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Mechanism of CO2 Fixation by IrI–X Bonds (X = OH, OR, N, C)

KGaA, Weinheim.Density functional theory calculations have been used to investigate the CO2 fixation mechanism proposed by Nolan et al. for the IrI complex [Ir(cod)(IiPr)(OH)] (1; cod = 1,5-cyclooctadiene; IiPr = 1,3-diisopropylimidazol-2-ylidene) and its derivatives. For 1, our results suggest that CO2 insertion is the rate-limiting step rather than the dimerization step. Additionally, in agreement with the experimental results, our results show that CO2 insertion into the Ir-OR1 (R1 = H, methyl, and phenyl) and Ir-N bonds is kinetically facile, and the calculated activation energies span a range of only 12.0-23.0 kcal/mol. Substantially higher values (35.0-50.0 kcal/mol) are reported for analogous Ir-C bonds

A. P. thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for grant CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

Wiley-VCH Verlag

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Vummaleti, Sai Vikrama Chaitanya
Talarico, Giovanni
Nolan, Steven P.
Cavallo, Luigi
Poater Teixidor, Albert
Abstract: KGaA, Weinheim.Density functional theory calculations have been used to investigate the CO2 fixation mechanism proposed by Nolan et al. for the IrI complex [Ir(cod)(IiPr)(OH)] (1; cod = 1,5-cyclooctadiene; IiPr = 1,3-diisopropylimidazol-2-ylidene) and its derivatives. For 1, our results suggest that CO2 insertion is the rate-limiting step rather than the dimerization step. Additionally, in agreement with the experimental results, our results show that CO2 insertion into the Ir-OR1 (R1 = H, methyl, and phenyl) and Ir-N bonds is kinetically facile, and the calculated activation energies span a range of only 12.0-23.0 kcal/mol. Substantially higher values (35.0-50.0 kcal/mol) are reported for analogous Ir-C bonds
A. P. thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for grant CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
Document access: http://hdl.handle.net/10256/13296
Language: eng
Publisher: Wiley-VCH Verlag
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1002/ejic.201500905
info:eu-repo/semantics/altIdentifier/issn/1434-1948
info:eu-repo/semantics/altIdentifier/eissn/1099-0682
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Química verda
Green chemistry
Catàlisi homogènia
Homogeneous catalysis
Title: Mechanism of CO2 Fixation by IrI–X Bonds (X = OH, OR, N, C)
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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