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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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Date
2015
Author
Truscott, Byron
Kruger, Hedi
Webb, Paul Brian
Buehl, Michael
Nolan, Steven Patrick
Keywords
Carbon dioxide
Iridium
Mechanistic study
Kinetic
DFT
Thermodynamic
QD Chemistry
NDAS
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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
Citation
Truscott , B , Kruger , H , Webb , P B , Buehl , M & Nolan , S P 2015 , ' The mechanism of CO 2 insertion into iridium(I) hydroxide and alkoxide bonds : a kinetic and computational study ' , Chemistry - A European Journal . https://doi.org/10.1002/chem.201406509
Publication
Chemistry - A European Journal
Status
Peer reviewed
DOI
https://doi.org/10.1002/chem.201406509
ISSN
0947-6539
Type
Journal article
Rights
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
Description
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.
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  • University of St Andrews Research
URL
http://onlinelibrary.wiley.com/doi/10.1002/chem.201406509/suppinfo
URI
http://hdl.handle.net/10023/8441

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