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  • Inorganic Chemistry  (1,777)
  • 1995-1999  (1,777)
  • 1
    Electronic Resource
    Electronic Resource
    Masthead (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280101
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  • 2
    Electronic Resource
    Electronic Resource
    Tripodal Triamidostannates as Building Blocks in the Generation of Sn - M-Bonded Heterobimetallics (M = Fe, Ru) (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 29-34 
    Details
    ISSN: 0009-2940
    Keywords: Tripodal ligands ; Triamidostannates ; Metal-metal bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By in situ lithiation of the trifunctional amines H3CC(CH2NHSiMe3)3, PhC(CH2NHSiMe3)3, and HC{SiMe2NH(p-Tolyl)}3 and subsequent reaction with SnCl2 the corresponding triamidostannates were obtained. These were coupled with CpM(CO)2Cl (M = Fe, Ru) to yield the M - Sn-bonded heterobimetallics 9-14 of which H3CC(CH2NSiMe3)3SnFe(CO)2Cp (9) was characterized by a single-crystal X-ray structure analysis. Of the in situ-generated amidostannates only [HC{SiMe2N(p-Tolyl)}3Sn][Li(THF)3] (8) could be isolated as a uniform product and characterized analytically and spectroscopically.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280105
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  • 3
    Electronic Resource
    Electronic Resource
    The Structures of [X2Y—N—YX2]+ Cations (X = F, Cl; Y = S, Se). A Comparison of X-ray and ab Initio Studies[1] (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 35-40 
    Details
    ISSN: 0009-2940
    Keywords: Selenium-nitrogen compounds ; Sulfur-nitrogen compounds ; Calculations, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structures of cationic species of the series [X2Y—N—YX2]+ (X = F, Cl; Y = S, Se) have been computed ab initio using all electron treatments for first-row elements and sulfur and quasi-relativistic pseudopotentials for Se and Cl. Splitvalence basis sets with polarization and diffuse functions were employed. The MP2 results for the (non-isostructural!) cations [Cl2Se—N—SeCl2]+ (1: Cs) and [F2S—N—SF2]+ (2: C2v) are in excellent agreement with the experimental (X-ray) observations. Both structures represent local minima. A deeper minimum for either of the cations is represented by another C2v isomer which for crystal lattice energy reasons is stable in the isolated state only. The geometries of the hitherto unknown species [Cl2S—N—SCl2]+ (3) and [F2Se—N—SeF2]+ (4) have been assessed by ab initio HF calculations. In analogy to 2, cations 3 and 4 are predicted to prefer C2v symmetry. Therefore, 1 exhibits unusual structural features. According to strictly localized natural bond orbital analysis (NBO), the central nitrogen atoms in 1 and 2 possess two lone pairs of electrons (LP: one sp hybrid and one p orbital). The relatively short Se—N and S—N bond distances in 1 (1.741-1.760 Å) and 2 (1.551 Å) can best be attributed to LP(N)→s̰*(Y—X) negative hyperconjugation (1: Y = Se, X = Cl; 2: Y = S, X = F).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280106
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  • 4
    Electronic Resource
    Electronic Resource
    Die fördernde Rolle von Phosphinoester-Liganden bei der Synthese neutraler Carben-, Vinyliden- und Allenyliden-Ruthenium(II)-KomplexeHerrn Professor Hubert Schmidbaur zum 60. Geburtstag gewidmet. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 49-62 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium(II) complexes, octahedral ; Phosphino esters as mono- and bidentate ligands ; Fluxional behaviour ; Carbene complexes ; Vinylidene complexes ; Allenylidene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylidene Transition-Metal Complexes, XXXV[1].  -  The Supporting Role of Phosphino Ester Ligands for the Synthesis of Neutral Carbene, Vinylidene and Allenylidene Ruthenium(II) ComplexesThe reaction of [RuCl2(PPh3)3] (1) with the phosphino esters iPr2P(CH2)nCO2R (2-4) leads to complete (n = 1; R = CH3, C2H5) or partial (n = 2; R =CH3) displacement of the PPh3 ligands and formation of the octahedral ruthenium(II) complexes [RuCl2{k2(P,O)-iPr2PCH2CO2R}2] (5, 6) and [RuCl2(PPh3){k(P)-iPr2PCH2CH2CO2Me}{k2(P,O)-iPr2PCH2CH2CO2Me}] (7). Treatment of 5 with LiBr and LiI affords the dibromo- and diiodoruthenium derivatives 8 and 9. While compound 5 reacts with CO and SO2 by cleavage of one Ru - O bond to yield the 1:1 adducts [RuCl2(L){k(P)-iPr2PCH2CO2Me}{k2(P,O)-iPr2PCH2CO2Me}] (10, 11), the reaction of the dibromo derivative 8 with CO in solution gives the dicarbonyl complex [RuBr2(CO)2{k(P)-iPr2PCH2CO2Me}2](13). If CO is passed over 8 in the solid state, the corresponding monocarbonyl compound 14 is formed. The hydridoruthenium(II) complex 16, which is obtained from equimolar amounts of [RuHCl(CO)(PiPr3)2] (15) and 2, reacts with HC≡CMe by insertion to give the vinyl derivative [RuCl{E - CH=CHMe}(CO)(PiPr3){k2(P,O)-iPr2CH2CO2Me}] (17). Treatment of 5 with HC̊' (R' = H, Me, tBu, Ph) and of 6, 8, 9 with HC≡CPh affords upon photochemical activation the octahedral vinylidene complexes [RuX2-(=C=CHR){k(P)-iPr2PCH2CO2R}{k2(P,O)-iPr2PCH2CO2R}] (18-21 and 23-25) in good to excellent yield. At room temperature, these compounds (with the exception of 25) are highly fluxional in solution. From 31P-NMR measurements, the free energies of activation ΔG
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280108
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  • 5
    Electronic Resource
    Electronic Resource
    Reaktionen von R2Al—AlR2 (R = CH(SiMe3)2) mit Trimethylsilylazid  -  Insertion in die Al—Al-Bindung und Abbau zum trimeren Dialkylaluminiumazid (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 81-85 
    Details
    ISSN: 0009-2940
    Keywords: Aluminium-aluminium bond ; Insertion of trimethylsilyl azide ; Trimeric dialkylaluminium azide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of R2Al—AlR2 (R = CH(SiMe3)2) with Trimethylsilyl Azide  -  Insertion into the Al—Al Bond and Formation of a Trimeric Dialkylaluminium AzideTetrakis[bis(trimethylsilyl)methyl]dialuminium(4) (1) reacts with trimethylsilyl azide under insertion of one nitrogen atom into the Al—Al bond. As shown by NMR spectra and crystal structure the product contains three and four coordinated Al atoms due to the coordination of the α-nitrogen atom of the azide group to one of the Al atoms. An electronically delocalized N3-system is formed with a N—N bond length of 132.0 pm and a bond order of 1.5 for both N—N bonds. With an excess of trimethylsilyl azide further reaction is observed only under mild irradiation conditions with an exchange of the azide group between Si and Al and formation of Me6Si2 and the dialkylaluminium azide 3, which is better synthesized by the reaction of Me3Si—N3 with Cl—Al[CH(SiMe3)2]2. The sterically highly shielded aluminium azide 3 is a trimer in the solid state showing a non-planar 12-membered Al3N9 heterocycle with short N—N bonds (114 pm).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280112
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  • 6
    Electronic Resource
    Electronic Resource
    Selective Activation of Aromatic C - H Bonds with Lithium Atoms at 77 K (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 91-92 
    Details
    ISSN: 0009-2940
    Keywords: C - H bond activation ; Lithum atoms ; Cocondensation ; Aryllithium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of donor bases like THF lithium atoms are able to activate benzene derivatives under cryogenic reaction conditions. Only ring-metalated products and solid lithium hydride are formed selectively. The thermodynamically favored product benzyllithium or biphenyl generated by dimerization of free phenyl radicals are not found. This is one of the very few examples of metal atoms undergoing a C - H activation without further photoexcitation.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280114
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  • 7
    Electronic Resource
    Electronic Resource
    Protolysis of Tri-tert-butylazadiboriridine: Formation of a B-H-B Bridge in Unusual Coordination (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 99-103 
    Details
    ISSN: 0009-2940
    Keywords: Tri-tert-butylazadiboriridine ; (Hydroboryl)(methoxyboryl)amine ; 2,3-μ-Hydro-1,2,3-azoniadiborata-l-cyclopropenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The B—B bond of tri-tert-butylazadiboriridine [—NR—BR—BR—] (R = tBu; 1) is oxidized by MeOH to give the (hydroboryl)(methoxyboryl)amine H—BR=NR-BR(OMe) (2a). μ-2,3-Hydroazoniadiborata-1-cyclopropenes [=NR—BR(X)—μH—BR=] (3a, 3c-e) are formed by the action of the acids HX upon 1. A similar hydrogen bridge as in 3a-e is formed during the hydroboration of 1 by catecholborane, yielding 3f. A B atom is identified in the products 3a-f to be planarly coordinated by four atoms, two of which are forming a BHB three-center bond with that B atom. This is a novel bonding situation in boron chemistry. The structures of the products are deduced from 1H-, 11B-, and 13C-NMR spectra and are confirmed by X-ray structural analyses of 2a, 3a, and 3c.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280203
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  • 8
    Electronic Resource
    Electronic Resource
    Synthese und Struktur zweikerniger Kupfer(II)-Komplexe eines neuen Hexaaza-Makrocyclus mit verbrückenden Oxalat- und Acetat-Ionen (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 115-119 
    Details
    ISSN: 0009-2940
    Keywords: Polyazamacrocycles ; Dinucleating ligands ; Copper complexes ; Oxalate complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of Dinuclear Copper(II) Complexes of a Novel Hexaaza Macrocycle Containing Bridging Oxalate and Acetate IonsNon-template Schiff base [2 + 2] condensation of pyridine-2,6-dicarbaldehyde with 1,4-diamino-2-butyne yields the hexaazamacrocyclic ligand 1, which is converted to 2 by NaBH4 reduction of the imino groups. Two dinuclear copper(II) complexes of 2 containing oxalate and acetate ions, [(2)Cu2(μ-C2O4)](BPh4)2 (3) and [(2)Cu2(μ-CH3CO2)(OH2)](PF6)2.25-(NO3)0.75 (4), were characterized by X-ray crystallography. The oxalate ligand in 3 forms a (μ-η4:η4) bridge between the copper atoms. Compound 4 contains a syn-anti-bridging acetate ion. The Cu-Cu distances are 5.315 Å in 3 and 4.746 Å in 4, respectively. Oxalate can be separated from other carboxylates in aqueous solution by selective binding to the [(2)Cu2] unit and precipitation of 3.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280205
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  • 9
    Electronic Resource
    Electronic Resource
    Synthesis, X-Ray Crystal Structure and Magnetic Characterization of the First “Ni3S4N3” Nickel Thiolate Cluster (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 125-129 
    Details
    ISSN: 0009-2940
    Keywords: Nickel cluster ; Nickel thiolate ; Hydrogenase ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tridentate N,O,S-ligand (RS)-2-[(2-mercapto-1-methylamino)ethyl]phenol (rac-1) was prepared from ortho-hydroxy-chloroacetophenone in three steps. When this ligand was treated with nickel(II) acetate, the novel “Ni3S4N3” cluster rac-3 was obtained. The X-ray crystal structure of rac-3 unambiguously revealed the pseudo-C3 symmetric structure of this novel nickel cluster, which is made up by three nickel ions, one sulfide sulfur atom, and three homochiral ligand molecules, each contributing one thiolate sulfur atom and one amine nitrogen atom to the ligation of the metal ions. According to NMR-spectroscopic results, this highly symmetric structure is maintained in solution. The magnetic studies revealed diamagnetic behavior in the solid state, although antiferromagnetic interaction of the metal centers cannot absolutely be excluded.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280207
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  • 10
    Electronic Resource
    Electronic Resource
    Stereospecific Ligand Substitutions in Manganese(I) Complexes (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 151-155 
    Details
    ISSN: 0009-2940
    Keywords: Tripodal ligands ; Phosphane ligands ; Thioethers ; Manganese complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of fac-[(P2SPh-P,P')Mn(CO)3Br] and fac-[(PS2Ph-P,S)Mn(CO)3Br] [P2SPh: Z = PPh2; PS2Ph: Z = SPh in CH3C-(CH2PPh2)(CH2SPh)(CH2Z)] with silver hexafluorophosphate yields the η3-tripodal manganese complexes [(P2SPh-P,P',S)Mn(CO)3]PF6 (7) and [(PS2Ph-P,S,S')Mn(CO)3]PF6 (9), respectively, whereas the reaction of CH3C(CH2PPh2)2-(CH2SH) with Mn(CO)5Br gives directly [CH3C(Ph2-PCH2)2(CH2S)-P,P',S]Mn(CO)3 (11). Both ionic complexes 7 and 9 undergo stereospecifically ligand substitution upon treatment with Br-, I-, N-3, SCN- and CN- to give syn-fac-[(P2SPh-P,P')Mn(CO)3X] and syn-fac-[(PS2Ph-P,S)Mn(CO)3X] (X = Br, I, SCN, N3, CN) respectively, but the neutral complex 11 fails to undergo such a substitution reaction with these ions. However, reaction of I- with the complex [(PSMe)-P,P',S]Mn(CO)3]BF4 (20) [P2SMe = CH3C(CH2-PPh2)2(CH2SCH3)), which is obtained from the S-alkylation of 11 with (CH3)3OBF4, affords syn-fac-[(P2SMe)-P,P']Mn(CO)3I (22s) exclusively. The possible reaction mechanism of this ligand substitution is discussed.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280211
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