Issue 11, 2014

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

Abstract

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

Supplementary files

Article information

Article type
Paper
Submitted
22 Nov 2013
Accepted
18 Dec 2013
First published
19 Dec 2013

Dalton Trans., 2014,43, 4506-4513

Author version available

[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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