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
Mechanism of CO2 Fixation by IrI–X Bonds (X = OH, OR, N, C) / Vummaleti, Sai Vikrama Chaitanya; Talarico, Giovanni; Nolan, Steven P.; Cavallo, Luigi; Poater, Albert. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1099-0682. - 2015:28(2015), pp. 4653-4657. [10.1002/ejic.201500905]
Mechanism of CO2 Fixation by IrI–X Bonds (X = OH, OR, N, C)
TALARICO, GIOVANNI;
2015
Abstract
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 bondsI documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
