Ethene Activation and Catalytic Hydrogenation by a Low-Valent Uranium Pentalene Complex
Nikolaos Tsoureas1, Laurent Maron2, Alexander F R Kilpatrick3
1Department of Chemistry, School of Life Sciences , University of Sussex , Brighton BN1 9QJ , U.K.
Abstract:
The reaction of the uranium(III) complex [U(η8-Pn††)(η5-Cp*)] (1) (Pn†† = C8H4(1,4-SiPr3)2, Cp* = C5Me5) with ethene at atmospheric pressure produces the ethene-bridged diuranium complex [{(η8-Pn††)(η5-Cp*)U}2(μ-η2:η2-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 δ 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.
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