Ab initio calculations at the MP2 level show that the CH3-Hg bond is broken by halogenic acids by a one-step mechanism, proceeding through a closed transition state in which, however, bond forming and breaking are not completely synchronous. Activation energies closely parallel Hg-C bond strengths and are strongly influenced by the electronegativity of the ligands bound to Hg. For instance, the energy barrier decreases by roughly 50% on going from CH3HgCl to CH3HgCH3. The general agreement between computed and experimental trends gives further support to the reaction mechanism.

Theoretical Characterization of the Mechanism of Hg-C Bond Cleavage by Halogenic Acids / V. Barone; A. Bencini; F. Totti; M. G. Uytterhoeven. - In: ORGANOMETALLICS. - ISSN 0276-7333. - STAMPA. - 15:(1996), pp. 1465-1469. [10.1021/om9508391]

Theoretical Characterization of the Mechanism of Hg-C Bond Cleavage by Halogenic Acids

BENCINI, ALESSANDRO;TOTTI, FEDERICO;
1996

Abstract

Ab initio calculations at the MP2 level show that the CH3-Hg bond is broken by halogenic acids by a one-step mechanism, proceeding through a closed transition state in which, however, bond forming and breaking are not completely synchronous. Activation energies closely parallel Hg-C bond strengths and are strongly influenced by the electronegativity of the ligands bound to Hg. For instance, the energy barrier decreases by roughly 50% on going from CH3HgCl to CH3HgCH3. The general agreement between computed and experimental trends gives further support to the reaction mechanism.
1996
15
1465
1469
V. Barone; A. Bencini; F. Totti; M. G. Uytterhoeven
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/319291
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