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  Reduction of CO2 by a masked two-coordinate cobalt(I) complex and characterization of a proposed oxodicobalt(II) intermediate

Roy, L., Al-Afyouni, M. H., DeRosha, D. E., Mondal, B., DiMucci, I. M., Lancaster, K. M., et al. (2019). Reduction of CO2 by a masked two-coordinate cobalt(I) complex and characterization of a proposed oxodicobalt(II) intermediate. Chemical Science, 10(3), 918-929. doi:10.1039/C8SC02599A.

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Roy, Lisa1, 2, Author
Al-Afyouni, Malik H. 3, Author
DeRosha, Daniel E. 4, Author
Mondal, Bhaskar1, Author
DiMucci, Ida M. 5, Author
Lancaster, Kyle M. 5, Author
Shearer, Jason6, Author
Bill, Eckhard7, Author           
Brennessel, William W. 3, Author
Neese, Frank8, Author           
Ye, Shengfa9, Author           
Holland, Patrick L.4, Author
1Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, Mülheim an der Ruhr, Germany , ou_persistent22              
2CSIR Central Mechanical Engineering Research Institute, Durgapur 713209, India, ou_persistent22              
3Department of Chemistry, University of Rochester, Rochester, USA , ou_persistent22              
4Department of Chemistry, Yale University, New Haven, USA, ou_persistent22              
5Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, USA , ou_persistent22              
6Department of Chemistry, Trinity University, San Antonio, USA , ou_persistent22              
7Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
8Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
9Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              


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 Abstract: Fixation and chemical reduction of CO2 are important for utilization of this abundant resource, and understanding the detailed mechanism of C–O cleavage is needed for rational development of CO2 reduction methods. Here, we describe a detailed analysis of the mechanism of the reaction of a masked two-coordinate cobalt(I) complex, LtBuCo (where LtBu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO2, which yields two products of C–O cleavage, the cobalt(I) monocarbonyl complex LtBuCo(CO) and the dicobalt(II) carbonate complex (LtBuCo)2(μ-CO3). Kinetic studies and computations show that the κN,η6-arene isomer of LtBuCo rearranges to the κ2N,N′ binding mode prior to binding of CO2, which contrasts with the mechanism of binding of other substrates to LtBuCo. Density functional theory (DFT) studies show that the only low-energy pathways for cleavage of CO2 proceed through bimetallic mechanisms, and DFT and highly correlated domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) calculations reveal the cooperative effects of the two metal centers during facile C–O bond rupture. A plausible intermediate in the reaction of CO2 with LtBuCo is the oxodicobalt(II) complex LtBuCoOCoLtBu, which has been independently synthesized through the reaction of LtBuCo with N2O. The rapid reaction of LtBuCoOCoLtBu with CO2 to form the carbonate product indicates that the oxo species is kinetically competent to be an intermediate during CO2 cleavage by LtBuCo. LtBuCoOCoLtBu is a novel example of a thoroughly characterized molecular cobalt–oxo complex where the cobalt ions are clearly in the +2 oxidation state. Its nucleophilic reactivity is a consequence of high charge localization on the μ-oxo ligand between two antiferromagnetically coupled high-spin cobalt(II) centers, as characterized by DFT and multireference complete active space self-consistent field (CASSCF) calculations.


Language(s): eng - English
 Dates: 2018-11-092019-01-21
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C8SC02599A
 Degree: -



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Title: Chemical Science
  Other : Chem. Sci.
Source Genre: Journal
Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 10 (3) Sequence Number: - Start / End Page: 918 - 929 Identifier: ISSN: 2041-6520
CoNE: https://pure.mpg.de/cone/journals/resource/2041-6520