Amine-tethered N-heterocyclic carbene complexes of rhodium(I)

A new family of rhodium-diene based complexes has been developed that incorporates an N-heterocyclic carbene ligand with an N-donor tether. The ligand is denoted (Mes)[CNH] 2 (where (Mes)[CNH] is 2,4,6-Me3C6H2NC3H2NCH2CH2NH-2,4,6-Me3C6H2) and (Mes)[CN] for the amido form. The synthesis of the (Mes)[CNH] ligand involves reaction of N-mesitylimidazole with 2-chloroethyl-N-mesitylamine under melt conditions, followed by deprotonation with KN(SiMe3)(2). The reaction of (Mes)[CNH] with [(diene)RhCl](2) results in the formation of the monodentate complexes, (Mes)[CNH]Rh(diene)Cl (where diene = 1,5-cyclooctadiene (COD): 3a; diene = 2,5-norbornadiene (NBD): 3b). Bidentate variants could be isolated as either a neutral species, (Mes)[CN]Rh(diene) 4a-4b, via deprotonation, or an ionic analogue such as [(Mes)[CNH]Rh(diene)]BF4 5a-5b by reaction with NaBF4. Compounds 4-5 are the first examples of rhodium compounds that contained a bidentate NHC ligand with a pendant amino or amido donor. Complexes 3-5 were characterized fully and the solid-state single crystal X-ray structures of 3a, 4a, and 5b are discussed. The utility of these complexes as catalyst precursors for hydrogenation reactions was examined and it was determined that these systems are not significantly more active than colloidal rhodium when parallel reactions were run. Various methods of transfer hydrogenations were also investigated with 3a, which did not yield an appreciable conversion of either benzophenone or N-benzylideneaniline as substrates.