Issue 10, 2010

Easy access to uranium nucleophilic carbene complexes

Abstract

Metathesis reactions of UCl4 with Li2C(Ph2PS)2 in Et2O only afforded the tris-carbene complex [{Li(OEt2)}2U{[double bond, length as m-dash]C(Ph2PS)2}3] (1), while the bis- and mono-carbene compounds [U{[double bond, length as m-dash]C(Ph2PS)2}2(THF)2] (2) and [{Li(THF)2}2U{[double bond, length as m-dash]C(Ph2PS)2}Cl4] (3) were obtained by treatment of UCl4 with Li2C(Ph2PS)2 in a mixture of THF and toluene. The bis-carbene complex 2 was also obtained either from the comproportionation reaction of 1 and UCl4 or protonolysis reaction of U(NEt2)4 with H2C(Ph2PS)2 and was transformed into the mono-carbene complex [U{[double bond, length as m-dash]C(Ph2PS)2}Cl2(THF)2] (4) by further reaction with UCl4. The utility of these complexes as precursors is illustrated by the synthesis of the biscyclopentadienyl derivative [Cp2U{[double bond, length as m-dash]C(Ph2PS)2}] (5) by treatment of 3 with TlCp. The crystal structures of [U{[double bond, length as m-dash]C(Ph2PS)2}2(py)2]·1.5py·0.5THF and 5·toluene are reported.

Graphical abstract: Easy access to uranium nucleophilic carbene complexes

Supplementary files

Article information

Article type
Communication
Submitted
30 Oct 2009
Accepted
15 Jan 2010
First published
26 Jan 2010

Dalton Trans., 2010,39, 2494-2496

Easy access to uranium nucleophilic carbene complexes

J. Tourneux, J. Berthet, P. Thuéry, N. Mézailles, P. Le Floch and M. Ephritikhine, Dalton Trans., 2010, 39, 2494 DOI: 10.1039/B926718M

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