Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study

Kefalidis, Christos E, Frey, Alistair S P, Roe, S Mark, Cloke, F Geoffrey N and Maron, Laurent (2014) Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study. Dalton Transactions, 2014 (43). pp. 11202-11208. ISSN 1477-9226

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Abstract

Computational studies on the reductive activation of a mixture of CO and NO by the U(III) complex [U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)], which affords a mixture of [U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)]2(μ-OCN)21 and [U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)]2(μ-O) 2, show that the reaction proceeds via an initial attack of CO on a μ–η2:η2 coordinated NO, side-on bridged between two uranium centres. This leads to the formation of the bridging oxo complex 2 and the cyanate radical; coordination of the latter to the starting complex and dimerisation affords 1. The DFT studies also predict the existence of the monocyanate-bridged, mixed valence species [U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)]2(μ-OCN) 3, which has now been experimentally observed.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry
Depositing User: Tom Gittoes
Date Deposited: 09 Mar 2015 10:28
Last Modified: 09 Mar 2015 10:28
URI: http://sro.sussex.ac.uk/id/eprint/53269
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