(Pentamethylcyclopentadienyl)rhodium and -iridium complexes. V. Complexes with oxy-ligands and the exchange of methyl protons by deuterium under basic conditions

Abstract

The (pentamethylcyclopentadienyl)rhodium and -iridium chlorides (C5Me5-MCl2)2 reacted with silver acetate to give the acetates, C5Me5M(OAc)2·H2O, which in turn gave the trifluoroacetates, C5Me5M(OCOCF3)2·H2O, with CF3COOH. The rhodium acetate was relatively stable, but the iridium complex was readily hydrolyzed to the dihydroxo complex. Reaction of (C5Me5RhCl2)2 with aqueous base gave the complexes [(C5Me5Rh)2(OH)3]+X-, which are formulated with three bridging hydroxo groups. An analogous structure is proposed for [(C5Me5Rh)2Cl3]-BPh4. The complex {[C5(CH3)5Rh]2(OH)3}Cl gave {[C5(CD3)5Rh]2(OD)3}Cl on heating with OD- in D2O; this reaction was reversed in H2O/OH-. The complexes [C5(CD3)5RhCl2]2 and C5(CD3)5Rh(C2H4)2 were also prepared.