Assistant Professor Manar Shoshani named October 2024 Sutton Family Research Impact Award recipient
The Department of Chemistry congratulates Assistant Professor Manar Shoshani on receiving the October 2024 Sutton Family Research Impact Award!
The Sutton Award is a monthly competition among chemistry faculty. Every month, the Chemistry Department Chair and Associate Chairs review the peer-reviewed papers published by chemistry faculty from the three previous months to select a winner. The recipient receives a $500 cash prize and is featured on the departmental website.
For a full list of winners, visit our Sutton Family Research Impact Award webpage.
Synthesis and characterization of NiAl-hydride heterometallics: perturbing electron density within Al-H-Ni subunits
By Aleida G. Gonzalez, Fernando Gonzalez, Edgardo De Leon, Kaitlyn M. Birkhoff, Sam Yruegas, Haoyuan Chen, and Manar M. Shoshani
Dalton Trans., 2024, 53, 18932-18945. DOI: 10.1039/d4dt01786b
Motivated by cooperativity in metal-surfaces and biological active sites, well-defined molecular platforms able to house redox-active and redox-inactive metals in a site-specific arrangement have been interrogated in small molecule activation and functionalization. In addition, metal-hydrides have been invoked as key intermediates in a myriad of catalytic transformations, and similarly an amplification in reactivity when multimetallic hydrides are utilized is often observed. While heterometallic hydrides are known to serve as highly active catalysts for hydrogenation and insertion-based reactivity, synthetic methods to reliably generate these architectures are not well-understood. Furthermore, methodology to make systematic changes to the nature of the hydride moiety in multimetallic systems are lacking.
In an earlier report, the Shoshani group produced a well-defined NiAl2(H2) heterotrimetallic complex, bearing a rare Al-H-Ni subunit, on a ligand architecture with site-specific binding sites. The heterotrimetallic species catalyzes the hydrofunctionalization of N-heterocycles and demonstrates a 400x amplification in consumption of quinoline in comparison to the Al-H precursor. Though the amplification in reactivity was clear; the nature of the activated hydride moiety within the Al-H-Ni subunit warranted more exploration.
In this latest study, the Shoshani lab explored the continuum of sigma-bonding within the Al-H-Ni subunit by synthetically accessing a series of heterobimetallics with electronically differentiating phosphine coligands and exploring the impact in crystallographic, spectroscopic, and computational studies. Furthermore, anionic systems were accessed that represent potential catalytic intermediates in hydrofunctionalization-based reactivity. Our study demonstrates that the addition of varying coligands perturbs the electronic structure and that the usage of electron rich coligands and anionic charge generate variants with increasing “Ni‒H” character. The group hopes to extend upon these findings and interrogate these heterometallic motifs in comparative catalytic reactivity studies. This work was published in Dalton Transactions as part of the special issue “New Talents: The Americas”.
Heterobimetallic NiAl-hydride complexes with varying electronic profiles and charge are synthesized and interrogated in their degree of Ni–H character.