Insights into H<inf>2</inf>Activation and Styrene Hydrogenation by Nickel-Borane and Nickel-Alane Bifunctional Catalysts
Issued Date
2022-02-14
Resource Type
ISSN
02767333
eISSN
15206041
Scopus ID
2-s2.0-85123928023
Journal Title
Organometallics
Volume
41
Issue
3
Start Page
259
End Page
269
Rights Holder(s)
SCOPUS
Bibliographic Citation
Organometallics Vol.41 No.3 (2022) , 259-269
Suggested Citation
Boonpalit K., Uthayopas C., Surawatanawong P. Insights into H<inf>2</inf>Activation and Styrene Hydrogenation by Nickel-Borane and Nickel-Alane Bifunctional Catalysts. Organometallics Vol.41 No.3 (2022) , 259-269. 269. doi:10.1021/acs.organomet.1c00620 Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/84207
Title
Insights into H<inf>2</inf>Activation and Styrene Hydrogenation by Nickel-Borane and Nickel-Alane Bifunctional Catalysts
Author(s)
Author's Affiliation
Other Contributor(s)
Abstract
Lewis 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.
