9.1 mg/kg body weight of the animal the sample obtained from the catalysis with the D-α-phenylglycinol derivative 8 gave a much lower anesthetic dose than the widely used narcotic Brevimytal®Natrium, the sodium salt of the α-dl racemate of Methohexital, with 13.0 mg/kg body weight.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 69-73 
    ISSN: 1434-1948
    Keywords: Boron ; Titanium ; Metallocenophanes ; [1]Boratitanocenophanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents two methods for the synthesis of the first [1]boratitanocenophanes. The novel biscyclopentadienylborane [(Me3Si)2NB(C5H5)2], the dilithio salt Li2[(Me3Si)2NB(C5H4)2] (1) of which was characterized by multinuclear NMR methods, was prepared in situ, and served as starting material for several [1]boratitanocenophanes. [Cl2Ti{(C5H4)2BN(SiMe3)2}] (2) was obtained in high yield by a convenient one-pot synthesis starting from 1 and [TiCl3(thf)3], followed by oxidation with PbCl2. The highly reactive [(Me2N)2Ti{(C5H4)2BN(SiMe3)2}] (3) was obtained by the reaction of [(Me3Si)2NB(C5H5)2], prepared in situ, with Ti(NMe2)4and converted into the chloro derivatives [(Me2N)ClTi{(C5H4)2BN(SiMe3)2}] (4) and [Cl2Ti{(C5H4)2BN(SiMe3)2}] (2) by treatment with one or two equivalents of a suitable diaminochloroborane. All [1]boratitanocenophanes were characterized in solution by multinuclear NMR spectroscopy, and in addition the structure of 2 in the crystalline state was determined by a single-crystal X-ray study.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 83-86 
    ISSN: 1434-1948
    Keywords: 2,4,6-Tri-tert-butyl-1,3,5-triphosphabenzene ; η6-Triphosphabenzene transition metal complexes ; Displacement reactions ; Phosphorus heterocycles ; Arene complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The η6-1,3,5-triphosphabenzene transition metal complexes 12a,b, 14, and 16 have been synthesized for the first time by the displacement of η6-arene ligands (toluene, benzene and naphthalene) with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene (9). The new complexes have been fully characterized by a combination of elemental analysis, mass spectrometry, and 1H-, 13C- and 31 P-NMR spectroscopy.
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 75-81 
    ISSN: 1434-1948
    Keywords: TSDE ; Ceramics ; Theoretical IR-spectroscopy ; RI-MP2 ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new compound for the molecular synthesis route to high-demand Si/B/N/C ceramics has been found and is described in this work. We report on an elegant “one-pot” synthesis of [(trichlorosilyl)dichloroboryl]ethane (TSDE, Cl3Si-CH[(CH3)(BCl2)]) and its structural characterisation by means of nuclear magnetic resonance and (theoretical and experimental) infra-red spectroscopy. Density functional and Hartree-Fock calculations combined with a perturbational treatment of the electron correlation have been performed. Both methods yield good agreement of theoretical and experimental spectra, with the perturbational approach being slightly superior. In a similar way to the amino compound [(trichlorosilyl)amino]dichloroborane (TADB), TSDE exhibits a planar coordination of the dichloroboryl terminus but tetrahedral neighbourhoods for both carbon and silicon. The electronic structure has been investigated and a σ - n order of the frontier orbitals shall be discussed.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 87-93 
    ISSN: 1434-1948
    Keywords: Selenium ; Silicon ; Silicides ; Tantalum ; Condensed cluster compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ta11Si2Se8 was synthesized from a pre-reacted mixture of the elements in a sealed tantalum tube at 1570 K. Mo-doped crystals were obtained in a welded molybdenum crucible by a chemical transport reaction using TeI4 as a transport agent. The structure of Mo0.11Ta10.89(2)Si2Se8 has been determined by single crystal X-ray means [Pnnm, Z = 2, a = 1184.4(1) pm, b = 1939.4(1) pm, c = 346.48(2) pm, wR2 = 0.069]. The structure of the ternary phase was verified by means of a Rietveld profile fit of a powder X-ray diffractogram. The silicide is isotypic with Ta11Ni2Se8. The structure is composed of Si-centred, tricapped trigonal prismatic Ta9Si clusters. The tetrakaidecahedral Ta9Si clusters are fused into twin chains by sharing the Tapr atoms of facing triangulated prism faces and one out of three capping atoms Tac. Intercluster linkage of the remaining Tac atoms generates a microporous ∞3[SiTa2cTa1/2cTa6/2pr] substructure. The channels of the metal network are sheathed by three-, four-, five-, and sixfold coordinated Se atoms. Four-probe dc resistivity measurements revealed the Mo-doped phase to be a moderate metallic conductor. The bonding interactions contributing to the stability of Ta11Si2Se8 and distinctions in bonding for Ta11Si2Se8 and Ta11Ni2Se8 are analysed on the basis of semi-empirical extended Hückel calculations.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 95-99 
    ISSN: 1434-1948
    Keywords: Tungsten ; Fluorine ; 2,2,2-Trifluoroethoxy ; Bis(2,2,2-trifluoroethyl)amino ; Aza-tungsta-cyclopropane ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: WF6 reacts with HOCH2CF3 to form F5W-OCH2CF3 and cis-WF4(OCH2CF3)2. CsF is added to F5WOCH2CF3, yielding the heptacoordinated anion [F6WOCH2CF3]-, which has a capped octahedral structure with the oxygen ligand in an equatorial position. The first step of the reaction of WF6 with HN(CH2CF3)2 results in F5WN(CH2CF3)2. Excess HN(CH2CF3)2 causes deprotonation, yielding the heptacoordinated [F5W(η2CF3-CHN-CH2CF3)]- anion. This can be described as a tungstaazacyclopropane derivative or a π complex between F5W- and CF3-CHN-CH2CF3. The only case in which MoF6 reacts similarly is the formation of F5Mo-OCH2CF3.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 7-9 
    ISSN: 1434-1948
    Keywords: Boranes ; Diazaboroles ; Heterocycles ; Ketiminoboranes ; Crystal Structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclocondensation reaction of benzil-bis(trimethylsilylimin) (3) and Cl2B-NiPr2 via silicon-boron exchangeresults in the solvent-dependent formation of the 1,3,2-diazaborole 1a or the 1,3,6,8,2,7-tetraazadiborecin 2a. Using the more rigid 9,10-bis(trimethylsilylimino)phenanthrene instead of 3 only the five-membered heterocycle 4,5-biphenylene-2-diisopropylamino-1,3,2-diazaborole (1b) is formed. The cyclic ketiminoboranes are characterized by NMR and X-ray diffraction data. The 1,3,2-diazaborole ring is almost planar, while the conformation of the 1,3,6,8,2,7-tetraazadiborecin has the shape of a figure-eight loop.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1-5 
    ISSN: 1434-1948
    Keywords: Terpyridine ligands ; Ferrocenes ; Iron ; Ruthenium ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2′:6′,2′′-Terpyridines bearing a substituent × in the 4′-position [3a: × = Fc-C≡C-p-C6H4; 3b: × = Fc#-C≡C-p-C6H4; Fc = (C5H5)Fe(C5H4), Fc# = (C5Me4H)Fe(C5Me4)] were prepared by Pd0-catalysed cross-coupling reactions. 3b was characterised by X-ray structure analysis. [(3a)RuCl2(DMSO)] (4a) and [(3b)RuCl2(DMSO)] (4b) were obtained by reaction of [RuCl2(DMSO)4] with 1 equivalent of 3a and 3b, respectively, while the analogous reaction with 2 equivalents afforded [(3a)2Ru][PF6]2 (5a) and [(3b)2Ru][PF6]2 (5b), respectively, after precipitation with aqueous [NH4][PF6]. Similarly, [(3a)Ru(tpy)][PF6]2 (6) was isolated from the reaction of 4a with 2,2′:6′,2′′-terpyridine (tpy). Compounds 3 and 5 were investigated by cyclic voltammetry, which revealed that the introduction of eight methyl groups leads to the expected cathodic shift of the E0′ values of ca. 0.44 V for the ferrocenyl-centered redox processes.
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  • 87
    ISSN: 1434-1948
    Keywords: Ruthenium ; Halogens ; Carbonyl complexes ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous hydrogen halides HX (X = Cl, Br, I) are shown to be excellent halogen sources for the synthesis of a series of halogen-containing ruthenium mono(2,2′-bipyridine) carbonyl complexes Ru(dmbpy)(CO)2X2 (dmbpy = 4,4′-dimethyl-2,2′-bipyridine), as well as effective reagents for the attack of the Ru-Ru bond in the dimer [Ru(dmbpy)(CO)2Cl]2. Selective syntheses were established for both cis- and trans-halogen complexes in the case of Cl- and of Br-containing derivatives, but the only stable isomer containing iodine was trans(I)-Ru(dmbpy)(CO)2I2. The failure to obtain the cis isomer was probably due to sterical effects. Furthermore, a novel S-bound trans(SCN) analogue was synthesized and structurally characterized. In all experiments, the reaction conditions selected led to complete halogen exchange; no mixed halogen or pseudohalogen complexes were detected.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 117-127 
    ISSN: 1434-1948
    Keywords: Zinc ; Aldehyde ligands ; Weakly coordinating anions ; Structural chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zinc salts of low or zero water content were obtained from the hexahydrates of zinc nitrate, zinc perchlorate, and zinc tetrafluoroborate by dehydration with triethoxymethane or by solvation with acetonitrile or nitromethane. The compounds incorporated aldehydes as ligands when treated with an excess of the aromatic aldehydes benzaldehyde, mesitylaldehyde, 2-chlorobenzaldehyde, and 4-fluorobenzaldehyde. Eighteen zinc-aldehyde complexes were isolated and identified by crystal structure determinations. All contain octahedral zinc to which 2, 3, 4, 5, or 6 aldehyde ligands are bound. Water, ethanol, and acetonitrile molecules act as coligands. Of the anions employed, BF4- and SbCl6- were found to be only noncoordinating and NO3- only coordinating, whereas complexes with one or two perchlorate ligands were obtained in addition to perchlorate salts.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 129-135 
    ISSN: 1434-1948
    Keywords: Zinc ; Aldehyde ligands ; Halide ligands ; Structural chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aldehyde complexes of the zinc halides were obtained by treating ZnCl2, ZnBr2, and ZnI2 under anhydrous conditions with large excesses of benzaldehyde and various substituted benzaldehydes. Their constitutions were determined by a total of 12 X-ray structure analyses. Three product types were found: ZnHal2(aldehyde)2 (A), [ZnHal2(aldehyde)]∞ (B), and [Zn(aldehyde)6] [Zn2Hal6] (C). All three dissolve readily in the corresponding aldehyde or in polar nonprotic solvents indicating the presence of solvated zinc species in solution.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 107-115 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Density functional calculations ; Phosphinidene ; Carbonyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio MO and DFT calculations have been performed on phosphinidene complexes of the type Cr(CO)5-PR, with R = H, CH3, SiH3, NH2, PH2, OH, and SH. The formation of the Cr-P bond essentially arises from a ligand-to-metal charge transfer. While a significant π backdonation is also observed for the Cr(CO)5-PH, Cr(CO)5-PCH3, and Cr(CO)5-PSiH3 complexes, this is less the case for Cr(CO)5-POH, Cr(CO)5-PSH, and Cr(CO)5-PNH2, and the backbonding almost disappears for Cr(CO)5-PPH2. In both the lowest lying singlet and triplet states, all complexes exhibit a staggered conformation. CASSCF/CASPT2 calculations performed with the ANO basis sets indicate a closed-shell singlet ground state along the whole series. The binding energy between Cr(CO)5 and PR ranges from 216 kJ/mol for Cr(CO)5-PNH2 to 127 kJ/mol for Cr(CO)5-PSiH3 (B3LYP values). In general, the B3LYP-DFT scheme yields reasonable qualitative and quantitative results when compared with CASPT2(12/12).
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 137-144 
    ISSN: 1434-1948
    Keywords: Zinc ; Aldehyde ligands ; N,O Chelate ligands ; Structural chemistry ; Chelates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of various zinc salts with the chelating aromatic aldehydes pyridine-2-carbaldehyde, 6-methylpyridine-2-carbaldehyde, pyridine-2,6-dicarbaldehyde, and 2-dimethylaminobenzaldehyde were studied. The monoaldehydes and zinc halides yielded the tetrahedral chelate complexes ZnHal2·aldehyde. Pyridine-2-carbaldehyde also formed the octahedral bis-chelate complexes ZnHal2·2 aldehyde. The octahedral tris-chelate complexes [Zn(aldehyde)3]2+ were obtained from [Zn(CH3CN)6](SbCl6)2. Pyridine-2,6-dicarbaldehyde was found to be tridentate in the trigonal-bipyramidal complexes ZnHal2·aldehyde. The structural variability in this system was underlined by the identification of the two unusual complexes [(pyridine-2-carbaldehyde)2(H2O)Zn-Cl-ZnCl3] and [ZnI(pyridine-2-carbaldehyde)2]2[ZnI4].
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  • 92
    ISSN: 1434-1948
    Keywords: Sandwich complexes ; Iron ; Tin ; NMR spectroscopy ; Mössbauer spectroscopy ; Electrochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1,1′-bis(chlorostannyl)-substituted ferrocenes Fe(C5H4-SnMe2Cl)2 (2), Fe(C5H4-SnMeCl2)2 (3) and Fe(C5H4-SnCl3)2 (4) were prepared, starting from 1,1′-bis(trimethylstannyl)ferrocene (1). Treatment of the chlorides with Li[AlH4] afforded the 1,1′-bis(hydridostannyl)-subsituted ferrocenes Fe(C5H4-SnMe2H)2 (5), Fe(C5H4-SnMeH2)2 (6) and Fe(C5H4-SnH3)2 (7), respectively. All complexes 1-7 were studied by 1H-, 13C-, and 119Sn-NMR spectroscopy with 1D and 2D techniques. The compounds 1-4 were investigated by temperature-dependent 119Sn- and 57Fe-Mössbauer spectroscopy. The electrochemistry of 1-5 gave evidence of reversible one-electron oxidation processes. The molecular structure of 1,1′-bis(trichlorostannyl)ferrocene (4) was determined by X-ray structural analysis, and there was no indication of intra- or intermolecular Sn···Cl···Sn interactions. This direct structural information proved to be consistent with both the Mössbauer and the solution NMR spectroscopic data.
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  • 93
    ISSN: 1434-1948
    Keywords: Copper ; Deprotonated amide ligands ; Oxime ligands ; Redox chemistry ; High valent metal ions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copper(II) and copper(III) complexes were prepared with two novel ligands, N,N′-bis(2-(1-hydroxyimino-2-methyl-1-phenyl)propyl)dimethylmalondiamide (H4mal55) and N,N′ bis(-(1-hydroxyiminoethyl)phenyl)dimethylmalondiamide (H4mal66), both of which contain two amide and two oxime functionalities as potential ligand donor groups. The two copper(II) complexes (NEt4)[Cu(Hmal55)] (1) and (NEt4)[Cu(Hmal66)] (2) can be reversibly oxidized in acetonitrile at a redox potential of -0.120 and -0.075 V vs. the Fc/Fc+ redox couple, respectively. While the quantitative electrolysis of 1 results in the preparation of the oxidized complex [Cu(Hmal55)] (3), which is sufficiently stable to be isolated, isolation of the oxidation product of 2 was not attempted because of its long-term instability. The properties of the complexes were investigated by means of various spectroscopic methods (UV-vis, ESR, NMR, and IR spectroscopy) and by X-ray structure analysis. The structure determinations and the spectroscopic investigations of the complexes reveal a square-planar CuN4coordination environment for each complex in the solid state and in acetonitrile solution. In both the oxidized and reduced oxidation states of the complexes, the coordinated ligands remain triply deprotonated with a hydrogen atom bridging both oxime oxygen atoms. The ligands can therefore be regarded as pseudo-macrocyclic. The characterization of the oxidation products clearly identifies the electron-transfer reaction as being metal-centered. For the first time, the structure of a copper(III) complex with a ligand containing oximes as donor groups was determined. The redox potentials of the copper complexes are compared to related CuIII/CuII redox couples.
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  • 94
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 173-178 
    ISSN: 1434-1948
    Keywords: P Ligands ; N Ligands ; Copper ; Zinc ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiation of triphenyl(trimethylsilylimino)phosphorane Ph3P=NSiMe3 with MeLi gives the ortho-metallated species [Li(o-C6H4PPh2NSiMe3)]2·Et2O (1), which exhibits all the requirements of an organometallic ligand capable of side-arm donation. The deprotonated ortho-phenyl carbon atom gives access to metal-carbon σ bonds in transmetallation reactions, while the Ph2P=NSiMe3 moiety can donate to the same metal center through the imine nitrogen atom. In transmetallation reactions with CuBr, the dimeric organocopper complex [Cu(o-C6H4PPh2NSiMe3)]2 (2) is obtained, while application of ZnCl2 yields the monomeric zinc complex [Zn(o-C6H4PPh2NSiMe3)2] (3). Reaction with CuCl2 gives access to the new diiminophosphorane (o-C6H4PPh2NSiMe3)2 (4) through oxidative coupling at the ortho positions. In all the metal complexes, the Ph2P=NSiMe3 residue acts as a side-arm donating group through the nitrogen atom. The intermolecular N→Cu donor bond in 2 is as short as copper-amide bonds, while the N→Zn bond lengths in 3 are in the region normally found for donor bonds. Compound 4 is a molecule, possessing two Ph2P=NSiMe3 moieties bridged by a biphenylene group.
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  • 95
    ISSN: 1434-1948
    Keywords: Organometallics ; Aluminum ; Tin ; Metal-metal exchange ; Electrophilic reagents ; Lewis acid-base complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With the goals of preparing novel carbaluminating reagents and mono- and bidentate organoaluminum Lewis acids, the scope and limitations of synthesizing the requisite organoalanes by the aluminum-tin exchange between an aluminum halide and the appropriate organostannane have been examined in detail. The interactions of such tin precursors as 1,2-bis(trimethylstannyl)ethyne, allyltri-n-butyltin, benzyltrimethyltin, and 1,2-bis(trimethylstannyl)benzene and various aluminum chlorides of the type, RnAlCl3-n (R = Me, Et), gave selective aluminum-tin exchange at the sp- or sp2-hybridized carbon-tin bond and produced such organoalanes as allyl(methyl)aluminum chloride, benzylaluminum dichloride, 1,2-bis(diethylalumino)ethyne, 1,2-bis(dimethylalumino)benzene, 1,2-bis[chloro(methyl)alumino]benzene, and 1,2-bis(dichloroalumino)benzene in high yield. A complicating factor was the tendency of the R3SnCl by-product to complex with the resulting organoalane. In some cases, exemplified by allyl(methyl)aluminum chloride, such complexation did not interfere with the carbaluminating action of the reagent; in other cases, exemplified by 1,2-bis[chloro(methyl)alumino]benzene, the R3SnCl could be removed by means of π-bases and reduced pressures; and in still other structures, as with 1,2-bis(dichloroalumino)benzene, the tin chloride could not be dislodged at moderate temperatures. The structure and bonding in such tin halide-aluminum halide complexes in solution were investigated with the 1:1 adducts of AlCl3 with Me3SnCl and with nBu3SnCl, respectively, by means of multinuclear NMR spectroscopy. Furthermore, an XRD of the solid complex, Me3SnCl · AlCl3, was carried out. Such complexes were shown to consist of 1:1 ion pairs of the type [R3Sn+][AlCl4-] in dilute solution and of a chiral polymeric helix in the solid state wherein planar Me3Sn+ units are linked to each other via bridging tetrachloroaluminate anions, Cl-(AlCl2)-Cl-. Treatment of such complexes with either benzyltriethylammonium chloride (one or two equivalents) or tetramethylphosphonium chloride leads to the displacement of Me3SnCl and the formation of the expected ionic complexes. Finally, the importance of such novel reagents and chelating Lewis acids to organic synthesis and olefin polymerization is discussed and elucidated.
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  • 96
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 179-187 
    ISSN: 1434-1948
    Keywords: Hexadentate N/S-ligand ; Dinuclear complexes ; Nickel ; Redox chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A discrete dinickel complex with a central N2NiII(μ2-SR)2NiIIN2 core has been synthesized and investigated in the context of ligand binding and oxidation state changes. Reaction of the hexadentate amine-thiolate ligand N,N′-bis-[2-thio-3-aminomethyl-5-tert-butylbenzyl]propane-1,3-diamine (8) with Ni(ClO4)2 · 6 H2O in methanol affords [NiII28][ClO4]2 · 3 CH3OH (9), the structure of which has been determined by X-ray crystallography. Complex 9 contains a central N2Ni(μ2-SR)2NiN2 core with two approximately planar cis-N2S2Ni coordination polyhedra bridged at the thiolate sulfur atoms. The cis-N2S2Ni units differ in that one nickel atom forms a six-membered chelate ring with the two secondary amine nitrogen atoms of 8 whereas the other nickel atom is bound to the remaining primary nitrogen atoms. Complex 9 binds a variety of substrates. Binding of anions to the N2Ni(μ2-SR)2NiN2 core in 9 occurs selectively at the Ni atom bound to the secondary nitrogen atoms because of a slightly weaker ligand-field strength. This is demonstrated by X-ray structure determination of the isothiocyanate complex [NiII28(NCS)2] · MeOH (10) formed by the reaction of 9 with 2 equiv. of KSCN in methanol. Complex 10 is the first example of a complex with adjacent octahedral cis-N4S2Ni and planar cis-N2S2Ni sites. The overall dinuclear structure of the parent complex 9 is retained in 10, except for trans-axially bound isothiocyanate ions at Ni(1) and an as yet unexplained inversion of configuration at both secondary amine nitrogen atoms. In DMF solution both complexes undergo two successive reductions at potentials of -0.95 V and -1.53 V vs SCE, assigned to the formation of mixed-valent [NiINiII8]1+ and [NiI28]0 species, respectively. The similar electrochemical properties of 9 and 10 suggest that the trans-axially bound isothiocyanate ions in 10 are replaced by DMF molecules in DMF solution. Upon reduction, these solvent molecules decoordinate to produce an unsolvated [NiINiII8]1+ species with two planar N2S2Ni units.
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  • 97
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 195-200 
    ISSN: 1434-1948
    Keywords: Calixarene ; Carboranes ; Host-guest chemistry ; Non-classical hydrogen bonding ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of globular 1,2-dicarbadodecaborane(12) (o-carborane) 1 with the bowl-shaped container molecule calix[5]arene 2 affords either the crystalline 1:1 or 1:2 host-guest complexes (o-carborane)(calix[5]arene)(CH2Cl2) 3, (o-carborane)(calix[5]arene)(toluene) 4 and (o-carborane)(calix[5]arene)2(CH2Cl2)0.55. The three complexes show a remarkable range of different supramolecular interplay beyond the common structural unit, a ball-and-socket nano-structure or supermolecule [(o-carborane)∩(calix[5]arene)]. Complex 3 forms dimeric [(o-carborane)∩(calix[5]arene)]2 units, and 5 has an additional edge on interaction between the supermolecule and a secondary calix[5]arene host.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 189-193 
    ISSN: 1434-1948
    Keywords: Mixed-valent compounds ; Nickel ; N2Se ligand ; Cyclic voltammetry ; EPR spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two dinuclear nickel amine-selenolate complexes of the tridentate amine-selenolate ligand, 4-tert-butyl-2,6-di(aminomethyl)selenophenol (1b), have been synthesized and their properties characterized. The green complex [NiII2(1b)3]Cl (4a) is readily prepared from 1b, NiCl2 · 6 H2O, and NaOMe in methanol or by reaction of coordinatively unsaturated [NiII2(1b)2][BPh4]2 (2b) with another one equivalent of 1b in the presence of triethylamine. The face-sharing, bioctahedral structure of 4a is derived from UV/Vis spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction of its oxidation product, [NiIINiIII(1b)3]2+. The dication was prepared by air-oxidation of 4a in MeOH and isolated as the dark-brown BPh4- salt, [NiIINiIII(1b)3][BPh4]2 · CH3OH (4b). Mixed-valent complex 4b consists of a dinuclear, face-sharing bioctahedral dication with a central N3NiII(μ2-SeR)3NiIIIN3 core and well-separated tetraphenylborate anions. Distortions from D3h symmetry suggest that 4b is a trapped-valence compound in the solid-state. On the CV time scale complex 4a undergoes two reversible one-electron oxidations at E11/2 = -0.15 and at E21/2 = +0.29 V vs SCE, affording 4b and the thermally not stable trication [NiIII2(1b)3]3+, respectively. The EPR spectrum of a powdered sample of 4b reveals an S = 3/2 ground state of the mixed-valent NiIINiIII complex.
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  • 99
    ISSN: 1434-1948
    Keywords: Amides ; Chirality ; Clusters ; Copper ; Sodium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new heterometallic sodium(I)-copper(II) compound Na4Cu2 (2) · 10.5 H2O (3), where H8[2] stands for N,N′,N′′,N′′′-methanetetrayltetrakismethylenetetrakis(oxamic acid), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction. The structure of 3 consists of cationic [Cu2(η4:η4-2)]4- dinuclear units, coordinated sodium cations, and water molecules. In the crystal, the dinuclear copper entities are joined through discrete aggregates of eight sodium atoms linked by oxamato and water bridges, leading to a three-dimensional polymeric network.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 201-207 
    ISSN: 1434-1948
    Keywords: Aluminium ; Gallium ; Low-valent compounds ; Insertion reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 reacted with trimethylsilyldiazomethane and bis(trimethylsilyl)diazomethane at room temperature by the insertion of the terminal nitrogen atoms into its aluminium-aluminium bond. As shown by a crystal structure determination, one of the aluminium atoms of each product enhanced its coordination number to four by the interaction with the central nitrogen atom of the C=N-N group, which results in the formation of a three-membered AlN2 heterocycle bearing an exocyclic N=C double bond. The reactions of the corresponding gallium compound (2) containing a gallium-gallium single bond needed more drastic conditions. Mixtures of many unknown products were formed, and only on treatment with trimethylsilyldiazomethane two compounds could be isolated after repeated recrystallization in yields below 10%, which were characterized by crystal structure determinations. One was identified as the trimeric dialkylgallium cyanide (8) with a nine-membered Ga3C3N3 heterocycle, and the other one (9) has a dialkylgallium fragment coordinated by both terminal nitrogen atoms of the chelating ligand NH2-N=C(SiMe3)-NH-. Due to the NMR spectroscopic characterization, 8 seems to be tetrameric in solution with an asymmetric structure containing four different gallium atoms. With this unusual structure, the IR spectrum of tetrameric dimethylgallium cyanide could now completely be interpreted, which was published more than 20 years ago.
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