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Issue 35, 2009
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Synthesis and structure of early transition metal NHC complexes

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The synthesis and structure of several new early transition metal (Ti, Zr, Hf, and V) NHC complexes supported by one or two IMes ligands is described. Reaction of M(NMe2)4 with IMes·HCl gives compounds VCl2(NMe2)(IMes)2 (2), and MCl2(NMe2)2(IMes) (M = V (3), Zr (4), Hf (5)). Treatment of TiCl3(THF)3 with 2 equiv. of IMes and 1 equiv. of LiNMe2 affords the titanium(III) compound TiCl2(NMe2)(IMes)2. Reaction of VCl3(THF)3 with 2 equiv. of IMes in toluene produces the trivalent complex VCl3(IMes)2 (6), while VCl2(Py)4 gives the divalent compound VCl2(IMes)(Py)3 (7), and ZrCl4(THF)2 leads to ZrCl4(IMes)2 (8). Imido compounds M([double bond, length as m-dash]N-2,6-iPr2-C6H3)Cl2(NHMe2)(IMes) (M = V (9), Zr (10)) are prepared from V([double bond, length as m-dash]NR)Cl2(NHMe2)2 or ZrCl2(NMe2)2(IMes) synthons. Ionic imido complexes [M([double bond, length as m-dash]N-2,6-iPr2-C6H3)Cl3(IMes)][HIMes]+ (M = V (12), Ti (13)) are obtained in modest yields from the treatment of [M([double bond, length as m-dash]NR)Cl2(NHMe2)2] with 2 equiv. of IMes. Treatment of a toluene solution of V(NMe2)4 and an amide RC(O)NH2 (R = tBu, Ph) in the presence of an excess of Me3SiCl produces the terminal oxo complex V([double bond, length as m-dash]O)Cl2(NHMe2)2 (13), which reacts with two equiv. of IMes to give the bis-NHC oxo-complex V([double bond, length as m-dash]O)Cl2(IMes)2 (14). All new compounds have been characterised by various spectroscopic techniques, elemental analyses, and magnetism studies for paramagnetic compounds. The solid-state structure of 12 of these complexes and of IMes·HCl have further been confirmed by X-ray diffraction analyses.

Graphical abstract: Synthesis and structure of early transition metal NHC complexes

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The article was received on 12 Mar 2009, accepted on 11 May 2009 and first published on 30 Jun 2009

Article type: Paper
DOI: 10.1039/B905056F
Citation: Dalton Trans., 2009,0, 6972-6984
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    Synthesis and structure of early transition metal NHC complexes

    C. Lorber and L. Vendier, Dalton Trans., 2009, 0, 6972
    DOI: 10.1039/B905056F

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