DUGi

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

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@298696

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)

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