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

Handle URI:
http://hdl.handle.net/10754/594107
Title:
Mechanism of CO 2 Fixation by Ir I -X Bonds (X = OH, OR, N, C)
Authors:
Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Talarico, Giovanni; Nolan, Steven P.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Poater, Albert
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
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:
Wiley-Blackwell
Journal:
European Journal of Inorganic Chemistry
Issue Date:
8-Sep-2015
DOI:
10.1002/ejic.201500905
Type:
Article
ISSN:
1434-1948
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorTalarico, Giovannien
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorPoater, Alberten
dc.date.accessioned2016-01-19T13:21:48Zen
dc.date.available2016-01-19T13:21:48Zen
dc.date.issued2015-09-08en
dc.identifier.citationVummaleti 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.en
dc.identifier.issn1434-1948en
dc.identifier.doi10.1002/ejic.201500905en
dc.identifier.urihttp://hdl.handle.net/10754/594107en
dc.description.abstractDensity 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.en
dc.publisherWiley-Blackwellen
dc.subjectCarbon dioxide fixationen
dc.subjectDensity functional calculationsen
dc.subjectGreen chemistryen
dc.subjectHomogeneous catalysisen
dc.subjectIridiumen
dc.titleMechanism of CO 2 Fixation by Ir I -X Bonds (X = OH, OR, N, C)en
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalEuropean Journal of Inorganic Chemistryen
dc.contributor.institutionDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italyen
dc.contributor.institutionChemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabiaen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
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