Reductive Cyclotetramerization of CO to Squarate by a U(III) Complex; the X-ray Crystal Structure of [(U(n-C8H6{SiiPr3-1,4}2)(n-C5Me4H)]2(m-n2:n2-C4O4)

Summerscales, Owen T, Cloke, F Geoffrey N, Hitchcock, Peter B, Green, Jennifer C and Hazari, Nilay (2006) Reductive Cyclotetramerization of CO to Squarate by a U(III) Complex; the X-ray Crystal Structure of [(U(n-C8H6{SiiPr3-1,4}2)(n-C5Me4H)]2(m-n2:n2-C4O4). Journal of the American Chemical Society, 128 (30). pp. 9602-9603. ISSN 0002-7863

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Abstract

The U(III) mixed-sandwich compound [U(¿-C5Me4H)(¿-C8H6{SiiPr3-1,4}2)(THF)] 1 may be prepared by sequential reaction of UI3 with K[C5Me4H] in THF followed by K2[C8H6{SiiPr3-1,4}2]. 1 reacts with carbon monoxide at -30 °C and 1 bar pressure in toluene solution to afford the crystallographically characterized dimer [(U(¿-C8H6{SiiPr3-1,4}2)(¿-C5Me4H)]2(µ-¿2:¿2-C4O4) 2, which contains a bridging squarate unit derived from reductive cyclotetramerization of CO. DFT computational studies indicate that addition of a 4th molecule of CO to the model deltate complex [U(¿-COT)(¿-Cp)]2(µ-¿1:¿2-C3O3)] to form the squarate complex [U(¿-COT)(¿-Cp)]2(µ-¿2:¿2-C4O4)] is exothermic by 136 kJ mol-1.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Geoff Cloke
Date Deposited: 06 Feb 2012 19:30
Last Modified: 23 Mar 2012 09:33
URI: http://sro.sussex.ac.uk/id/eprint/20949
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