Original scientific paper

Kinetics and Mechanism of the Reaction between Mercury(II) and a Series of Macrocyclic Organochromium Cations

Vjera Butković ; Ruđer Bosković Institute, P.O. Box 180, 10002 Zagreb, Croatia
Andreja Bakač ; Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA
James H. Espenson ; Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA

Abstract

Kinetic data are presented for the reaction of alkylchromium complexes (H₂O)([14]aneN₄)CrR2+ ([14]aneN₄ = 1,4,8,11-tetraazacyclo-tetradecane) with Hg2+ via electrophilic substitution. The rate constants decrease in the order CH₃ (1.1 × 106 mol-1 dm3 s-1) > C₂H₅ (7.7 × 102) > C₃H₇ (59) > 2-C₃H₇ (0.12) > CH₂C(CH₃)₃ (0.0086). A series of meta and para substituted benzyl complexes obey a Ham-mett relationship with the reaction constant ρ = -1.66, consistent with electrophilic substitution at α-carbon.

Keywords

alkylchromium; electrophilic substitution; mercury(II); kinetics

Hrčak ID:

131938

URI

https://hrcak.srce.hr/131938

Publication date:

1.8.2001.

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