Type
ArticleKAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2015-09-08Online Publication Date
2015-09-08Print Publication Date
2015-10Permanent link to this record
http://hdl.handle.net/10754/594107
Metadata
Show full item recordAbstract
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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Citation
Vummaleti SVC, Talarico G, Nolan SP, Cavallo L, Poater A (2015) Mechanism of CO 2 Fixation by Ir I -X Bonds (X = OH, OR, N, C) . European Journal of Inorganic Chemistry 2015: 4653–4657. Available: http://dx.doi.org/10.1002/ejic.201500905.Publisher
Wileyae974a485f413a2113503eed53cd6c53
10.1002/ejic.201500905