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

Markus Kinauer; Markus G. Scheibel; J. Abbenseth; Frank W. Heinemann; Peter  Stollberg; C. Würtele; S. Schneider

doi:10.1039/c3dt53304b

[IrCl{N(CHCHPtBu₂)₂}]^-: A versatile source of the Ir^I(PNP) pincer platform

Markus Kinauer, Markus G. Scheibel, J. Abbenseth, Frank W. Heinemann, Peter Stollberg, C. Würtele, S. Schneider^*

^*Corresponding author for this work

Inorganic Chemistry Group

Research output: Contribution to journal › Article › peer-review

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 Ir^I/Ir^II/Ir^III 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.

Original language	English
Pages (from-to)	4506-4513
Number of pages	8
Journal	Dalton Transactions
Volume	43
Issue number	11
Early online date	19 Dec 2013
DOIs	https://doi.org/10.1039/c3dt53304b
Publication status	Published - 21 Mar 2015

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title = "[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.",

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T2 - A versatile source of the IrI(PNP) pincer platform

AU - Kinauer, Markus

AU - Scheibel, Markus G.

AU - Abbenseth, J.

AU - Heinemann, Frank W.

AU - Stollberg, Peter

AU - Würtele, C.

AU - Schneider, S.

PY - 2015/3/21

Y1 - 2015/3/21

N2 - 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.

AB - 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.

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[IrCl{N(CHCHPtBu₂)₂}]^-: A versatile source of the Ir^I(PNP) pincer platform

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