Formation of N-imidoylimidatoruthenium(II) complexes via ruthenium-promoted hydration of nitriles

Abstract

The hydridoruthenium(II) complex [RuCl(H)(CO)(PPh₃)₃]1 reacted with aromatic nitriles at 120 °C in the presence of water to give novel N-imidoylimidatoruthenium(II) complexes [RuCl(NHCRNCRO)(CO)(PPh₃)₂](R = C₆H₄Me-p2, Ph 3, or C₆H₄Me-m4). In contrast, reaction of o-toluonitrile with 1 gave a small amount of the corresponding N-imidoylimidato complex and a considerable amount of o-toluamide. When 1 was heated at 120° in a 1 : 1 mixture of an amide R ¹CONH₂ and a nitrile R²CN a cross-linked N-imidoylimidato complex [RuCl(NHCR ²NCR ¹O)(CO)(PPh₃)₂]6(R¹= Ph, R²= C₆H₄Me-p) or 7(R¹= C₆H₄Me-p, R²= Ph) was obtained. Single-crystal structure analyses of 2 and 6 have been performed.