Boonpalit K.Uthayopas C.Surawatanawong P.Mahidol University2023-06-182023-06-182022-02-14Organometallics Vol.41 No.3 (2022) , 259-26902767333https://repository.li.mahidol.ac.th/handle/20.500.14594/84207Lewis acid-transition metal bifunctional complexes have recently emerged as a new class of catalysts. The nickel-borane complex, Ni[(Mes)B(o-Ph2PC6H4)2], has been reported as an efficient catalyst for H2 activation and styrene hydrogenation. Here, we performed density functional theory calculations to investigate the cooperation between nickel and a group 13 element (Z = B and Al), including the effect of its substituent (R = Mes, Ph, and C6F5 in Ni[(R)Z(o-Ph2PC6H4)2]), on H2 activation and styrene hydrogenation. We found that H2 activation by the nickel-borane complex is dominated by charge transfer from the σ-bonding orbital of H2 to the p-based vacant orbital of boron, whereas H2 activation by the nickel-alane complex is governed by charge transfer from the d-based orbital of Ni to the σ*-antibonding orbital of H2. The resulting trans-dihydride nickel-alane complex has higher negative charges on both terminal and bridging hydrogen atoms than the corresponding nickel-borane complex. This accounts for the lower energy barriers observed for the nickel-alane complex toward both H2 activation and the subsequent hydrogenation of styrene. While the C6F5 electron-withdrawing substituent on boron of the nickel-borane complex facilitates H2 activation and styrene hydrogenation better than the phenyl or mesityl substituent, the substituent on aluminum does not affect the reactivity of the nickel-alane complex. As H2 activation and styrene hydrogenation by nickel-alane complexes proceed with lower energy barriers than those by nickel-borane complexes, the nickel-alane complex with [(R)Z(o-Ph2PC6H4)2] ligand scaffold should be more reactive than the nickel-borane counterpart. Insights into the role of Lewis acid in this Z-type σ-acceptor ligand scaffold will assist with the development of metal-ligand bifunctional catalysts.ChemistryArticleSCOPUS10.1021/acs.organomet.1c006202-s2.0-8512392802315206041