Synthesis and Structure of Uranium-Silylene Complexes |
| |
| Authors: | I. Joseph Brackbill Iskander Douair Daniel J. Lussier Michael A. Boreen Prof. Dr. Laurent Maron Prof. Dr. John Arnold |
| |
| Affiliation: | 1. Department of Chemistry, University of California, Berkeley, and the Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, 94720-1460 USA;2. 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: (CpSiMe3)3U-Si[PhC(NR)2]R’ (R=tBu, R’=NMe2 1 ; R=iPr, R’=PhC(NiPr)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. |
| |
| Keywords: | actinides donor–acceptor interactions heavy carbenes silylenes uranium |
|
|
