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Iridium complexes of perimidine-based N-heterocyclic carbene pincer ligands via aminal C–H activation

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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 [IrHCl23-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.

Graphical abstract: Iridium complexes of perimidine-based N-heterocyclic carbene pincer ligands via aminal C–H activation

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Publication details

The article was received on 04 Dec 2017, accepted on 23 Dec 2017 and first published on 03 Jan 2018


Article type: Paper
DOI: 10.1039/C7DT04572G
Citation: Dalton Trans., 2018, Advance Article
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    Iridium complexes of perimidine-based N-heterocyclic carbene pincer ligands via aminal C–H activation

    A. F. Hill, C. Ma, C. M. A. McQueen and J. S. Ward, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C7DT04572G

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