| Title | Interaction of rhodium(I) bisphosphine complexes with semicarbazones to give orthometallated rhodium(III) complexes |
| Publication Type | Journal Article |
| Year of Publication | 2003 |
| Authors | Ezhova, MB, Patrick, BO, James, BR, Ford, ME, Waller, EJ |
| Journal | Russian Chemical Bulletin |
| Volume | 52 |
| Pagination | 2707-2714 |
| Date Published | Dec |
| Type of Article | Proceedings Paper |
| ISBN Number | 1066-5285 |
| 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 |
| 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’)C=N-N(H)CONH2}]PF6 (R’ = 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’ = 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. |
| URL | <Go to ISI>://000220631200019 |
