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Interaction of rhodium(i) bisphosphine complexes with semicarbazones to give orthometallated rhodium(iii) complexes

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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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Authors and Affiliations

  1. Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1, Canada

    M. B. Ezhova, B. O. Patrick & B. R. James

  2. Air Products & Chemical Inc., Allentown, PA, 18195-1501, USA

    M. E. Ford & F. J. Waller

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Ezhova, M.B., Patrick, B.O., James, B.R. et al. Interaction of rhodium(i) bisphosphine complexes with semicarbazones to give orthometallated rhodium(iii) complexes. Russian Chemical Bulletin 52, 2707–2714 (2003). https://doi.org/10.1023/B:RUCB.0000019890.55972.90

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  • DOI: https://doi.org/10.1023/B:RUCB.0000019890.55972.90

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