Definitive examples of polyhydride complexes which do not eliminate H2 in the primary photochemical reaction. Photodissociation of PR3 from [ReH3(PR3)4] and [ReH5(PR3)3] complexes
作者： David A. Roberts , Gregory L. Geoffroy
DOI: 10.1016/S0022-328X(00)86632-2
关键词: Photodissociation 、 Chemistry 、 Phosphine 、 Photochemistry 、 Turn (biochemistry) 、 Quantum yield 、 Monomer 、 Primary (chemistry)
摘要: Irradiation of the complexes [ReH5L3] (L PMe2Ph, PMePh2, PPh3)and [ReH3(PMe2Ph)4]gives efficient loss phosphine in primary photochemical reaction, contrast to most monomeric polyhydride which lose H2 upon photolysis. The 366 nm quantum yields for range from 0.13–0.18; yield PMe2Ph [ReH3(PMe2Ph)4] is 0.4. Under an atmosphere, converted into [ReH5(PMe2Ph)3] photolysis; pentahydrides turn another equivalent give corresponding [ReH7L2] complexes. heptahydrides are themselves photosensitive and react a mixture [Re2H8L4] [Re2H6L5 dimers. Photolysis degassed solutions [ReH5L2] leads complex [ReH7L2], [ReH3L4], [Re2H8L4], [Re2H6L5]. efficientphotoelimination L [ReH3L4] discussed view reported photochemistry [ReH3(Ph2PCH2CH2PPh2)2]which loses irradiation.
elsevier.com
sci-hub.se 参考文章(8)
Jack R. Norton, Organometallic elimination mechanisms: studies on osmium alkyls and hydrides Accounts of Chemical Research. ,vol. 12, pp. 139- 145 ,(1979) , 10.1021/AR50136A005
Robert Bau, W. Eamon Carroll, Raymond G. Teller, Thomas F. Koetzle, A quadruply hydrogen-bridged metal-metal bond. The neutron diffraction analysis of octahydridotetrakis(diethylphenylphosphine)dirhenium(IV) Journal of the American Chemical Society. ,vol. 99, pp. 3872- 3874 ,(1977) , 10.1021/JA00453A074
Gregory L. Geoffroy, Photochemistry of Transition Metal Hydride Complexes Progress in Inorganic Chemistry. ,vol. 11, pp. 123- 151 ,(2007) , 10.1002/9780470166284.CH2
Mark G. Bradley, David A. Roberts, Gregory L. Geoffroy, Photogeneration of reactive [ReH(diphos)2]. Its reversible coordination of carbon dioxide and activation of aromatic carbon-hydrogen bonds Journal of the American Chemical Society. ,vol. 103, pp. 379- 384 ,(1981) , 10.1021/JA00392A023
P. G. Douglas, B L. Shaw, E. R. Wonchoba, G. W. Parshall, Tris(Dimethylphenylphosphine)Pentahydrido‐Rhenium (V) John Wiley & Sons, Inc.. pp. 64- 66 ,(2007) , 10.1002/9780470132487.CH17
J. Chatt, R. S. Coffey, Hydrido-complexes of rhenium-containing tertiary phosphines Journal of the Chemical Society A: Inorganic, Physical, Theoretical. pp. 1963- 1972 ,(1969) , 10.1039/J19690001963
A New Sensitive Chemical Actinometer. II. Potassium Ferrioxalate as a Standard Chemical Actinometer Proceedings of The Royal Society A: Mathematical, Physical and Engineering Sciences. ,vol. 235, pp. 518- 536 ,(1956) , 10.1098/RSPA.1956.0102
D Guisto, Hydrido complexes of rhenium: Synthesis and reactivity Inorganica Chimica Acta Reviews. ,vol. 6, pp. 91- 101 ,(1972) , 10.1016/0073-8085(72)80012-3