Iridium: Organometallic Chemistry

Abstract

The organometallic chemistry of iridium is reviewed. The general classes of complexes of iridium containing iridium to carbon bonds are surveyed. The preparations of iridium olefin complexes, iridium arene complexes, iridium carbonyl complexes, iridium cyclopentadienyl complexes, and other types of complexes are covered along with the use of those classes of compounds in preparing other organometallic iridium species. In addition, three areas in which organoiridium compounds find particular application are specifically reviewed: catalysis utilizing organometallic compounds of iridium, carbon–hydrogen (CH) bond activation chemistry with iridium, and hydrodesulfurization (HDS) studies using iridium. References to other reviews, to monographs, and to the primary literature are provided in all cases.

Synthesis of Pentamethylcyclopentadienyl Dialkynyl Phosphane Iridium(III) complexes. Reactivity of the Complex [Ir(η5-C5Me5)(C≡CPh)2(PPh3)] toward Electrophiles

“…Initially, the intramolecular coupling ([1,2]­metal-to-carbon alkynyl migration) from the transient vinylidene species A , generated “in situ” by the electrophilic methylation of an alkynyl unit, with the remaining alkynyl ligand would provide the intermediate complex B . Then, the intramolecular ortho metalation of the phenyl group (oxidative C–H addition) would lead to the Ir­(V) complex C . Finally, the reductive elimination (to give complex D ) followed by metal alkyne/metal allene isomerization would provide the Z and E isomers 6 and 7 .…”