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Issue 9, 2002
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Platinum(IV)-mediated hydrolysis of nitriles giving metal-bound iminols

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Abstract

The platinum(IV) complexes cis/trans-[PtCl4(MeCN)2] and trans-[PtCl4(EtCN)2] react smoothly and under mild conditions with water, contained in non-dried commercial acetone, to afford trans-[PtCl4{N(H)[double bond, length as m-dash]C(OH)Me}2]·Me2CO (1) or trans-[PtCl4{N(H)[double bond, length as m-dash]C(OH)Et}2] (2); no hydroxide is required, in contrast to relevant platinum(II) systems, to furnish the metal-bound carboxamides which are stable in the iminol form. In non-dried acetone, reaction between trans-[PtCl4(EtCN)2] and MeC([double bond, length as m-dash]O)NH2 gives a mixture of 1 (derived from substitution) and 2 (derived from the hydrolysis), while in non-dried dichloromethane an isomorphic mixture of cis-[PtCl4{N(H)[double bond, length as m-dash]C(OH)Me}2] and cis-[PtCl4{N(H)[double bond, length as m-dash]C(OH)Et}2], i.e.cis-[PtCl4{Z-N(H)[double bond, length as m-dash]C(OH)Me}2]0.66·cis-[PtCl4{Z-N(H)[double bond, length as m-dash]C(OH)Et}2]0.33 (3) is obtained. Complexes 13 were characterised by elemental analyses (C, H, N), FAB+-MS, IR, 1H- and 13C{1H}-NMR spectroscopy. Complexes 2 and 3 were also characterised by 195Pt-NMR spectroscopy. Crystal structures of 2 and 3 provide the first examples of structurally characterised platinum(IV) complexes with amides in their iminol form. The equilibrium structures for the geometrical and linkage isomers of the platinum(II) complexes [PtIICl2{N(H)[double bond, length as m-dash]C(OH)Me}2] and [PtIICl2{O[double bond, length as m-dash]C(NH2)Me}2] and the platinum(IV) compounds [PtIVCl4{N(H)[double bond, length as m-dash]C(OH)Me}2] and [PtIVCl4{O[double bond, length as m-dash]C(NH2)Me}2] were calculated at the B3PW91 level of theory and the study shows that the most stable isomers for both platinum(II) and platinum(IV) complexes are the trans-(iminol)Pt forms, in accord with the experimental results.

Graphical abstract: Platinum(iv)-mediated hydrolysis of nitriles giving metal-bound iminols

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Publication details

The article was received on 13 Sep 2001, accepted on 15 Feb 2002 and first published on 27 Mar 2002


Article type: Paper
DOI: 10.1039/B108327A
Citation: J. Chem. Soc., Dalton Trans., 2002,0, 1882-1887
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    Platinum(IV)-mediated hydrolysis of nitriles giving metal-bound iminols

    K. V. Luzyanin, M. Haukka, N. A. Bokach, M. L. Kuznetsov, V. Yu. Kukushkin and A. J. L. Pombeiro, J. Chem. Soc., Dalton Trans., 2002, 0, 1882
    DOI: 10.1039/B108327A

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