Rhodium(III) Peroxo Complexes Containing Carbene and Phosphine Ligands

The Rh(I) carbene precursors [RhCl(COE)(NHC)]2, where the N-heterocyclic carbene is 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes),
were used to synthesize the RhCl(NHC)(P-N) complexes 4 (NHC = IPr) and 5 (NHC = IMes), where
P-N is P,N-chelated o-(diphenylphosphino)-N,N-dimethylaniline, and the corresponding cis-RhCl(NHC)(PPh3)2 complexes 6 and 7. The synthesis of 4 surprisingly requires the reaction to be carried out under
a hydrogen atmosphere and occurs via the intermediate dihydride RhCl(H)2(IPr)(P-N) (3). Complexes
4−7 in benzene readily undergo irreversible oxidative addition of O2 to form the corresponding Rh(III)
peroxide complexes 9−12. For comparative purposes, RhCl(PPh3)(P-N) (8) was synthesized from RhCl(PPh3)3, and this also added O2 to form a peroxo complex (13). All of the complexes were generally
characterized by elemental analysis and 1H, 31P{1H}, and 13C{1H} NMR and IR spectroscopies and, in
the cases of 9, 10, and 13, by X-ray crystallography.