Synthesis and characterization of carbazolide-based iridium PNP pincer complexes. Mechanistic and computational investigation of alkene hydrogenation: Evidence for an Ir(III)/Ir(V)/Ir(III) catalytic cycle

New carbazolide-based iridium pincer complexes (carbPNP)Ir(C2H4), 3a, and (carbPNP)Ir(H)2, 3b, have been prepared and characterized. The dihydride, 3b, reacts with ethylene to yield the cis-dihydride ethylene complex cis-(carbPNP)Ir(C2H4)(H)2. Under ethylene this complex reacts slowly at 70 °C to yield ethane and the ethylene complex, 3a. Kinetic analysis establishes that the reaction rate is dependent on ethylene concentration and labeling studies show reversible migratory insertion to form an ethyl hydride complex prior to formation of 3a. Exposure of cis-(carbPNP)Ir(C2H4)(H)2 to hydrogen results in very rapid formation of ethane and dihydride, 3b. DFT analysis suggests that ethane elimination from the ethyl hydride complex is assisted by ethylene through formation of (carbPNP)Ir(H)(Et)(C2H4) and by H2 through formation of (carbPNP)Ir(H)(Et)(H2). Elimination of ethane from Ir(III) complex (carbPNP)Ir(H)(Et)(H2) is calculated to proceed through an Ir(V) complex (carbPNP)Ir(H)3(Et) which reductively elimi...