Mechanism of CO 2 Fixation by Ir I -X Bonds (X = OH, OR, N, C)

Sai V. C. Vummaleti, Giovanni Talarico, Steven P. Nolan, Luigi Cavallo, Albert Poater

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Original languageEnglish (US)
Pages (from-to)4653-4657
Number of pages5
JournalEuropean Journal of Inorganic Chemistry
Volume2015
Issue number28
DOIs
StatePublished - Sep 8 2015

Fingerprint Dive into the research topics of 'Mechanism of CO 2 Fixation by Ir I -X Bonds (X = OH, OR, N, C)'. Together they form a unique fingerprint.

Cite this