Reactions of imido complexes of iridium, rhodium and ruthenium

Interactions of the known compounds Ir(eta-C(5)Me(5))(NR)(R = Bu(t) 1a or 2,6-(Pr2C6H3)-C-i 1b) with 2,6-xylyl isocyanide [(xyl)NC], mesityl isocyanate and mesityl azide (mesityl = mes = C(6)H(2)Me(3)-2,4,6) have been studied. The bridged dimers [Ir(eta-C(5)Me(5))(mu-NC5H9)](2) 2 and [Ir-2(eta-C(5)Me(5))(2)(mu-NC6H11)(mu-NHC6H11)]Cl 3 have been synthesized. Reactions of Ru(NR')(MeC(6)H(4)Pr(i)-p)(R' = 2,4,6-Bu(3)(t)C(6)H(2)) with (mes)NCO and (mes)N-3 are reported. Attempts to isolate Rh(eta-C(5)Me(5))(NR) species failed but evidence for Rh(eta-C(5)Me(5))[N(2,6-(Pr2C6H3)-C-i)N-3(mes)] was obtained in a trapping reaction in solution using (mes)N-3. The crystal structures of the compounds Ir(eta-C(5)Me(5))(eta(2)-Bu(t)NCNBu(t))(CNBu(t)), [Ir(eta-C5H5)(mu-NC5H9)](2) 2, 3, [Ir-2(eta-C(5)Me(5))(mu-NC6H11)(mu-NHC6H11)]Cl 3, Ir(eta-C(5)Me(5))[N(xyl)CHN(2,6-(Pr2C6H3)-C-i)CNC6H3(Me)CH2] 4b, Ir(eta-C(5)Me(5))[N(2,6-(Pr2C6H3)-C-i)C(O)N(mes)] 5, Ir(eta-C(5)Me(5))[N(2,6-(Pr2C6H3)-C-i)N-3(mes)] 6, Ru[N(2,4,6-Bu(3)(t)C(6)H(2))C(O)N(mes)](MeC(6)H(4)Pr(i)-p) 8 and Ru[N(2,4,6-Bu(3)(t)C(6)H(2))N-3(mes)](MeC(6)H(4)Pr(i)-p) 9 have been determined. A reaction mechanism for the formation of 4b is given.