2-Phosphinothioyl- and 2-phosphinoylethylcyclopentadienyl zirconium and titanium complexes. Crystal structure of [η5:η1-C5H4CH2CH2P(O)Ph2]TiCl3 |
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Authors: | D. P. Krut ko, M. V. Borzov, E. N. Veksler A. V. Churakov |
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Affiliation: | (1) Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russian Federation;(2) N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 119991 Moscow, Russian Federation;(3) N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow, Russian Federation |
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Abstract: | The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η5-C5H5)[η 5-C5H4CH2CH2P(S)Ph2]ZrCl2, [η5-C5H4CH2CH2P(S)Ph2]ZrCl3, [η5:η1C5H4CH2CH2P(O)Ph2]ZrCl3·THF, and [η5:η 1-C5H4CH2CH2P(O)Ph2]TiCl3 (7), was performed. The NMR spectroscopy data revealed the following order of the coordination ability of the functional groups with respect to the Zr center: Ph2P=O > Ph2P > Ph2P=S. An analogous order was found for the monodentate ligands (Ph3P=O > Ph3P > Ph3P=S) with respect to (η5-C5H5)ZrCl3. The molecular structure of complex 7 was established by X-ray diffraction analysis. Coordination of the Ph2P=O group to the titanium atom was found retained both in the crystalline state and solution.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116–122, January, 2005. |
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Keywords: | zirconium titanium 2-thiophosphanoylethylcyclopentadienes 2-phosphanoylethylcyclopentadienes intramolecular coordination NMR spectroscopy X-ray diffraction analysis |
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