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Reactivity of dialkylzirconium species and solvent polarity
Author(s) -
Derat Etienne,
Bouquant James,
Bertus Philippe,
Szymoniak Jan,
Humbel Stéphane
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20834
Subject(s) - alkene , chemistry , solvent , polar , reactivity (psychology) , reagent , polarity (international relations) , formaldehyde , solvent effects , solvent polarity , organic chemistry , computational chemistry , photochemistry , catalysis , medicine , biochemistry , physics , alternative medicine , pathology , astronomy , cell
The specific solvent effect of dimethylether is studied for two possible chemical reactions involving dialkylzirconium (ZrCl 2 Et 2 ) and formaldehyde (H 2 CO). Using Density Functional Theory (B3LYP) and qualitative arguments, it is shown that such a polar solvent favors the ZrCl 2 (Alkene) formation by coordinating to the metal. Such a stable system can react further through alkene—solvent—formaldehyde exchange to spontaneously give the cyclization product. In a polar solvent, where such coordination cannot be envisaged, the preferred path gives the hydrometalated product directly from the dialkylzirconium reagent. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006