Kinetics of the Addition of Hydrogen, Oxygen, and Methyl Iodide to Some Square-Planar Iridium(I) Complexes¹

Abstract

these are the two basic papers in this field; other isolated references have appeared since).tion to give the methylnitrilium ion CH3C==NCH3+ occurs to the extent of about 90%. Similar results were obtained from the infrared spectra taken in this solvents.Trimethylsulfonium hexafluorophosphate did not react with acetonitrile. However, a slow reaction of (CH3)2SSCH3+PF6-was observed in this solvent. No product was characterized from this reaction.Acknowledgment. We are pleased to acknowledge the partial support for this work provided by the Wisconsin Alumni Research Foundation. We are indebted to Miss P. Carney for assistance in running the proton nmr spectra.

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

“…were too fast to be reliably monitored with the available instrumentation. This order of reactivity parallels that observed for the reactions of H, and 0, with these iridium(1) complexes (4,6,7). The rates of reaction also varied with the nature of the para-substituent on the benzenethiol; the trend is towards an increase in rate as the acidity of the substituted benzenethiol increases (14).…”

“…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).…”

Activation entropy as a dominant factor in the oxidative addition of some group IV hydrides to an iridium(I) complex

“…A natural approach to avoiding such -'The values of AN" and AS' were both found to increase considerably for the addition of CH,I to Ir(CO)@l(PBh,),, on going from benzene to dirnethylformamide (6).…”

Oxidative Addition von H2 und HCl an Iridium-Schwefelmonoxid- und Schwefeldioxid-Komplexe/ Oxidative Addition von H2 und HCl an Iridium-Schwefelmonoxid- und Schwefeldioxid-Komplexe

“…E indeutig belegt sind bisher nu r die O xidation zu S 0 2-K om plexen [4,5] sowie die schon erw äh n te A d dition von C O an die V erbindungen l a und l b [4], die letztlich zur F reisetzung des k o o rd in ie rte n SO füh rt [1 ], Die A nlagerung von H 2 an quadratisch -p lan are d8-K om plexe verläuft generell einstufig und fü h rt k in e tisch k o n trolliert zu cis-A d d itio n sp ro d u k ten [9], wie es auch im hier vorliegenden Fall b eo b a ch tet w ird. D ie A ddition von H alogenw asserstoff kann dagegen, abhängig von d er P o larität des L ösungsm ittels, eino d er zweistufig verlaufen [18]. L etzteres eröffnet einen W eg zur trans-A d d itio n , es ist jedoch zu b e achten, daß die S tereochem ie des E n d p ro d u k tes nicht notw endigerw eise die des P rim ärschrittes w ie dergibt [19].…”