LAUSR

An early investigation in the author‘s laboratory into photochemical C−H bond activation and functionalization is recounted. Specifically, d8 Ir(I) and Rh(I) carbonyl phosphine complexes were found to promote benzene C−H bond activtion and functionalization to give benzaldehyde upon near-UV irradiation. The carbonylation of benzene is thermodynamically unfavorable resulting in only low yields of benzaldehyde. The photochemical process was suggested as ligand dissociation to yield a 14 e− Ir(I) or Rh(I) intermediate capable of benzene C−H oxidative additions. The research set the stage for subsequent photochemical C−H activation and functionalization studies by others in the late 1980’s.