title: Oxygen-atom transfer from carbon dioxide to a Fischer carbene at (PNP)Ir.
abstract: Dehydrogenation of the dihydride (PNP)IrH2 with norbornylene in the presence of t-butyl methyl ether leads to formation of an iridium(I) Fischer carbene complex, (PNP)Ir C(H)OtBu, by double C-H activation and loss of H2. The square planar pincer-type carbene effects quantitative oxygen-atom transfer from CO2 (1 atm) at ambient temperature to generate t-butyl formate and (PNP)Ir-CO. The iridium carbene reacts similarly with carbonyl sulfide and phenyl isocyanate, causing sulfur-atom and nitrene-group transfer, respectively. In the absence of a hydrogen acceptor, thermolysis of (PNP)IrH2 in t-butyl methyl ether under an atmosphere of CO2 also results in the formation of (PNP)Ir-CO and oxidation of t-butyl methyl ether to t-butyl formate via an iridium carbene. Preliminary mechanistic studies indicate that these reactions proceed through an intermediate four-membered metallalactone.
authors.affiliation: Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Matthew T
authors.initials: MT
authors.lastname: Whited
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs