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Journal Articles Dalton Transactions Year : 2014

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

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.
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Dates and versions

hal-01969545 , version 1 (04-01-2019)

Identifiers

  • HAL Id : hal-01969545 , version 1

Cite

Christos E. Kefalidis, Alistair Frey, S. Mark Roe, F. Geoffrey N. Cloke, Laurent Maron. Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study. Dalton Transactions, 2014, 43 (29), pp.11202-11208. ⟨hal-01969545⟩
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