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Issue 3, 2012
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The first group 4 metal bis(imido) and tris(imido) complexes

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We report a combined experimental and computational study of the first bis(imido) and tris(imido) complexes of a group 4 metal. Reaction of [Ti(NAr)(NHAr)2(py)2] (1, Ar = 2,6-C6H3iPr2) with 3 equivs. of MeLi gave the lithium-stabilised tris(imide) [TiMe(NAr)3{Li(py)}3] (2). Reaction of 1 with 2 equivs. of MeLi in the presence of ArNH2 gave the corresponding bis(imide) [Ti(NAr)2(NHAr)2{Li(py)}2] (3). All three compounds 1, 2 and 3 have substantial Ti–Nimide multiple bond character. Orbital and Mayer bond order analysis show that the formal bond orders are best viewed as ca. 3, 2.5 and 2, respectively, with a further attenuating effect on the multiple bonding by the [Li(py)]+ ion coordination. Compounds 2 and 3 are the first examples of any group 4 metal simultaneously containing two or three multiply-bonded ligands.

Graphical abstract: The first group 4 metal bis(imido) and tris(imido) complexes

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The article was received on 11 Oct 2011, accepted on 09 Nov 2011 and first published on 09 Nov 2011

Article type: Edge Article
DOI: 10.1039/C1SC00786F
Citation: Chem. Sci., 2012,3, 819-824
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    The first group 4 metal bis(imido) and tris(imido) complexes

    A. D. Schwarz, A. J. Nielson, N. Kaltsoyannis and P. Mountford, Chem. Sci., 2012, 3, 819
    DOI: 10.1039/C1SC00786F

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