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Issue 11, 2014
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[IrCl{N(CHCHPtBu2)2}]: a versatile source of the IrI(PNP) pincer platform

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The iridium(II) complex [IrCl{N(CHCHPtBu2)2}] is reduced by KC8 to give the anionic iridium(I) pincer complex [IrCl{N(CHCHPtBu2)2}] which was isolated and fully characterized upon stabilization of the counter cation with crown ether as [K(15-cr-5)2][IrCl{N(CHCHPtBu2)2}]. This unprecedented anionic iridium(I) pincer complex completes the unusual, structurally characterized IrI/IrII/IrIII redox series [IrCl{N(CHCHPtBu2)2}]−/0/+, all in a square-planar coordination geometry, emphasizing the versatility of this PNP pincer ligand in stabilizing a broad range of oxidation states. The anionic chloro complex is a versatile source of the Ir(PNP) platform. Its reactivity was examined towards chloride ligand substitution against CO and N2, and oxidative addition of C-electrophiles, C–H bonds and dioxygen, allowing for the isolation of iridium(I) and iridium(III) (PNP) carbonyl, hydrocarbyl and peroxo complexes which were spectroscopically and crystallographically characterized.

Graphical abstract: [IrCl{N(CHCHPtBu2)2}]−: a versatile source of the IrI(PNP) pincer platform

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The article was received on 22 Nov 2013, accepted on 18 Dec 2013 and first published on 19 Dec 2013

Article type: Paper
DOI: 10.1039/C3DT53304B
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Citation: Dalton Trans., 2014,43, 4506-4513
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    [IrCl{N(CHCHPtBu2)2}]: a versatile source of the IrI(PNP) pincer platform

    M. Kinauer, M. G. Scheibel, J. Abbenseth, F. W. Heinemann, P. Stollberg, C. Würtele and S. Schneider, Dalton Trans., 2014, 43, 4506
    DOI: 10.1039/C3DT53304B

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