The mechanism of CO2 insertion into iridium(I) hydroxide and alkoxide bonds: a kinetic and computational study

Byron Truscott; Hedi  Kruger; Paul Brian Webb; Michael Buehl; Steven Patrick Nolan

doi:10.1002/chem.201406509

The mechanism of CO₂ insertion into iridium(I) hydroxide and alkoxide bonds: a kinetic and computational study

Byron Truscott, Hedi Kruger, Paul Brian Webb, Michael Buehl, Steven Patrick Nolan

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

Abstract

The facile insertion of CO₂ into iridium(I) hydroxide, alkoxide, and amide bonds was recently reported. In particular, [Ir(cod)(IiPr)(OH)] (IiPr=1,3-bis(isopropyl)imidazol-2-ylidene) reacted with CO₂ in solution and in the solid state in a matter of minutes to give the novel [{Ir(cod)(IiPr)}₂(μ-κ¹O:κ²O,O-CO₃)] complex. In the present study, this reaction is probed using kinetics and theoretical studies, which enabled us to analyse its facile nature and to fully elucidate the reaction mechanism with excellent correlation between the two methods

Original language	English
Journal	Chemistry - A European Journal
Early online date	20 Mar 2015
DOIs	https://doi.org/10.1002/chem.201406509
Publication status	Published - 2015

Keywords

Carbon dioxide
Iridium
Mechanistic study
Kinetic
DFT
Thermodynamic

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10.1002/chem.201406509

Nolan_2015_ChemEU_Shedding_AM
Copyright 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: Truscott, B. J., Kruger, H., Webb, P. B., Bühl, M. and Nolan, S. P. (2015), The Mechanism of CO2 Insertion into Iridium(I) Hydroxide and Alkoxide Bonds: A Kinetics and Computational Study. Chem. Eur. J., which has been published in final form at: http://onlinelibrary.wiley.com/doi/10.1002/chem.201406509/abstract
Accepted author manuscript, 735 KB

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@article{a8cbd43458d74dad918d35d50258864a,

title = "The mechanism of CO2 insertion into iridium(I) hydroxide and alkoxide bonds: a kinetic and computational study",

abstract = "The facile insertion of CO2 into iridium(I) hydroxide, alkoxide, and amide bonds was recently reported. In particular, [Ir(cod)(IiPr)(OH)] (IiPr=1,3-bis(isopropyl)imidazol-2-ylidene) reacted with CO2 in solution and in the solid state in a matter of minutes to give the novel [\{Ir(cod)(IiPr)\}2(μ-κ1O:κ2O,O-CO3)] complex. In the present study, this reaction is probed using kinetics and theoretical studies, which enabled us to analyse its facile nature and to fully elucidate the reaction mechanism with excellent correlation between the two methods",

keywords = "Carbon dioxide , Iridium, Mechanistic study , Kinetic, DFT, Thermodynamic",

author = "Byron Truscott and Hedi Kruger and Webb, \{Paul Brian\} and Michael Buehl and Nolan, \{Steven Patrick\}",

note = "The ERC (Advanced Researcher Award FUNCAT to SPN), the EPSRC and Sasol technology (Stipend to BJT) are gratefully acknowledged for support. Umicore AG are thanked for their generous gift of materials. SPN is a Royal Society Wolfson Award holder. PBW holds a Royal Society Industry Fellowship.",

year = "2015",

doi = "10.1002/chem.201406509",

language = "English",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons, Ltd",

}

TY - JOUR

T1 - The mechanism of CO2 insertion into iridium(I) hydroxide and alkoxide bonds

T2 - a kinetic and computational study

AU - Truscott, Byron

AU - Kruger, Hedi

AU - Webb, Paul Brian

AU - Buehl, Michael

AU - Nolan, Steven Patrick

N1 - The ERC (Advanced Researcher Award FUNCAT to SPN), the EPSRC and Sasol technology (Stipend to BJT) are gratefully acknowledged for support. Umicore AG are thanked for their generous gift of materials. SPN is a Royal Society Wolfson Award holder. PBW holds a Royal Society Industry Fellowship.

PY - 2015

Y1 - 2015

N2 - The facile insertion of CO2 into iridium(I) hydroxide, alkoxide, and amide bonds was recently reported. In particular, [Ir(cod)(IiPr)(OH)] (IiPr=1,3-bis(isopropyl)imidazol-2-ylidene) reacted with CO2 in solution and in the solid state in a matter of minutes to give the novel [{Ir(cod)(IiPr)}2(μ-κ1O:κ2O,O-CO3)] complex. In the present study, this reaction is probed using kinetics and theoretical studies, which enabled us to analyse its facile nature and to fully elucidate the reaction mechanism with excellent correlation between the two methods

AB - The facile insertion of CO2 into iridium(I) hydroxide, alkoxide, and amide bonds was recently reported. In particular, [Ir(cod)(IiPr)(OH)] (IiPr=1,3-bis(isopropyl)imidazol-2-ylidene) reacted with CO2 in solution and in the solid state in a matter of minutes to give the novel [{Ir(cod)(IiPr)}2(μ-κ1O:κ2O,O-CO3)] complex. In the present study, this reaction is probed using kinetics and theoretical studies, which enabled us to analyse its facile nature and to fully elucidate the reaction mechanism with excellent correlation between the two methods

KW - Carbon dioxide

KW - Iridium

KW - Mechanistic study

KW - Kinetic

KW - DFT

KW - Thermodynamic

UR - http://onlinelibrary.wiley.com/doi/10.1002/chem.201406509/suppinfo

UR - https://www.scopus.com/pages/publications/84927670005

U2 - 10.1002/chem.201406509

DO - 10.1002/chem.201406509

M3 - Article

SN - 0947-6539

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

ER -

The mechanism of CO₂ insertion into iridium(I) hydroxide and alkoxide bonds: a kinetic and computational study

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FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis

Paul Webb

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The mechanism of CO2 insertion into iridium(I) hydroxide and alkoxide bonds: a kinetic and computational study

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FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis

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Paul Webb

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The mechanism of CO₂ insertion into iridium(I) hydroxide and alkoxide bonds: a kinetic and computational study