The first group 4 metal bis(imido) and tris(imido) complexes
The first group 4 metal bis(imido) and tris(imido) complexes
复制标题
DOI：
10.1039/c1sc00786f
复制
发表时间：
2012-02
期刊：
影响因子：
8.4
通讯作者：
Andrew D. Schwarz;A. J. Nielson;N. Kaltsoyannis;P. Mountford
中科院分区：
文献类型：
--
作者：
Andrew D. Schwarz;A. J. Nielson;N. Kaltsoyannis;P. Mountford
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.
