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Issue 6, 2006
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‘Pincer’ dicarbene complexes of some early transition metals and uranium

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Abstract

The complexes [(C–N–C)MXn(thf)m] with the ‘pincer’ 2,6-bis(imidazolylidene)pyridine, (C–N–C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pri2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C–N–C) or by (b) reaction of the bisimidazolium salt (CH–N–CH)Br2 with {Cr[N(SiMe3)2]2(thf)2} followed by amine elimination (2b). Attempted alkylation of 1a, 2, 3a and 4 with Grignard or alkyl lithiums gave intractable mixtures, and in one case [reaction of 1a with (mesityl)MgBr] resulted in exchange of Cl by Br (1b). Oxidation of 1a or [(C–N–C)VCl3] with 4-methylmorpholine N-oxide afforded the trans-V(C–N–C)([double bond, length as m-dash]O)Cl2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C–N–C)([double bond, length as m-dash]O)(MeCN)2][BF4]2, 7. Reaction of 1a with p-tolyl azide gave trans-V(C–N–C)([double bond, length as m-dash]N-p-tolyl)Cl28. The complex trans-Ti(C–N–C)([double bond, length as m-dash]NBut)Cl2, 9, was prepared by substitution of the pyridine ligands in Ti(NBut)Cl2(py)3 by C–N–C.

Graphical abstract: ‘Pincer’ dicarbene complexes of some early transition metals and uranium

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Supplementary files

Article information


Submitted
26 Aug 2005
Accepted
14 Oct 2005
First published
08 Nov 2005

Dalton Trans., 2006, 775-782
Article type
Paper

‘Pincer’ dicarbene complexes of some early transition metals and uranium

D. Pugh, J. A. Wright, S. Freeman and A. A. Danopoulos, Dalton Trans., 2006, 775
DOI: 10.1039/B512133G

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