Rhodium(III)-mediated oxime-nitrile coupling giving chelated iminoacylated species

摘要

Treatment of the acetonitrile complex mer-[RhCl_3(MeCn)_3] with cyclopentanone oxime (C_4H_8)C=NOH resulted in the formation of two rhodium(III) products that contain newly formed chelated iminoacyl ligands, i.e. [RhCl_3{NH=C(Me)ON=C(C_4H_8)} {HON=C(C_4H_8)}] and [RhCl_2{NH=C(Me)ON=C(C_4_8)}_2]Cl centre dot 1.5H_2O. Only one iminoacylated product, i.e. the rhodium(III) complex [RhCl_2{NH=C(Ph)ON=C(C_4H_8)}_2]Cl centre dot H_2O centre dot EtOH, has been isolated in the reaction between the oxime and the benzonitrile complex mer-[RhCl_3(PhCN)_3] in ethanol. A formally reverse reaction between [RhCl_3{HON=C(C_4H_8)]_3], prepared on treatment of RhCl_3 centre dot 4H_O with the oxime in EtOH, and free organonitrile has also been carried out. All products were characterized by elemental analyses (C, H, N, Cl, Ph), FAB~+-MS, IR, ~1H and ~(13)C-{~1H} NMR spectroscopies, X-Ray single-crystal analyses were performed for [RhCl_3{NH=C(Me)ON=C(C_4H_8)}{HON=C(C_4H_8)}], [RhCl_2{NH=C(Me)ON=C(C_4H_8)}_2]Cl centre dot 1.5H_2O, [RhCl_2{NH=C(Ph)ON=C(C_4H_8)}_2]Cl centre dot H_2O centre dot 2EtOH and mer-[RhCl_3{HON=C(C_4H_8)}_3].