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Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study
journal contribution
posted on 2023-06-08, 20:15 authored by Christos E Kefalidis, Alistair S P Frey, S Mark Roe, Geoff Cloke, Laurent MaronComputational studies on the reductive activation of a mixture of CO and NO by the U(III) complex [U(?-C8H6{SiiPr3-1,4}2)(?-Cp*)], which affords a mixture of [U(?-C8H6{SiiPr3-1,4}2)(?-Cp*)]2(µ-OCN)21 and [U(?-C8H6{SiiPr3-1,4}2)(?-Cp*)]2(µ-O) 2, show that the reaction proceeds via an initial attack of CO on a µ–?2:?2 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(?-C8H6{SiiPr3-1,4}2)(?-Cp*)]2(µ-OCN) 3, which has now been experimentally observed.
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Publication status
- Published
Journal
Dalton TransactionsISSN
1477-9226Publisher
Royal Society of ChemistryExternal DOI
Issue
43Volume
2014Page range
11202-11208Department affiliated with
- Chemistry Publications
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- No
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- Yes
Legacy Posted Date
2015-03-09Usage metrics
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