Reactions of imido complexes of iridium, rhodium and ruthenium

Interactions of the known compounds Ir(η-C5Me5)(NR)(R = But1a 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-But3C6H2) 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-ButNCNBut)(CNBut), [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-But3C6H2)C(O)N(mes)](MeC6H4Pri-p)8 and Ru[N(2,4,6-But3C6H2)N3(mes)](MeC6H4Pri-p)9 have been determined. A reaction mechanism for the formation of 4b is given.