@article {609, title = {Interaction of rhodium(I) bisphosphine complexes with semicarbazones to give orthometallated rhodium(III) complexes}, journal = {Russian Chemical Bulletin}, volume = {52}, number = {12}, year = {2003}, note = {ISI Document Delivery No.: 809IUTimes Cited: 7Cited Reference Count: 57International Memorial Symposium on Modern Trends in Organometallic and Catalytic Chemistry Dedicated to Mark Vol{\textquoteright}pinMAY 18-AUG 23, 2003Moscow, RUSSIA}, month = {Dec}, pages = {2707-2714}, type = {Proceedings Paper}, abstract = {Interaction of the cis-[Rh(PR3)(2)(Solv)(2)]PF6 complexes (R = Ar or R-3 = Ph2Me, Solv solvent) under Ar with semicarbazones bearing a phenyl group on the imine-C atom gives the rhodium(III)-hydrido-bis(phosphine)-orthometallated semicarbazone species [RhH(PR3)(2){(o-C6H4(R{\textquoteright})C=N-N(H)CONH2}]PF6 (R{\textquoteright} = Me or Et), which are characterized generally by elemental analysis, P-31{H-1} and H-1 NMR spectroscopy, and mass-spectrometry. The PPh3-containing complex with R{\textquoteright} = Me, structurally characterized by X-ray analysis, reveals coordination of the semicarbazone by the ortho-C atom, the imine-N atom, and the amide-carbonyl group. For a semicarbazone containing no Ph group, the rhodium(I) complex [Rh(PR3)(2)(Et(Me)C=N-N(H)CONH2)]PF6, containing the eta(2)-semicarbazone bonded via the imine-N and carbonyl, is formed. Attempts to hydrogenate the C=N moiety in the complexes or to catalytically hydrogenate the semicarbazones were unsuccessful.}, keywords = {ACTIVATION, ASYMMETRIC HYDROGENATION, BENZALDEHYDE SEMICARBAZONE, C-H, C-H BONDS, CATALYTIC-HYDROGENATION, COMPLEXES, CRYSTAL-STRUCTURE, FINE CHEMICALS, INTRAMOLECULAR ACTIVATION, molecular structure, orthometallation, phosphines, rhodium, SELECTIVE HYDROGENATION, semicarbazones, SYNTHESIS, TRANSITION-METAL-COMPLEXES, UNPRECEDENTED CHEMICAL TRANSFORMATION}, isbn = {1066-5285}, url = {://000220631200019}, author = {Ezhova, M. B. and Patrick, B. O. and James, Brian R. and Ford, M. E. and Waller, E. J.} }