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  • Inorganic Chemistry  (4)
  • 1-[1,7-Dicarba-closo-dodecaboran(12)-1-yl]aldoses  (1)
  • Bis(cyclopentadienyl)methane dianion as bridging ligand  (1)
  • 1990-1994  (5)
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  • 1
    Electronic Resource
    Electronic Resource
    1,6-Heptadien-Nickel(0)-Komplexe: rac/meso-(μ-η2,η2-C7{Ni( η2,η2-C7H12)}2 und L-Ni(η2,η2-C7H12) (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2667-2675 
    Details
    ISSN: 0009-2940
    Keywords: Alkene ligands ; 1,6-Dienes ; Nickel complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,6-Heptadiene Nickel(0) Complexes:rac/meso-(μ-η2,η2-C7{Ni(η 2,η2-C7H12)}2 und L-Ni(η2,η2-C7H12)Ni(CDT) dissolves in 1,6-heptadiene with displacement of the CDT to yield the dinuclear homoleptic product rac/meso-(μ- η2,η2-C7H12){Ni(η2, η2-C7H12)}2 (1) as a mixture of stereoisomers, in which the nickel atoms are trigonal-planar coordinated by a chelating 1,6-diene ligand and one C=C bond of a bridging diene ligand. The stereoisomers differ in the coordination mode of the bridging diene ligand.-The bridging diene ligand in 1 can be displaced by various donor/acceptor molecules. In pentane, 1 reacts with ethene to yield a solution of mononuclear (C2H4)Ni(η2,η2-C7H12) (2). With alkynes unstable complexes are formed of which the anticipated ethyne derivative (C2H2)Ni(η2,η2-C7H12) (3) decomposes explosively at - 100°C. With isocyanides, methylenephosphoranes, methyllithium, amines, pyridines, phosphanes, and phosphites (i.e. C, N, P donors) crystalline complexes of type L-Ni(η2.η2 C7H12) have been obtained, of which the derivatives with L=tBuN = C 4, Me3PCH2 5, LiCH3 6, C7H13N7, C5H5N 8, Me3P 9, iPr3P 10, Ph3P 11, (PhO)3P 12 are characterized here. For 11 the crystal structure has been determined.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911241206
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  • 2
    Electronic Resource
    Electronic Resource
    1-[1,7-dicarba-closo-dodecaboran(12)-1-yl]aldoses: Novel Boron Neutron Capture Candidates (1993)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1993 (1993), S. 831-835 
    Details
    ISSN: 0170-2041
    Keywords: Boron neutron capture therapy ; 1-[1,7-Dicarba-closo-dodecaboran(12)-1-yl]aldoses ; 1-[m-Carboran-1-yl]aldoses ; Boranes ; Carbohydrates ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolithiated 1,7-dicarba-closo-dodecaborane(12) reacts with O-isopropylidene derivatives of D-erythrono-1,4-lactone (1), L-mannono-1,4-lactone (3) and with tetra-O-trimethylsilylated D-glucono-1,5-lactone (2) and D-gulono-1,4-lactone (4) to give the title compounds after deprotection. An X-ray structure analysis of the protected L-mannofuranose carborane derivative 9 reveals that the more stable anomer has the β-L configuration.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.1993199301131
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  • 3
    Electronic Resource
    Electronic Resource
    Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe, IV. Synthese, Struktur und Reaktivität von Zweikernkomplexen des Rhodiums und Iridiums in der Oxidationsstufe +I und +III mit dem Bis(cyclopentadienyl)methan-Dianion als Brückenliganden (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 337-346 
    Details
    ISSN: 0009-2940
    Keywords: Dinuclear rhodium and iridium complexes ; Bis(cyclopentadienyl)methane dianion as bridging ligand ; Substitution and bridge-splitting reactions ; Rhodium complexes ; Iridium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(cyclopentadienyl)methane-Bridged Dinuclear Complexes, IV[1].  -  Synthesis, Structure, and Reactivity of Dinuclear Rhodium and Iridium Complexes in the Oxidation State +I and +III with the Bis(cyclopentadienyl)methane Dianion as Bridging LigandThe rhodium compounds [CH2(C5H4)2][Rh(L)(C2H4)]2 (2, 4) were prepared from [RhCl(L)(C2H4)]2 (1, 3) and CH2(C5H4)2Li2 in 92 and 73% yield, respectively. The reaction of 4 with Cl2, Br2, and I2 led to the almost quantitative formation of the dihalogeno derivatives [CH2(C5H4)2][RhX2(PiPr3)]2 (6-8), which on treatment with excess NaBH4 and methanol gave the dihydride [CH2(C5H4)2][RhH2(PiPr3)]2 (10). From [RhCl(C8H14)2]2 (12), PiPr3, and CH2(C5H5)2 the chloro(hydrido)rhodium complex [CH2(C5H4)2][RhH(Cl)(PiPr3)]2 (13) was obtained. Protonation of 10 with CF3CO2H in the presence of NH4PF6 gave the PF6 salt of the hydrido-bridged cation {[CH2(C5H4)2]-[RhH(PiPr3)]2(μ-H)}+ (14) of which the crystal structure was determined. In solution, fluxional behavior of the cation was observed. The dimethyl compound [CH2(C5H4)2][Rh(CH3)2-(PiPr3)]2 (17), prepared from 6, 7, or 8 and LiCH3 or CH3MgI in 80% yield, reacted with CF3CO2H at  -  78° C to give the tri-fluoroacetato derivative 18; this on treatment with P(OMe)3 and dmpe formed the dicationic complexes 19 and 20, respectively. The dinuclear iridium compounds [CH2(C5H4)2]-[Ir(olefin)2]2 (26, 27) and [CH2(C5H4)2][Ir(C8H12)]2 (28) were prepared from [IrCl(L)2]2 (23-25) and CH2(C5H4)2Li2 and used for the synthesis of {[CH2(C5H4)2][IrX2]2}n (29, 30). Compounds 29 and 30 served as starting materials for the preparation of the dinuclear derivatives [CH2(C5H4)2][IrX2(L)]2 (31-34) and {[CH2(C5H4)2][IrBr2]2(μ-dipy)} (35) and finally also for the dihydrido complex [CH2(C5H4)2][IrH2(PiPr3)]2 (36).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250210
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  • 4
    Electronic Resource
    Electronic Resource
    Charge-Transfer-Komplexe von Metalldithiolenen, XIII. cis-trans-Photoisomerisierbare Viologene als redoxaktive Akzeptoren  - Synthese und elektrische LeitfähigkeitHerrn Prof. Dr. C. Krüger zum 60. Geburtstag gewidmet. (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 287-294 
    Details
    ISSN: 0009-2940
    Keywords: Metal dithiolenes ; Dipyridinioethylene dihalides ; Charge-Transfer complexes ; Electrical conductivity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Charge-Transfer Complexes of Metal Dithiolenes, XIII[1]. - cis-trans-Photoisomerisable Viologens as Redoxactive Acceptors  -  Synthesis and Electrical ConductivityIon Pair Charge-Transfer (IPCT) complexes of the type [A2+[ML2]2-} (1a-f to 4a-f) are synthesized from dianionic metal dithiolenes [M = Ni, Zn, L = cis-1,2-dicyano-1,2-ethene-dithiolate (mnt2-), 2-thioxo-1,3-dithiol-4,5-dithiolate (dmit2-)] and dicationic viologens [A2+ = 4,4′-(1,2-ethenediyl)bis(1-alkylpyridinium)]. The acceptors can exist as cis/trans isomers and may have coordinating properties in the case of 1-cyanoalkyl groups. The IPCT bands are in the range of 500 to 1200 nm and their energy follows the Hush-Marcus relation. For the nickel complexes the reorganization energy amounts to 73, for the zinc compounds to 115 kJ/mol. As shown by X-ray analysis of {A2+[Ni(mnt)2]2-} (2d), A2+ = trans-4,4′-(1,2-ethenediyl)-bis[1-(3-cyanopropyl)pyridinium], the structure consists of stacks of alternating donors and acceptors with a typical plane-to-plane distance of 350 pm. There is no interaction between the cyano group of the acceptor and the nickel atom of the donor. The electrical conductivities of the nickel compounds are in the range of 5 · 10-6 to 3 · 10-11 Ω-1 cm-1, and the corresponding activation energies vary from 0.24 to 0.61 eV. For the dmit complexes these values agree well with the free activation enthalpy of the electron transfer reaction A2+ + [ML2]2- → A+ + [ML2]- calculated from the Hush-Marcus model. This suggests that charge carrier generation occurs by electron transfer. When a trans acceptor is replaced by its cis isomer in [A2+[NiL2]2-}, conductivity changes from 5 · 10-7 to 5 · 10-6 Ω-1 cm-1 and the activation energy from 0.43 to 0.24 eV, when L - dmit2- but stays at about 1 · 10-8 Ω-1 cm-1 for L = mnt2-.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270203
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  • 5
    Electronic Resource
    Electronic Resource
    Reduktion von (Cyclobutadien)(cyclopentadienyl)- und (1,5-Cyclooctadien)- (cyclopentadienyl)nickel-Kationen (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 227-237 
    Details
    ISSN: 0009-2940
    Keywords: Nickel sandwich complex / Voltammetry, cyclic / Electrochemistry / Reductive dimerization / ESR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reduction of (Cyclobutadiene)(cyclopentadienyl)- and (1,5-Cyclooctadiene)(cyclopentadienyl)nickel CationsCyclic voltammetry of the four cationic Ni sandwich complexes [Ni(C5R5)(C4R4')]+ (2: R = H, R' = Ph; 3: R = H, R' = Me; 4; R = Me, R' = Ph; 5: R = R' = Me) shows reversible one-electron reductions for the phenyl derivatives 2 and 4 and a peak pattern characteristic of reductive dimerization/oxidative monomerization for the methyl derivatives 3 and 5. The product of the reduction of 3 was isolated and characterized analytically and by an X-ray structure determination as the dimer 6 of 3, linked through cyclobutenyl rings, the first example for a dimerization of an electron-rich sandwich complex at a substituted C atom. EPR spectra of the neutral complexes 2 and 4 are compared to those of (1,5-cyclooctadiene)(cyclopentadienyl)nickel (7) and are interpreted in terms of a substantial static Jahn-Teller distortion.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230202
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