Exploring the Reactivity of C(sp³)‐Cyclometalated Ir^III Compounds in Hydrogen Transfer Reactions

Abstract

The manuscript describes the synthesis and full characterization of a new PC(sp(3))P-based cyclometalated Ir(III) complex that manifests an exceptional thermal stability, as well as outstanding reactivity in hydrogen transfer reactions. The described compound represents the first example of a new family of stable C(sp(3))-metalated compounds.

New PC(sp3)P pincer complexes of platinum and palladium

“…Moreover, they proved themself as highly active catalysts for the transfer hydrogenation of ketones [12], as well as transfer [16] and acceptorless dehydrogenation of alcohols [17].…”

Ion–Molecule Reactions of “Rollover” Cyclometalated [Pt(bipy−H)]+ (bipy=2,2′‐bipyridine) with Dimethyl Ether in Comparison with Dimethyl Sulfide: An Experimental/Computational Study

“…For example, Periana and coworkers investigated the heterolytic C À H bond activation of methane and benzene with a cyclometalated Pt II complex as well as catalytic methane hydroxylation using an Ir III NNC pincer complex in acidic solution; [7,8] another study deals with transfer hydrogenation mediated by a cyclometalated Ir III compound. [9] 2,2'-Bipyridine (bipy) and related heterocycles, which are versatile ligands in the coordination chemistry of transition metals, [10] are well suited for the formation of cyclometalated compounds. Moreover, it has been shown that cyclometalated [PtA C H T U N G T R E N N U N G (bipyÀH)] + (1) can formally dehydrosulfurize a variety of thioethers in the gas phase; [11] especially in the reaction with dimethyl sulfide, efficient oxidative C À C bond coupling and concomitant formation of neutral ethene was observed.…”

Cyclometalated Complexes of Ruthenium, Rhodium and Iridium as Catalysts for Transfer Hydrogenation of Ketones and Imines

“…[9] However, a few groups have recently described promising catalytic results using N À C À N, [10] P À C À P, [10a,11] C À P, [12] and C À N À N [13] cycloruthenated or cycloiridiated [14] ligands. Our contribution to this field was triggered by the discovery that cycloruthenated chiral benzylamines are also attractive catalyst precursors for the reduction of acetophenone.…”