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Mono- and bis-(2-dimethylaminoethyl)tetramethylcyclopentadienyl zirconium(IV) complexes: synthesis and structural studies in crystalline state and in solutions |
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| Authors: | Dmitrii P Krut’ko Maxim V Borzov Mikhail Yu Antipin |
| Institution: | a Department of Chemistry, M.V. Lomonosov, Moscow State University, Vorob’evy Gory, Moscow 119899, Russia b A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia c N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia |
| Abstract: | A novel half-sandwich Zr(IV) complex η5:η1-N-C5(CH3)4CH2CH2N(CH3)2]ZrCl3 (6) together with zirconocene dichlorides η5-C5(CH3)4CH2CH2N(CH3)2]η5-C5(CH3)5]ZrCl2 (4) and η5-C5(CH3)4CH2CH2N(CH3)2]2ZrCl2 (5) have been prepared. Complex 6 has been isolated and characterized in three different forms, namely, as an adduct with THF 6a, an adduct with tetrahydrothiophene 6b, and a solvent-free form 6c. Molecular structures of complexes 4, 6b, and 6c have been established by X-ray diffraction analysis. Complex 6c has been shown to be a monomeric solvent-free half sandwich Zr(IV) complex. The dynamic behavior of complex 6a in a non-solvating medium (an equilibrium between 6a and 6c along with a degenerate interconversion of the Zr-Ccp-CH2-CH2-N(CH3)2-(Zr) pseudo-five-member metallacycle) have been studied by the variable-temperature 1H and 13C{1H} NMR spectroscopy. The activation parameters for the degenerate five-member cycle interconversion have been elucidated. |
| Keywords: | Zirconium Cyclopentadienyl ligands Intramolecular coordination N ligands Dynamic behavior |
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