期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 28, 页码 4653-4657出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201500905
关键词
Density functional calculations; Homogeneous catalysis; Green chemistry; Iridium; Carbon dioxide fixation
资金
- Spanish Ministerio de Economia y Competitividad (MINECO) [CTQ2014-59832-JIN]
- European Commission for a Career Integration Grant [CIG09-GA-2011-293900]
- King Abdullah University of Science and Technology (CCF project)
- King Abdullah University of Science and Technology (KAUST) [KAUST-2015-C0546]
Density functional theory calculations have been used to investigate the CO2 fixation mechanism proposed by Nolan et al. for the Ir-I 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 (R-1 = 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.
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