Covalency-Driven Differences in the Hydrogenation Chemistry of Lanthanide- and Actinide-Based Frustrated Lewis Pairs

Brackbill, I. Joseph; Rajeshkumar, Thayalan; Douair, Iskander; Maron, Laurent; Boreen, Michael A.; Bergman, Robert G.; Arnold, John

doi:10.1021/jacs.4c06777

Covalency-Driven Differences in the Hydrogenation Chemistry of Lanthanide- and Actinide-Based Frustrated Lewis Pairs

Journal Article · Thu Jul 25 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c06777· OSTI ID:2459304

^[1]; Rajeshkumar, Thayalan ^[2]; Douair, Iskander ^[2]; ^[2]; ^[3]; ^[4]; ^[3]

University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley
Université de Toulouse (France)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of California, Berkeley, CA (United States)

The electronic organization of Frustrated Lewis Pairs (FLPs) allows them to activate strong bonds in mechanisms that are usually free of redox events at the Lewis acidic site. The unique 6d/5f manifold of uranium could serve as an interesting FLP acceptor site, but to date FLP-like catalysis with actinide ions is unknown. In this paper, the catalytic, FLP-like hydrogenation reactivity of trivalent uranium complexes is explored in the presence of base-stabilized silylenes. Comparison to isoelectronic, isostructural lanthanide and thorium complexes lends insight into the electronic factors governing dihydrogen activation. Mechanistic studies of the uranium- and lanthanide-catalyzed hydrogenations are presented, including discussion of likely intermediates. Computational modeling of the f-element complexes, combined with experimental comparison to p-block Lewis acids, elucidates the relevance of steric hindrance to productive reactivity with dihydrogen. As a result, consideration of the complete experimental and theoretical evidence provides a clear picture of the electronic and steric factors governing dihydrogen activation by these FLPs.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; NA0003996

OSTI ID:: 2459304

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 31 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2355459: Experimental Crystal Structure Determination Joseph, Brackbill, I.; Thayalan, Rajeshkumar,; Iskander, Douair, https://doi.org/10.5517/ccdc.csd.cc2k21k8 The current record is supplemented by this dataset	dataset	January 2024
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CCDC 2355461: Experimental Crystal Structure Determination Joseph, Brackbill, I.; Thayalan, Rajeshkumar,; Iskander, Douair, https://doi.org/10.5517/ccdc.csd.cc2k21mb The current record is supplemented by this dataset	dataset	January 2024
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Covalency-Driven Differences in the Hydrogenation Chemistry of Lanthanide- and Actinide-Based Frustrated Lewis Pairs

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