Ethene Activation and Catalytic Hydrogenation by a Low-Valent Uranium Pentalene Complex

• DOI: 10.1021/jacs.9b11929
• Publication Date: 2019-12-20T01:46:51Z
• Authors: Nikolaos Tsoureas; Laurent Maron; Alexander F. R. K...; Richard A. Layfield; F. Geoffrey N. Cloke
• Keywords: Pentalene; Carbon fibers

The reaction of the uranium(III) complex [U(η8-Pn††)(η5-Cp*)] (1) (Pn†† = C8H4(1,4-SiiPr3)2, Cp* C5Me5) with ethene at atmospheric pressure produces ethene-bridged diuranium [{(η8-Pn††)(η5-Cp*)U}2(μ-η2:η2-C2H4)] (2). A computational analysis 2 revealed that coordination to uranium reduces carbon–carbon bond order from a value consistent single bond, concomitant change in formal oxidation state +3 1 +4 2. Furthermore, uranium–ethene bonding is δ type, dominant contribution being f–d hybrid orbitals. Complex reacts hydrogen produce ethane and reform 1, leading discovery also catalyzes hydrogenation under ambient conditions.