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'Pincer' dicarbene complexes of some early transition metals and uranium

'Pincer' dicarbene complexes of some early transition metals and uranium
'Pincer' dicarbene complexes of some early transition metals and uranium
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)pyriditie, aryl = 2,6-(Pr2C6H3)-C-1, M = V, X = Cl, n = 2, to = I 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 tined (1a), thf (2a, 3, 5) or dine (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br-2 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)(=O)Cl-2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)(2)][BF4](2), 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl-2 8. The complex trans-Ti(C-N-C)(=NBu1)Cl-2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu1)Cl-2(py)(3) by C-N-C.
n-heterocyclic carbene, crystal-structures, structural-characterization, ligands, cl, reactivity, alkyls, imido, amido, organometallics
1477-9226
775-782
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Wright, Joseph A.
3e730775-dda4-4d1e-83ad-8b1e96fb2cbe
Freeman, Sandra
979656fa-39aa-4649-b846-2c098e98ab57
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Wright, Joseph A.
3e730775-dda4-4d1e-83ad-8b1e96fb2cbe
Freeman, Sandra
979656fa-39aa-4649-b846-2c098e98ab57
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236

Pugh, David, Wright, Joseph A., Freeman, Sandra and Danopoulos, Andreas A. (2006) 'Pincer' dicarbene complexes of some early transition metals and uranium. Dalton Transactions, (6), 775-782. (doi:10.1039/b512133g).

Record type: Article

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)pyriditie, aryl = 2,6-(Pr2C6H3)-C-1, M = V, X = Cl, n = 2, to = I 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 tined (1a), thf (2a, 3, 5) or dine (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br-2 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)(=O)Cl-2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)(2)][BF4](2), 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl-2 8. The complex trans-Ti(C-N-C)(=NBu1)Cl-2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu1)Cl-2(py)(3) by C-N-C.

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Published date: 2006
Keywords: n-heterocyclic carbene, crystal-structures, structural-characterization, ligands, cl, reactivity, alkyls, imido, amido, organometallics

Identifiers

Local EPrints ID: 44529
URI: http://eprints.soton.ac.uk/id/eprint/44529
ISSN: 1477-9226
PURE UUID: 58e23109-cfe5-4e96-aef4-44c07c551ff2

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Date deposited: 01 Mar 2007
Last modified: 13 Mar 2019 21:07

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