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Low-nuclearity titanium alkoxides and their rhodium derivatives text Klemperer, Walter G. Hao, Jinling 2011-05-07T12:17:27Z 2011-05-07T12:17:27Z 10000-01-01 1994 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. Made available in DSpace on 2011-05-07T12:17:27Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9503209.pdf: 2964140 bytes, checksum: 14cc5ec3fbe88c13c767ad06303eda51 (MD5) Previous issue date: 1994 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:39:12Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:16:27-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission ETDs are only available to UIUC Users without author permission U of I Only AAI9503209 (UMI)AAI9503209 http://hdl.handle.net/2142/19753 eng Copyright 1994 Hao, Jinling Chemistry, Inorganic Chemistry, Physical Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.