Preparation and characterization of rhodium pentamethylcyclopentadienyl isocyanide complexes, (C5Me5)Rh(CNR)2 and [(C5Me5)Rh(CNR)]2 complexes

Abstract

Several complexes of the type (C{sub 5}Me{sub 5})M(CNR)X{sub 2} have been prepared, where M = Rh and Ir, X = Cl, Br, and I and R = Me, t-Bu, neo-Pn, i-Pr, 2,6-xylyl, and CH{sub 2}-adamantyl. Two members of this series have been structurally characterized. The crystal structures of (C{sub 5}Me{sub 5})Rh(CrMe)Cl{sub 2} and (C{sub 5}Me{sub 5})Ir(Cn-2,6-xylyl)I{sub 2} are reported. Reduction of the dihalide derivatives in the presence of isocyanide provides a general route to the bis-substituted products (C{sub 5}Me{sub 5})Rh(CNR){sub 2} (R = Me, t-Bu, neo-Pn, i-Pr, 2,6-xylyl, CH{sub 2}-adamantyl). Reduction of the dihalide complexes in the absence of added isocyanide gives the dimers ((C{sub 5}Me{sub 5})Rh({mu}-CNR)){sub 2}, one of which has been characterized by x-ray crystallography (R = 2,6-xylyl). 25 refs., 3 figs., 6 tabs.