Abstract
Interaction of the cis-[Rh(PR3)2(Solv)2]PF6 complexes (R = Ar or R3 = 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, 31P{1H} and 1H 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 η2-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.
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