Oxidative addition of hydrogen cyanide, hydrogen sulphide, and other acids to triphenylphosphine complexes of iridium(I) and rhodium(I)

Abstract

The interactions of hydrogen cyanide, hydrogen sulphide, toluene thiols, fluorocarboxylic, nitric, and perchloric acids with trans-chlorocarbonylbis(triphenylphosphine)iridium( I), and of some of these molecules with chlorotris-(triphenylphosphine)rhodium(l) and other iridium and rhodium complexes, have been studied. The products of oxidative addition, which normally have a metal-hydrogen bond, have been studied by infrared and n.m.r. spectroscopy as well as by chemical techniques.

A Kinetic Study of the Oxidative Addition of Substituted Benzenethiols Towards trans-Halocarbonylbis(triphenylphosphine)iridium(I)

“…Several kinetic studies have been carried out in order to ascertain the mechanism of the oxidative addition towards these particular substrates (4)(5)(6)(7)(8). Previous work from this laboratory as well as others has shown that substituted benzenethiols will oxidatively add to trans-[IrCl(CO)(Ph,P),] to form [IrHCl(SAr)(CO)-(Ph,P),] where -SAr is a substituted benzenethiolato ligand (9)(10)(11). As part of a general program investigating the reactivity of aromatic thiols towards low valent transition metal complexes, we have undertaken a kinetic study of reaction 1 where X = C1, Br, or I and Y = a para-substituent, NO,, F, C1, Br, H, CH,, or CH30.…”

O–H Activation and Addition to Unsaturated Systems

“…Wilkinson [55] (RF = CF 3 , C 2 F 5 ), but did not completely succeed in characterizing the products of the oxidative addition. The complex is claimed to be a mixture of four closely similar species by NMR.…”

Transition-Metal-Catalyzed S–H and Se–H Bonds Addition to Unsaturated Molecules

“…Equimolar reaction of Wilkinson's catalyst with PhSH is reported to afford transHRhCl(SPh)(PPh 3 ) 2 as yellow solid [55]. Attempted catalytic hydrothiolation of 1-dodecyne using trans-HRhCl(SPh)(PPh 3 ) 2 successfully provides anti-Markovnikov adduct 3 selectively.…”