University of Illinois Urbana-Champaign

Low-nuclearity titanium alkoxides and their rhodium derivatives

Hao, Jinling

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Description

Title
Low-nuclearity titanium alkoxides and their rhodium derivatives
Author(s)
Hao, Jinling
Issue Date
1994
Doctoral Committee Chair(s)
Klemperer, Walter G.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
  • Chemistry, Inorganic
  • Chemistry, Physical
Language
eng
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.
Type of Resource
text
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http://hdl.handle.net/2142/19753
Copyright and License Information
Copyright 1994 Hao, Jinling

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