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Updated: Feb 15, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Iridium complexes of perimidine-based N-heterocyclic carbene pincer ligands via aminal C-H activation
Anthony F Hill1, Chenxi Ma, Caitlin M A McQueen
1Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory, Australia. a.hill@anu.edu.au.
Abstract:
The reactions of N,N'-bis(phosphinomethyl)dihydroperimidine pro-ligands H2C(NCH2PR2)2C10H6-1,8 (R = Ph 1a, R = Cy 1b) with iridium(i) substrates have been investigated and shown to readily result in chelate-assisted C-H activation processes. The reaction of 1b with [Ir2Cl2(COE)4] (COE = cyclo-octene) affords the 18-electron iridium(iii) dihydrido complex [IrH2Cl{κ3-C,P,P'-C(NCH2PCy2)2C10H6}], which forms [IrHCl2{κ3-C,P,P'-C(NCH2PCy2)2C10H6}] under acidic (HCl) conditions. In contrast, reaction of 1a with [Ir2Cl2(COD)2] (COD = 1,5-cyclo-octadiene) affords the complex [IrCl(COD){κ2-P,P'-H2C(NCH2PPh2)2C10H6}], thermolysis of which affords cyclo-octene and the pincer-NHC complex [IrCl{κ3-C,P,P'-C(NCH2PPh2)2C10H6}]. The reaction of 1a with two equivalents of [Ir2Cl2(COD)2] provides the binuclear complex [Ir2{μ-H2C(NCH2PPh2)2C10H6}Cl2(COD)2] which is also observed to accumulate and then dissipate during the preceding thermolysis. Related binuclear complexes [M2{μ-H2C(NCH2PPh2)2C10H6}Cl4(η-C5Me5)2] (M = Ir, Rh) which obviate C-H activation were similarly synthesised.
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