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

The (pentamethylcyclopentadienyl)rhodium and -iridium chlorides (C 5 Me 5 -MCl 2 ) 2 reacted with silver acetate to give the acetates, C 5 Me 5 M(OAc) 2 ·H 2 O, which in turn gave the trifluoroacetates, C 5 Me 5 M(OCOCF 3 ) 2 ·H 2 O, with CF 3 COOH. The rhodium acetate was relatively stable, but the iridium complex was readily hydrolyzed to the dihydroxo complex. Reaction of (C 5 Me 5 RhCl 2 ) 2 with aqueous base gave the complexes [(C 5 Me 5 Rh) 2 (OH) 3 ] + X - , which are formulated with three bridging hydroxo groups. An analogous structure is proposed for [(C 5 Me 5 Rh) 2 Cl 3 ]-BPh 4 . The complex {[C 5 (CH 3 ) 5 Rh] 2 (OH) 3 }Cl gave {[C 5 (CD 3 ) 5 Rh] 2 (OD) 3 }Cl on heating with OD - in D 2 O; this reaction was reversed in H 2 O/OH - . The complexes [C 5 (CD 3 ) 5 RhCl 2 ] 2 and C 5 (CD 3 ) 5 Rh(C 2 H 4 ) 2 were also prepared.