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Iridium(iii)-(hydrido)cyclometallated-imine complexes and metal-promoted hydrolytic cleavage of imines

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Abstract

The room temperature reaction of the complex cis,trans,cis-[Ir(H)2(PPh3)2(Solv)2]PF6 (Solv is a solvent) with the imine PhCH2N=CHPh in acetone generates (with loss of H2) the orthometallated complex [Ir(H){PhCH2N=CH(o-C6H4)}(PPh3)2(Me2CO)]PF6 (3) containing a five-membered cyclometallated imine moiety. In MeOH, the reaction at an imine : Ir ratio = 1 leads to the corresponding MeOH analog of 3, while with excess imine, the mixed orthometallated imine/bezylamine complex [Ir(H){PhCH2N=CH(o-C6H4)}(PPh3)2(PhCH2NH2)]PF2 (4) is formed; the source of the coordinated amine is an Ir-promoted hydrolysis of the imine, the water likely coming from imine. Complexes 3 and 4 are fully characterized by elemental analysis, 1H and 31P{1H} NMR spectroscopy, and X-ray crystal structure analysis.

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Authors and Affiliations

  1. Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, B. C, V6T 1Z1, Canada

    P. Marcazzan, B. O. Patrick & B. R. James

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  1. P. Marcazzan
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Marcazzan, P., Patrick, B.O. & James, B.R. Iridium(iii)-(hydrido)cyclometallated-imine complexes and metal-promoted hydrolytic cleavage of imines. Russian Chemical Bulletin 52, 2715–2721 (2003). https://doi.org/10.1023/B:RUCB.0000019891.73897.e4

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