Synthesis and Structure of Uranium‐Silylene Complexes
Abstract
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.
- Authors:
-
[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
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1597168
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 26 Journal Issue: 11; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Brackbill, I. Joseph, Douair, Iskander, Lussier, Daniel J., Boreen, Michael A., Maron, Laurent, and Arnold, John. Synthesis and Structure of Uranium‐Silylene Complexes. Germany: N. p., 2020.
Web. doi:10.1002/chem.202000214.
Brackbill, I. Joseph, Douair, Iskander, Lussier, Daniel J., Boreen, Michael A., Maron, Laurent, & Arnold, John. Synthesis and Structure of Uranium‐Silylene Complexes. Germany. https://doi.org/10.1002/chem.202000214
Brackbill, I. Joseph, Douair, Iskander, Lussier, Daniel J., Boreen, Michael A., Maron, Laurent, and Arnold, John. Tue .
"Synthesis and Structure of Uranium‐Silylene Complexes". Germany. https://doi.org/10.1002/chem.202000214.
@article{osti_1597168,
title = {Synthesis and Structure of Uranium‐Silylene Complexes},
author = {Brackbill, I. Joseph and Douair, Iskander and Lussier, Daniel J. and Boreen, Michael A. and Maron, Laurent and Arnold, John},
abstractNote = {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.},
doi = {10.1002/chem.202000214},
journal = {Chemistry - A European Journal},
number = 11,
volume = 26,
place = {Germany},
year = {Tue Feb 04 00:00:00 EST 2020},
month = {Tue Feb 04 00:00:00 EST 2020}
}
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