Iridium Complexes with Bidentate Pyridinylidene/N-Amidate Ligands for Transfer Hydrogenation Catalysis

Abstract

A series of iridium pentamethylcyclopentadienyl (Cp*) complexes, [Cp*Ir(κ2- R L p/m )Cl], that contain the strongly coordinating bidentate ligands R L p/m were synthesized. The donor groups of the bidentate ligands were an N-amidate and either a para-pyridinylidene remote N-heterocyclic carbene ( R L p ) or a meta-pyridinylidene remote N-heterocyclic carbene ( R L m ). For each type of bidentate ligand, a set of iridium complexes was synthesized, which differed only according to the substituents (R) on the phenyl ring associated with the amidate group. The iridium complexes were all fully characterized and molecular structures were obtained by single-crystal X-ray diffraction studies for representative examples. The complexes were found to be good precatalysts in iso-propanol for the transfer hydrogenation of benzaldehyde to give benzyl alcohol. The catalytic activity correlated with the Hammett σm/p parameters of the phenyl ring substituents, with more electron-donating substituents leading to increased catalytic activity. In all cases, the meta-pyridinylidene complexes, [Cp*Ir(κ2- R L m )Cl], performed better than the corresponding para analogues, [Cp*Ir(κ2- R L p )Cl].