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Kinetics and mechanism of the reaction between mercury(II) and a series of macrocyclic organochromium cations

Butković, Vjera; Bakač, Andreja; Espenson, James H. (2001) Kinetics and mechanism of the reaction between mercury(II) and a series of macrocyclic organochromium cations. Croatica Chemica Acta, 74 (3). pp. 735-741. ISSN 0011-1643

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Abstract

Kinetic data are presented for the reaction of alkylchromium complexes (H2O)([14]aneN(4))CrR2+ ([14]aneN(4) = 1,4,8,11-tetraazacyclotetradecane) with Hg2+ via electrophilic substitution. The rate constants decrease in the order CH3 (1.1 x 10(6) mol(-1) dm(3) s(-1)) > C2H5 (7.7 x 10(2)) > C3H7 (59) > 2-C3H7 (0.12) > CH2C(CH3)(3) (0.0086). A series of meta and para substituted benzyl complexes obey a Hammett relationship with the reaction constant rho = -1.66, consistent with electrophilic substitution at alpha -carbon.

Item Type: Article
Uncontrolled Keywords: alkylchromium; electrophilic substitution; mercury(II); kinetics; complexes; hydrolysis; cleavage
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Physical Chemistry
Depositing User: Vjera Butković
Date Deposited: 19 Nov 2013 14:51
Last Modified: 28 Feb 2014 16:13
URI: http://fulir.irb.hr/id/eprint/985

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