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Ethene activation and catalytic hydrogenation by a low-valent uranium pentalene complex
journal contribution
posted on 2023-06-09, 20:02 authored by Nikolaos Tsoureas, Laurent Maron, Alexander F R Kilpatrick, Richard LayfieldRichard Layfield, Geoff ClokeThe reaction of the uranium(III) complex [U(?8-Pn††)(?5-Cp*)] (1) (Pn†† = C8H4(1,4-SiiPr3)2, Cp* = C5Me5) with ethene at atmospheric pressure produces the ethene-bridged diuranium complex [{(?8-Pn††)(?5-Cp*)U}2(µ-?2:?2-C2H4)] (2). A computational analysis of 2 revealed that coordination of ethene to uranium reduces the carbon–carbon bond order from 2 to a value consistent with a single bond, with a concomitant change in the formal uranium oxidation state from +3 in 1 to +4 in 2. Furthermore, the uranium–ethene bonding in 2 is of the d type, with the dominant uranium contribution being from f–d hybrid orbitals. Complex 2 reacts with hydrogen to produce ethane and reform 1, leading to the discovery that complex 1 also catalyzes the hydrogenation of ethene under ambient conditions.
Funding
EPSRC; EP/M023885/1
RadMag; ERC; 646740
History
Publication status
- Published
File Version
- Accepted version
Journal
Journal of the American Chemical SocietyISSN
0002-7863Publisher
American Chemical SocietyExternal DOI
Issue
1Volume
142Page range
89-92Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2020-01-02First Open Access (FOA) Date
2020-12-20First Compliant Deposit (FCD) Date
2019-12-23Usage metrics
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