Theoretical Insight into Ni(0)-Catalyzed Hydroarylation of Alkenes and Arylboronic Acids.

The density functional theory (ωB97XD functional) is employed to clarify nickel(0)/PtBu3-catalyzed hydroarylation of alkenes and arylboronic acids with methanol. The computational results reveal that this reaction goes primarily through the ligand-to-ligand H transfer from the O-H bond to the alkene coordinated with nickel, complexation of arylboronic acid to the nickel-alkyl-methoxyl intermediate, attack of methoxyl on boron, transmetalation, and reductive elimination. The formation of the branched 1,1-diarylalkane, linear 1,1-diarylalkane, and alkene-dimer is also discussed in this work.