UNSPECIFIED. (1994) CONTROLLED HYDROLYSIS REACTIONS OF SOLVATED [TICLN](4-N)+ SPECIES - CRYSTAL AND MOLECULAR-STRUCTURES OF [MG(MECN6][(TICL4-(MECN))2(MU-O).4MECN AND [(TICL2(MECN)2(MU-O))4].2MECN. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (12). pp. 1799-1804. ISSN 0300-9246

Abstract

Partial hydrolysis reactions of the solvated [TiCl5(MeCN)]- anion and of the adduct TiCl4.2MeCN gave the mu-oxo-dititanium anion [{TiCl4(MeCN))2(mu-O)]2- and the neutral tetranuclear mu-oxo compound [{TiCl2(MeCN)2(mu-O)}], respectively, as established by X-ray crystallographic studies. Crystals of [Mg(MeCN)6][{TiCl4(MeCN)}2(mu-O)].4MeCN 1 are monoclinic, space group P21/n, a = 14.777(6), b = 14.603(6), c = 21.214(10) angstrom, beta = 105.3(1)-degrees. The structure contains discrete octahedral [Mg(MeCN)6]2+ cations, [{TiCl4(MeCN)}2(mu-O)]2- anions and solvent (MeCN) molecules. Crystals of [{TiCl2(MeCN)2(mu-O)}4].2MeCN 2 are orthorhombic, space group P2(1)2(1)2(1) a = 12.165(6), b = 12.367(6), c = 27.927(11) angstrom. The structure contains discrete [{TiCl2(MeCN)2(mu-O)}4] units and solvent (MeCN) molecules. In 1 both titanium atoms have an octahedral environment. The Ti-O-Ti bridge is approximately linear [174.7(3)-degrees] with equivalent Ti-O distances of 1.783(4) and 1.764(4) angstrom. By contrast in 2 there are four Ti-O-Ti bridges but in each case the two Ti-O distances are significantly different with mean values of 1.668, 1.954 angstrom.

Data sourced from Thomson Reuters' Web of Knowledge

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