Synthesis and Structure of Uranium‐Silylene Complexes

Brackbill, I. Joseph; Douair, Iskander; Lussier, Daniel J.; Boreen, Michael A.; Maron, Laurent; Arnold, John

doi:10.1002/chem.202000214

Title: Synthesis and Structure of Uranium‐Silylene Complexes

Journal Article · 04 February 2020 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202000214 · OSTI ID:1597168

Brackbill, I. Joseph ^[1]; Douair, Iskander ^[2]; Lussier, Daniel J. ^[1]; Boreen, Michael A. ^[1]; Maron, Laurent ^[2];

^[1]

Department of Chemistry University of California, Berkeley, and the Chemical Sciences Division, Lawrence Berkeley National Laboratory Berkeley California 94720-1460 USA
LPCNO Université de Toulouse, INSA Toulouse 135 Avenue de Rangueil 31077 Toulouse France

Abstract While carbene complexes of uranium have been known for over a decade, there are no reported examples of complexes between an actinide and a „heavy carbene.“ Herein, we report the syntheses and structures of the first uranium‐heavy tetrylene complexes: (CpSiMe ₃ ) ₃ U‐Si[PhC(NR) ₂ ]R’ (R= t Bu, R’=NMe ₂ 1 ; R= i Pr, R’=PhC(N i Pr) ₂ 2 ). Complex 1 features a kinetically robust uranium‐silicon bonding interaction, while the uranium‐silicon bond in 2 is easily disrupted thermally or by competing ligands in solution. Calculations reveal polarized σ bonds, but depending on the substituents at silicon a substantial π‐bonding interaction is also present. The complexes possess relatively high bond orders which suggests primarily covalent bonding between uranium and silicon. These results comprise a new frontier in actinide‐heavy main‐group bonding.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1597168

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 11 Vol. 26; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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