A Kinetic Study of the Oxidative Addition of Substituted Benzenethiols Towards trans-Halocarbonylbis(triphenylphosphine)iridium(I)
- 15 June 1972
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 50 (12) , 1868-1873
- https://doi.org/10.1139/v72-299
Abstract
The kinetics of the oxidative addition of a series of para-substituted benzenethiols, HSC6H4Y, where Y = 4-NO2, 4-Br, 4-Cl, 4-F, 4-H, 4-CH3, or 4-CH3O towards the complexes, trans-IrX(CO)(Ph3P)2 where X = Cl, Br, or I have been studied in benzene between 15 and 45°. These reactions follow simple second order kinetics, rate = k2[IrX(CO)(Ph3P)2][HSC6H4Y]. The two principal factors which influence the rates of these reactions are the mesomeric and inductive effects of the para-substituent and the nature of the ligand, X, coordinated to iridium. The rate of reaction increases as the substituent becomes more electron withdrawing and as X varies from Cl to Br to I. The kinetic data together with spectroscopic data (i.r. and n.m.r.) suggest that oxidative addition proceeds via a three-centered activated complex to give the cis-product.Keywords
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