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  • 1
    Electronic Resource
    Electronic Resource
    A Novel Route to Formaldehyde and Thioformaldehyde Rhodium Complexes (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1605-1617 
    Details
    ISSN: 1434-1948
    Keywords: Rhodium ; Carbenoide metal complexes ; Formaldehyde complexes ; Thioformaldehyde complexes ; Cyclopentadienyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The acetoxymethyl rhodium compounds [(η5-C5R5)Rh(CH2OAc)(L)I] (4, 13-16) which were prepared from the chloromethyl derivatives [(η5-C5R5)Rh(CH2Cl)(L)I] and sodium acetate in benzene/acetic acid as solvent, reacted with AgPF6 to give the chelate complexes [(η5-C5R5)Rh{ĸ2-C,O-CH2OC(Me)O}(L)]PF6 (19-23) in excellent yields. Treatment of these complexes with KOH in methanol led to the elimination of the acetyl group and to the formation of the formaldehyde compounds [(η5-C5R5)Rh(η2-CH2O)(L)] (24-27). The related thioformaldehyde complexes [(η5-C5Me5)Rh(η2-CH2S)(L)] (46, 47) and [(η5-C5H5)Rh(η2-CH2S)(PMe3)] (50) were obtained on a similar route. Studies on the reactivity of the formaldehyde derivatives revealed that the Rh-CH2O bond is rather labile and the CH2O ligand easily converted to a CO group.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Iminoacylcobalt Compounds as Starting Materials for the Synthesis of Alkynylcobalt Halfsandwiches and CobaltaheterocyclesDedicated to Professor Günter Schmid on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 565-570 
    Details
    ISSN: 0009-2940
    Keywords: Cobalt ; Cycloadditions ; Heterocycles ; Alkynyl complexes ; Cyclopentadienyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The iminoacylcobalt compound [C5H5Co(C(CH3)=NCH3)(PMe2Ph)] (3) reacts with propargylic acid ester HC=CCO2R (R = Me, Et) to give the alkynylcobalt halfsandwich-type complexes [C5H5Co(C(CH3)=NHCH3)(C=CCO2R)-(PMe2Ph)]I (5, 6). With HC=CCO2Me as the substrate, besides 6 (R = Me) the five-membered cobaltaheterocycle [C5H5Co{K2(N, C)-N(CH3)C(CH3)CHC(CO2Me)}(PMe2Ph)]I (7) is also obtained. The reactions of 3 and the analogous benzyl derivative 4 with terminal alkynes HC=CR' (R' = CH2OH, CMe2OH, [CH2]2OH, CH2OMe, H, Me, nBu, Ph) afford exclusively the heterocyclic complexes [C5H5Co(K2(N,C)-N(R)C(CH3CHCR')(PMe2Ph)]I (R = CH3, CH2Ph) (8-18) in 60-70% yield. The molecular structures of 5 (R = Et) and 16 (R = Me, R' = Ph) have been determined by X-ray crystallography.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300506
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  • 3
    Electronic Resource
    Electronic Resource
    Mono- and Bicyclic Organometallic Ring Systems with Exocyclic C=C and C=S BondsDedicated to Professor Joachim Strähle on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 871-877 
    Details
    ISSN: 0009-2940
    Keywords: Cobalt ; Cyclopentadienyl complexes ; Heterocycles ; Electrophilic addition ; Insertion reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cobaltaheterocycles [C5H5Co{κ2(C,S)-C(=CH2)-N(R)C(=S)S](PMe2Ph)] (5-7), which contain both an exocyclic C=C and C=S bond, were prepared from the iminoacylcobalt compounds [C5H5Co(C(CH3)=NCH} (PMe2Ph)]I (2-4) on treatment with either CS2/NaOCH3 or K[S2CNMe2], respectively. While protonation of 5 (R = CH3) and 7 (R = CH2Ph) with HBF4 occurs at the exocyclic C=CH2 bond to give cations containing a CoC(CH3)N(R)C(=S)S ring, the methylation of 5 and 7 with [OMe3]BF4 takes place at the exocyclic C=S bond and generates five-membered heterocycles heterocycles with an SCH4 substituent. The reaction of 5-7 with S8 leads to the elimination of the phosphane ligand and affords the bicyclic dithiolenecobalt complexes 14 - 16 in moderate to good yields. On treatment of 5-7 with C2(CO2R′)2 (R′ = Me,Et), an insertion of the alkyne into the C=CH2 bond occurs and five-membered ring systems 19-22 with an unsaturated exocyclic =C(CO2R′)-C(CO2R′)=CH2 group are formed. As in the case of 5 and 7, protonation and methylation reactions of 19 also take place at different sites leading to cations with either a delocalized CoCN or NCS unit.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300710
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