Author:
Lam Chiu T.,Senoff Caesar V.
Abstract
The kinetics of the reaction between trans-[IrCl(CO)(PPh3)2] and a series of 2,4-dinitrophenyl-4-substituted-phenyl disulfides, YC6H4SSC6H3(NO2)2 (Y = Br, F, H, CH3, or CH3O) have been investigated in toluene between 70 and 90°. These reactions were found to follow simple second order kinetics, rate = k2[IrCl(CO)(PPh3)2][YC6H4SSC6H3(NO2)2]. The rates of reaction were also found to be insensitive to the nature of the para substituent, Y. This fact together with the observed activation parameters, ΔH≠ ~ 17 kcal mol−1 and ΔS≠ ~ − 19 cal mol−1 deg−1, have been interpreted as indicating that the initial step in these reactions involves a nucleophilic attack by the iridium atom at the sulfur atom bonded to the 2,4-dinitrophenyl group, followed by the formation of a three-centered transition state. An overall mechanism for these reactions is presented and discussed.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
17 articles.
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