Reactions of imido complexes of iridium, rhodium and ruthenium

Abstract

Interactions of the known compounds Ir(η-C₅Me₅)(NR)(R = Bu^t1a or 2,6-Prⁱ₂C₆H₃1b) with 2,6-xylyl isocyanide [(xyl)NC], mesityl isocyanate and mesityl azide (mesityl = mes = C₆H₂Me₃-2,4,6) have been studied. The bridged dimers [Ir(η-C₅Me₅)(µ-NC₅H₉)]₂2 and [Ir₂(η-C₅Me₅)₂(µ-NC₆H₁₁)(µ-NHC₆H₁₁)]Cl 3 have been synthesized. Reactions of Ru(NR′)(MeC₆H₄Prⁱ-p)(R′= 2,4,6-Bu^t₃C₆H₂) with (mes)NCO and (mes)N₃ are reported. Attempts to isolate Rh(η-C₅Me₅)(NR) species failed but evidence for Rh(η-C₅Me₅)-[N(2,6-Prⁱ₂C₆H₃)N₃(mes)] was obtained in a trapping reaction in solution using (mes)N₃. The crystal structures of the compounds Ir(η-C₅Me₅)(η²-Bu^tNCNBu^t)(CNBu^t), [Ir(η-C₅H₅)(µ-NC₅H₉)]₂2, 3, [Ir₂(η-C₅Me₅)(µ-NC₆H₁₁)(µ-NHC₆H₁₁)]Cl 3, Ir(η-C₅Me₅)[N(xyl)CHN(2,6-Prⁱ₂C₆H₃)CNC₆H₃(Me)CH₂]4b, Ir(η-C₅Me₅)[N(2,6-Prⁱ₂C₆H₃)C(O)N(mes)]5, Ir(η-C₅Me₅)[N(2,6-Prⁱ₂C₆H₃)N₃(mes)]6, Ru[N(2,4,6-Bu^t₃C₆H₂)C(O)N(mes)](MeC₆H₄Prⁱ-p)8 and Ru[N(2,4,6-Bu^t₃C₆H₂)N₃(mes)](MeC₆H₄Prⁱ-p)9 have been determined. A reaction mechanism for the formation of 4b is given.