C-C Bond Cleavage in Hydrocarbons by Iridium Complexes

Article abstract of DOI:10.1021/ja00283a015

A variety of transformations involving C-C bond cleavage in iridium complexes is described. 1,1-Dimethylcyclopentane reacts with SbF6 (L = (p-FC6H4)3P, 1) to give first <(5,5-C5H4Me2)IrL2>SbF6 (2) and then <(MeC5H4)IrMeL2>SbF6 (3).The corresponding 5,5-dimethylcyclopentadiene gives 1,2- and 1,3-diethylcyclopentadienyl complexes by a route that involves alkyl migration from ring to metal and back. 4,4-Dimethylcyclopentene also reacts to give 3 but the 3,3-isomer follows a different path to give <(MeC5H4)IrHL2>SbF6.Crystal structures of two diene complexes of type 2 are reported and mechanisms for the reactions observed are proposed.