Synthesis and Reactivity of Terminal U(IV) Hydrides Including the Isolation of a κ<sup>1</sup>-Formate
Formation of a rare terminal U(IV) hydride complex, [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>(2,6-<sup>t</sup>Bu<sub>2</sub>-4-MeC<sub>6</sub>H<sub>2</sub>O)U(H)], was accomplished through the hydrogenation of a uranium(IV) metallocene hydrocarbyl complex. The reactivity of this hydride was probed with a variety of substrates to examine sigma-bond metathesis, PhEEPh (E = S, Se, Te), and insertion (CO<sub>2</sub>, CH<sub>2</sub>═CH<sub>2</sub>) reactivity. While the reaction of CO did not produce an isolable result, using the U(IV) hydride with a less sterically encumbering mesityl aryloxide, an ethenediolate is formed, [{(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>(MesO)U}<sub>2</sub>(μ<sub>2</sub>-OC(H)═C(H)O], Mes = mesityl, 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>. Each complex has been characterized by NMR, IR, and X-ray crystallographic analysis.
Authors
- Justin R. Walensky (ORCID: https://orcid.org/0000-0003-0221-2675)
- M. Gayanethra Kaumini
- Iker Del Rosal (ORCID: https://orcid.org/0000-0001-6898-4550)
- Pokpong Rungthanaphatsophon
- Steven P. Kelley (ORCID: https://orcid.org/0000-0001-6755-4495)
- Laurent Maron (ORCID: https://orcid.org/0000-0003-2653-8557)
Institutions
- Centre National de la Recherche Scientifique (FR)
- Université Toulouse III - Paul Sabatier (FR)
- Université Fédérale de Toulouse Midi-Pyrénées (FR)
- Institut National des Sciences Appliquées de Toulouse (FR)
- University of Missouri (US)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-08-22
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c02420
- Citations
- 2
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Basic Energy Sciences