Pentamethylcyclopentadienylrhodium and -iridium Halides. I. Synthesis and Properties'

Abstract

Details of the reactions of hexamethyl(Dewar benzene), HMDB (hexamethylbicyclo[2.2.0]hexadiene) (l), and of 1 -(1-chloroethy1)pentamethylcyclopentadiene (4a) with RhCI3.3HrO and IrC13.5H20 to give the pentamethylcyclopentadienyl complexes, (C3Me3MC12)(29 ,a nd proposals for the mechanisms of these reactions are presented. The pentamethylcyclopentadienyl-metal bond in 5 is very strong, but reactions readily proceed at the halogens. Adducts of the type C3MesRhClsL (L = p-toluidine, pyridine, triphenylphosphine) are described as well as their reactions to form C3MesRhMenPPha3n d CSMe3RhMeIPPh3.T he synthesis of CSMeSIr(C0)i2s also