Alcoholysis of Titanium Alkoxides by Fluoroalcohols. Synthesis, Characterization and X-Ray Crystal Structure of [Ti (O-i-Pr)2{OCH(CF3)2}2]2

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Abstract
Reaction of 2 equiv. of hexafluoro-2-propanol in hexane with tetrakis-isopropoxy titanium (IV) results in the formation of Ti(O-i-Pr)2[OCH(CF3)2]2, a volatile complex which has been characterized by a number of techniques, including X-ray crystallography [space group P21/n; a = 9.786(3) Å, b = 18.393(6) Å, c = 10.755 Å, β = 103.64(1)°; Z = 2]. The molecule adopts a dinuclcar structure in which oxygen atoms of isopropoxidc ligands are asymmetrically bridging [1.900(2) and 2.120(2) Å] between the titanium atoms. The coordination geometry about the titanium atoms is roughly that of a trigonal bipyramid with the short interactions of the bridging alkoxtdes occupying equatorial positions and the longer interactions occupying axial positions. The Ti-O distance [1.752(2) Å] of the terminal isopropoxy ligand is significantly shorter than the Ti-O distances [1.84(1) Å (avg)] of the terminal fluoroalkoxide ligands. NMR data and mass spectral data suggest that this complex is monomene both in solution and in the gas-phase.