Comparative study of CO(2) insertion into pincer supported palladium alkyl and aryl complexes

The insertion of CO(2) into metal alkyl bonds is a crucial elementary step in transition metal-catalyzed processes for CO(2) utilization. Here, we synthesize pincer-supported palladium complexes of the type ((tBu)PBP)Pd(alkyl) ((tBu)PBP = B(NCH(2)P(t)Bu(2))(2)C(6)H(4)(−); alkyl = CH(2)CH(3), CH(2)CH(2)CH(3,) CH(2)C(6)H(5), and CH(2)-4-OMe-C(6)H(4)) and ((tBu)PBP)Pd(C(6)H(5)) and compare the rates of CO(2) insertion into the palladium alkyl bonds to form metal carboxylate complexes. Although, the rate constant for CO(2) insertion into ((tBu)PBP)Pd(CH(2)CH(3)) is more than double the rate constant we previously measured for insertion into the palladium methyl complex ((tBu)PBP)Pd(CH(3)), insertion into ((tBu)PBP)Pd(CH(2)CH(2)CH(3)) occurs approximately one order of magnitude slower than ((tBu)PBP)Pd(CH(3)). CO(2) insertion into the benzyl complexes ((tBu)PBP)Pd(CH(2)C(6)H(5)) and ((tBu)PBP)Pd(CH(2)-4-OMe-C(6)H(4)) is significantly slower than any of the n-alkyl complexes, and CO(2) does not insert into the palladium phenyl bond of ((tBu)PBP)Pd(C(6)H(5)). While ((tBu)PBP)Pd(CH(2)CH(3)) and ((tBu)PBP)Pd(CH(2)CH(2)CH(3)) are resistant to β-hydride elimination, we were unable to synthesize complexes with n-butyl, iso-propyl, and tert-butyl ligands due to β-hydride elimination and an unusual reductive coupling, which involves the formation of new C–B bonds. This reductive process also occurred for ((tBu)PBP)Pd(CH(2)C(6)H(5)) at elevated temperature and a related process involving the formation of a new H–B bond prevented the isolation of ((tBu)PBP)PdH. DFT calculations provide insight into the relative rates of CO(2) insertion and indicate that steric factors are critical. Overall, this work is one of the first comparative studies of the rates of CO(2) insertion into different metal alkyl bonds and provides fundamental information that may be important for the development of new catalysts for CO(2) utilization.