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DOI: 10.1039/A903844B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3047-3052

Rhodium(III)-mediated oxime–nitrile coupling giving chelated iminoacylated species[hair space]†

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Vadim Yu. Kukushkin, Igor V. Ilichev, Gabriele Wagner, João J. R. Fraústo da Silva and Armando J. L. Pombeiro

Abstract

Treatment of the acetonitrile complex mer-[RhCl3(MeCN)3] with cyclopentanone oxime (C4H8)C[double bond, length half m-dash]NOH resulted in the formation of two rhodium(III) products that contain newly formed chelated iminoacyl ligands, i.e. [RhCl3{NH[double bond, length half m-dash]C(Me)ON[double bond, length half m-dash]C(C4H8)}{HON[double bond, length half m-dash]C(C4H8)}] and [RhCl2{NH[double bond, length half m-dash]C(Me)ON[double bond, length half m-dash]C(C4H8)}2]Cl·1.5H2O. Only one iminoacylated product, i.e. the rhodium(III) complex [RhCl2{NH[double bond, length half m-dash]C(Ph)ON[double bond, length half m-dash]C(C4H8)}2]Cl·H2O·EtOH, has been isolated in the reaction between the oxime and the benzonitrile complex mer-[RhCl3(PhCN)3] in ethanol. A formally reverse reaction between [RhCl3{HON[double bond, length half m-dash]C(C4H8)}3], prepared on treatment of RhCl3·4H2O with the oxime in EtOH, and free organonitrile has also been carried out. All products were characterized by elemental analyses (C, H, N, Cl, Rh), FAB+-MS, IR, 1H and 13C-{1H} NMR spectroscopies. X-Ray single-crystal analyses were performed for [RhCl3{NH[double bond, length half m-dash]C(Me)ON[double bond, length half m-dash]C(C4H8)}{HON[double bond, length half m-dash]C(C4H8)}], [RhCl2{NH[double bond, length half m-dash]C(Me)ON[double bond, length half m-dash]C(C4H8)}2]Cl·1.5H2O, [RhCl2{NH[double bond, length half m-dash]C(Ph)ON[double bond, length half m-dash]C(C4H8)}2]Cl·H2O·2EtOH and mer-[RhCl3{HON[double bond, length half m-dash]C(C4H8)}3].

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