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)

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 bonds
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11588/658544
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