title: Acid-catalyzed oxidative addition of a C-H bond to a square planar d⁸ iridium complex.
abstract: While the addition of C-H bonds to three-coordinate Ir(I) fragments is a central theme in the field of C-H bond activation, addition to square planar four-coordinate complexes is far less precedented. The dearth of such reactions may be attributed, at least in part, to kinetic factors elucidated in seminal work by Hoffmann. C-H additions to square planar carbonyl complexes in particular are unprecedented, in contrast to the extensive chemistry of oxidative addition of other substrates (e.g., H2, HX) to Vaska's Complex and related species. We report that Bronsted acids will catalyze the addition of the alkynyl C-H bond of phenylacetylene to the pincer complex (PCP)Ir(CO). The reaction occurs to give exclusively the trans-C-H addition product. Our proposed mechanism, based on kinetics and DFT calculations, involves initial protonation of (PCP)Ir(CO) to generate a highly active five-coordinate cationic intermediate, which forms a phenylacetylene adduct that is then deprotonated to give product.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors.forename: Jason D
authors.initials: JD
authors.lastname: Hackenberg
authors.forename: Sabuj
authors.initials: S
authors.lastname: Kundu
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Emge
authors.forename: Karsten
authors.initials: K
authors.lastname: Krogh-Jespersen
authors.forename: Alan S
authors.initials: AS
authors.lastname: Goldman