Aromaten(phosphan)metall-Komplexe, III. Die Metall-Basen C6H6M(PMe3)C2H3R und ihre korrespondierenden Säuren [C6H6MH(PMe3)C2H3R]+

作者: Rainer Werner , Helmut Werner

DOI: 10.1002/CBER.19831160605

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摘要: Die Komplexe C6H6M(PMe3)C2H3R [4: M Ru, R H; 5, 6: Os, H, CH3] werden durch Reduktion von [C6H6MX(PMe3)C2H3R]PF6 (1–3) mit NaC10H8 synthetisiert. Sie reagieren Sauren zu den Hydrido(olefin)metall-Kationen [C6H6MH(PMe3)C2H3R]+, die als BF4- bzw. PF6-Salze (7–9) isoliert werden. Fur 7 (M Ru) liegt in Losung ein Gleichgewicht zwischen dem (Ethylen)hydrido- und Ethylmetall-Komplex vor. Bei Umsetzungen 4–6 CH3I/NH4PF6 entstehen Verbindungen [C6H6MCH3(PMe3)C2H3R]PF6 (10–12). Hydrido(olefin)-Komplexe 7–9 Nal unter Insertion Alkylmetall-Verbindungen C6H6MC2H4R(PMe3)I (13, 15, 16). Reaktionen der 10–12 NaI ergeben dagegen Verdrangung des Olefins C6H6MCH3(PMe3)I (20, 21). Einwirkung PMe3 auf Kationen [C6H6MR′(PMe3)C2H3R]+ fuhrt entweder Insertion, Substitution oder Addition Phosphans an das koordinierte Olefin. Arene(phosphane)metal Complexes, III, The Metal Bases C6H6M(PMe3C2H3R and Their Corresponding Acids [C6H6MH(PMe3)C2H3R]+ The complexes are prepared by the reduction of with NaC10H8. They react acids to form hydrido(olefin)metal cations [C6H6MH (PMe3)C2H3R]+, which isolated as BF4 or PF6 salts (7–9). For Ru), solution there is equilibrium between (ethylene)hydrido ethylmetal complex. On reaction compounds (10–12) obtained. hydrido(olefin) insertion give alkylmetal reactions yield 21) olefin displacement. treating PMe3, either insertion, substitution, addition phosphane coordinated observed.

参考文章(15)
Paul S. Pregosin, Roland W. Kunz, 31P and 13C NMR of Transition Metal Phosphine Complexes ,(1979)
H. Werner, R. Werner, Basic metals : XXIII. Synthesis and reactivity of Lewis-base osmium(0) complexes Journal of Organometallic Chemistry. ,vol. 194, ,(1980) , 10.1016/S0022-328X(00)90347-4
Duward F. Shriver, Transition metal basicity Accounts of Chemical Research. ,vol. 3, pp. 231- 238 ,(1970) , 10.1021/AR50031A004
Richard B. Pardy, Michael J. Taylor, Edwin C. Constable, John D. Mersh, Jeremy N.M. Sanders, The protonation of Co(C5Me4Et)(C2H4)2 Journal of Organometallic Chemistry. ,vol. 231, ,(1982) , 10.1016/S0022-328X(00)81960-9
Helmut Werner, Rainer Feser, Basische metalle : XXXVI. Die synthese stabiler hydrido(olefin)rhodium-komplexe und von[C5H5Rh(PMe3)(η3-CH3CHC6H5)]PF6 Journal of Organometallic Chemistry. ,vol. 232, pp. 351- 370 ,(1982) , 10.1016/S0022-328X(82)80029-6