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How easy is CO2 fixation by M–C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?

A comparison between different M–C bonds (M = Cu(I), Ni(II), Co(I), Rh(I) and Ir(I)) has been reported by using density functional theory (DFT) calculations to explore the role of the metal in the fixation or incorporation of CO2 into such complexes. The systems investigated are various metal based congeners of the Ir-complex 8 [(cod)(IiPr)Ir-CCPh], with a ligand scaffold based on cod and IiPr ligands (cod = 1,5-cyclooctadiene; IiPr = 1,3-bis(isopropyl)imidazol-2-ylidene). The results of this study show that the calculated CO2 insertion barriers follow the trend: Cu(I) (20.8 kcal mol−1) < Rh(I) (30.0 kcal mol−1) < Co(I) (31.3 kcal mol−1) < Ir(I) (37.5 kcal mol−1) < Ni(II) (45.4 kcal mol−1), indicating that the Cu(I) based analogue is the best CO2 fixer, while Ni(II) is the worst in the studied series

A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN, and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

Royal Society of Chemistry

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Vummaleti, Sai Vikrama Chaitanya
Talarico, Giovanni
Nolan, Steven P.
Cavallo, Luigi
Poater Teixidor, Albert
Abstract: A comparison between different M–C bonds (M = Cu(I), Ni(II), Co(I), Rh(I) and Ir(I)) has been reported by using density functional theory (DFT) calculations to explore the role of the metal in the fixation or incorporation of CO2 into such complexes. The systems investigated are various metal based congeners of the Ir-complex 8 [(cod)(IiPr)Ir-CCPh], with a ligand scaffold based on cod and IiPr ligands (cod = 1,5-cyclooctadiene; IiPr = 1,3-bis(isopropyl)imidazol-2-ylidene). The results of this study show that the calculated CO2 insertion barriers follow the trend: Cu(I) (20.8 kcal mol−1) < Rh(I) (30.0 kcal mol−1) < Co(I) (31.3 kcal mol−1) < Ir(I) (37.5 kcal mol−1) < Ni(II) (45.4 kcal mol−1), indicating that the Cu(I) based analogue is the best CO2 fixer, while Ni(II) is the worst in the studied series
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN, and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Document access: http://hdl.handle.net/2072/298694
Language: eng
Publisher: Royal Society of Chemistry
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Title: How easy is CO2 fixation by M–C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?
Type: info:eu-repo/semantics/article
Repository: Recercat

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