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Title:Low-nuclearity titanium alkoxides and their rhodium derivatives
Author(s):Hao, Jinling
Doctoral Committee Chair(s):Klemperer, Walter G.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Inorganic
Chemistry, Physical
Abstract:The reaction of Ti(OPri)4 with 0.078 equiv. of 10 atom% 17O enriched water and 0.6 equiv. of MeOH in i-PrOH solution gave [Ti3O](OPr i)9(OMe) (1). A single crystal X-ray diffraction study of this material indicated that 1 contains two crystallographically-independent Ti3(mu3-O)(mu3-OMe)(mu2-OPr i)3(OPri)6 molecules. The analogous molecule [Ti3O[(OPri)10 (1a) was generated in solution by hydrolysis of Ti(OPri)4 with 0.02 equiv. of water in i-PrOH, and identified using 17O, 13C{1H}, and 1H NMR techniques. Variable temperature NMR spectroscopic studies show that 1 retains its solid state structure at low temperature. It decomposes quickly at room temperature, however, to form Ti(OMe)x(OPr i)4-x, and other polyoxotitanates. 1 has the lowest stability toward parent alcohol and inert hydrocarbon solvents among all known titanium polyoxoalkoxides.
The reaction of [Rh(COD)(OH)]2 with 3 equiv. of Ti(OPr n)4 affords [Rh(COD)]2Ti(OPrn) 6 (2). An X-ray diffraction study indicates that 2 adopts a butterfly structure with two Rh(COD) acting as wings. In solution, 2 exists in equilibrium with [Rh(COD)(OPrn)] 2 (2a), and Ti(OPrn)4. 2a can also be prepared from the reaction of [Rh(COD)(OH)]2 with one equiv. of Ti(OPrn)4.
The reaction of Ti(OMe)4 with 0.63 equiv. of [C6H 5CH2N(CH3)3]OCH3 in toluene/methanol gave analytically-pure [C6H5CH2N(CH 3)3][Ti2(OMe)9] (3). A face-shared bioctahedral solid state structure for anion Ti2(OMe) 9- is proposed based on its NMR spectroscopic properties.
Issue Date:1994
Rights Information:Copyright 1994 Hao, Jinling
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9503209
OCLC Identifier:(UMI)AAI9503209

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