skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate

Abstract

Fixation and chemical reduction of CO 2 are important for utilization of this abundant resource, and understanding the detailed mechanism of C–O cleavage is needed for rational development of CO 2 reduction methods. Here, we describe a detailed analysis of the mechanism of the reaction of a masked two-coordinate cobalt(I) complex, L tBuCo (where L tBu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO 2, which yields two products of C–O cleavage, the cobalt(I) monocarbonyl complex L tBuCo(CO) and the dicobalt(II) carbonate complex (L tBuCo) 2(μ-CO 3). Kinetic studies and computations show that the κN,η 6-arene isomer of L tBuCo rearranges to the κ 2N,N' binding mode prior to binding of CO 2, which contrasts with the mechanism of binding of other substrates to L tBuCo. Density functional theory (DFT) studies show that the only low-energy pathways for cleavage of CO 2 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 CO 2 with L tBuCo is the oxodicobalt(II) complex L tBuCoOCoL tBu, which has been independently synthesized through the reaction of L tBuComore » with N 2O. The rapid reaction of L tBuCoOCoL tBu with CO 2 to form the carbonate product indicates that the oxo species is kinetically competent to be an intermediate during CO 2 cleavage by L tBuCo. L tBuCoOCoL tBu 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.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [5]; ORCiD logo [6];  [4]; ORCiD logo [2];  [7]; ORCiD logo [7]; ORCiD logo [3]
  1. Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany, CSIR Central Mechanical Engineering Research Institute, Durgapur 713209
  2. Department of Chemistry, University of Rochester, Rochester, USA
  3. Department of Chemistry, Yale University, New Haven, USA
  4. Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany
  5. Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, USA
  6. Department of Chemistry, Trinity University, San Antonio, USA
  7. Max Planck Institute for Coal Research, Mülheim an der Ruhr, Germany
Publication Date:
Research Org.:
Univ. of Rochester, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1481442
Alternate Identifier(s):
OSTI ID: 1610579
Grant/Contract Number:  
FG02-09ER16089; SC0001834
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Roy, Lisa, Al-Afyouni, Malik H., DeRosha, Daniel E., Mondal, Bhaskar, DiMucci, Ida M., Lancaster, Kyle M., Shearer, Jason, Bill, Eckhard, Brennessel, William W., Neese, Frank, Ye, Shengfa, and Holland, Patrick L. Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate. United Kingdom: N. p., 2019. Web. doi:10.1039/C8SC02599A.
Roy, Lisa, Al-Afyouni, Malik H., DeRosha, Daniel E., Mondal, Bhaskar, DiMucci, Ida M., Lancaster, Kyle M., Shearer, Jason, Bill, Eckhard, Brennessel, William W., Neese, Frank, Ye, Shengfa, & Holland, Patrick L. Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate. United Kingdom. doi:10.1039/C8SC02599A.
Roy, Lisa, Al-Afyouni, Malik H., DeRosha, Daniel E., Mondal, Bhaskar, DiMucci, Ida M., Lancaster, Kyle M., Shearer, Jason, Bill, Eckhard, Brennessel, William W., Neese, Frank, Ye, Shengfa, and Holland, Patrick L. Wed . "Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate". United Kingdom. doi:10.1039/C8SC02599A.
@article{osti_1481442,
title = {Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate},
author = {Roy, Lisa and Al-Afyouni, Malik H. and DeRosha, Daniel E. and Mondal, Bhaskar and DiMucci, Ida M. and Lancaster, Kyle M. and Shearer, Jason and Bill, Eckhard and Brennessel, William W. and Neese, Frank and Ye, Shengfa and Holland, Patrick L.},
abstractNote = {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.},
doi = {10.1039/C8SC02599A},
journal = {Chemical Science},
number = 3,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8SC02599A

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Spin Isomers and Ligand Isomerization in a Three-Coordinate Cobalt(I) Carbonyl Complex
journal, August 2015

  • Al-Afyouni, Malik H.; Suturina, Elizaveta; Pathak, Shubhrodeep
  • Journal of the American Chemical Society, Vol. 137, Issue 33
  • DOI: 10.1021/jacs.5b06078

Reaction Mechanism of the Reverse Water–Gas Shift Reaction Using First-Row Middle Transition Metal Catalysts L′M (M = Fe, Mn, Co): A Computational Study
journal, September 2011

  • Liu, Cong; Cundari, Thomas R.; Wilson, Angela K.
  • Inorganic Chemistry, Vol. 50, Issue 18
  • DOI: 10.1021/ic200602v

Catalytic Degenerate and Nondegenerate Oxygen Atom Transfers Employing N2O and CO2 and a MII/MIV Cycle Mediated by Group 6 MIV Terminal Oxo Complexes
journal, October 2011

  • Yonke, Brendan L.; Reeds, Jonathan P.; Zavalij, Peter Y.
  • Angewandte Chemie International Edition, Vol. 50, Issue 51
  • DOI: 10.1002/anie.201106074

Spectroscopy and electronic structures of mono- and binuclear high-valent non-heme iron–oxo systems
journal, April 2006


Enhanced Catalytic Activity of Cobalt Porphyrin in CO 2 Electroreduction upon Immobilization on Carbon Materials
journal, May 2017

  • Hu, Xin-Ming; Rønne, Magnus H.; Pedersen, Steen U.
  • Angewandte Chemie International Edition, Vol. 56, Issue 23
  • DOI: 10.1002/anie.201701104

Formation of a nickel carbon dioxide adduct and its transformation mediated by a Lewis acid
journal, January 2014

  • Kim, Yeong-Eun; Kim, Jin; Lee, Yunho
  • Chem. Commun., Vol. 50, Issue 78
  • DOI: 10.1039/C4CC04800H

Low-Coordinate Cobalt Fluoride Complexes: Synthesis, Reactions, and Production from C–F Activation Reactions
journal, November 2011

  • Dugan, Thomas R.; Goldberg, Jonathan M.; Brennessel, William W.
  • Organometallics, Vol. 31, Issue 4
  • DOI: 10.1021/om200991k

Oxygen-Atom Transfer Reactivity of Axially Ligated Mn(V)–Oxo Complexes: Evidence for Enhanced Electrophilic and Nucleophilic Pathways
journal, September 2014

  • Neu, Heather M.; Yang, Tzuhsiung; Baglia, Regina A.
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja507177h

CO2 Fixation and Transformation by a Dinuclear Copper Cryptate under Acidic Conditions
journal, June 2007

  • Chen, Jia-Mei; Wei, Wei; Feng, Xiao-Long
  • Chemistry – An Asian Journal, Vol. 2, Issue 6
  • DOI: 10.1002/asia.200700042

Ligand-Based Reduction of CO 2 and Release of CO on Iron(II)
journal, August 2012

  • Thammavongsy, Zachary; Seda, Takele; Zakharov, Lev N.
  • Inorganic Chemistry, Vol. 51, Issue 17
  • DOI: 10.1021/ic3015404

[Me 2 NN]Co(η 6 -toluene):  OO, NN, and ON Bond Cleavage Provides β-Diketiminato Cobalt μ-Oxo and Imido Complexes
journal, April 2004

  • Dai, Xuliang; Kapoor, Pooja; Warren, Timothy H.
  • Journal of the American Chemical Society, Vol. 126, Issue 15
  • DOI: 10.1021/ja036308i

Reduction of Nitrous Oxide to Dinitrogen by a Mixed Valent Tricopper-Disulfido Cluster
journal, March 2009

  • Bar-Nahum, Itsik; Gupta, Aalo K.; Huber, Stefan M.
  • Journal of the American Chemical Society, Vol. 131, Issue 8
  • DOI: 10.1021/ja808917k

Highly Efficient and Selective Photocatalytic CO 2 Reduction by Iron and Cobalt Quaterpyridine Complexes
journal, July 2016

  • Guo, Zhenguo; Cheng, Siwei; Cometto, Claudio
  • Journal of the American Chemical Society, Vol. 138, Issue 30
  • DOI: 10.1021/jacs.6b06002

Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co–O–Co Unit
journal, December 2015

  • Stauber, Julia M.; Bloch, Eric D.; Vogiatzis, Konstantinos D.
  • Journal of the American Chemical Society, Vol. 137, Issue 49
  • DOI: 10.1021/jacs.5b09827

Nonheme oxo-iron(IV) intermediates form an oxyl radical upon approaching the C-H bond activation transition state
journal, January 2011

  • Ye, S.; Neese, F.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 4
  • DOI: 10.1073/pnas.1008411108

Activation of CO 2 by a Heterobimetallic Zr/Co Complex
journal, September 2011

  • Krogman, Jeremy P.; Foxman, Bruce M.; Thomas, Christine M.
  • Journal of the American Chemical Society, Vol. 133, Issue 37
  • DOI: 10.1021/ja2071847

Splitting Water with Cobalt
journal, July 2011

  • Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc
  • Angewandte Chemie International Edition, Vol. 50, Issue 32
  • DOI: 10.1002/anie.201007987

Distinctive Reaction Pathways at Base Metals in High-Spin Organometallic Catalysts
journal, May 2015


Direct XANES Evidence for Charge Transfer in Co−CO 2 Complexes
journal, May 1997

  • Fujita, Etsuko; Furenlid, Lars R.; Renner, Mark W.
  • Journal of the American Chemical Society, Vol. 119, Issue 19
  • DOI: 10.1021/ja970151a

Reactivity of High-Valent Iron–Oxo Species in Enzymes and Synthetic Reagents: A Tale of Many States
journal, July 2007

  • Shaik, Sason; Hirao, Hajime; Kumar, Devesh
  • Accounts of Chemical Research, Vol. 40, Issue 7
  • DOI: 10.1021/ar600042c

Valence bond description of antiferromagnetic coupling in transition metal dimers
journal, May 1981

  • Noodleman, Louis
  • The Journal of Chemical Physics, Vol. 74, Issue 10
  • DOI: 10.1063/1.440939

Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO 2 Reduction Catalyst
journal, June 2011

  • Schmeier, Timothy J.; Dobereiner, Graham E.; Crabtree, Robert H.
  • Journal of the American Chemical Society, Vol. 133, Issue 24
  • DOI: 10.1021/ja2035514

CO 2 Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO 2 Reduction
journal, August 2015


Electronic structure analysis of multistate reactivity in transition metal catalyzed reactions: the case of C–H bond activation by non-heme iron(iv)–oxo cores
journal, January 2013

  • Ye, Shengfa; Geng, Cai-Yun; Shaik, Sason
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 21
  • DOI: 10.1039/c3cp00080j

Carbonate Formation from CO 2 via Oxo versus Oxalate Pathway: Theoretical Investigations into the Mechanism of Uranium-Mediated Carbonate Formation
journal, November 2010

  • Castro, Ludovic; Lam, Oanh P.; Bart, Suzanne C.
  • Organometallics, Vol. 29, Issue 21
  • DOI: 10.1021/om100479r

The Mechanism of Homogeneous CO 2 Reduction by Ni(cyclam): Product Selectivity, Concerted Proton–Electron Transfer and C–O Bond Cleavage
journal, June 2014

  • Song, Jinshuai; Klein, Eric L.; Neese, Frank
  • Inorganic Chemistry, Vol. 53, Issue 14
  • DOI: 10.1021/ic500829p

Theoretical bioinorganic chemistry: the electronic structure makes a difference
journal, April 2007

  • Kirchner, Barbara; Wennmohs, Frank; Ye, Shengfa
  • Current Opinion in Chemical Biology, Vol. 11, Issue 2
  • DOI: 10.1016/j.cbpa.2007.02.026

Spectroscopic and Quantum Chemical Characterization of the Electronic Structure and Bonding in a Non-Heme Fe IV O Complex
journal, May 2004

  • Decker, Andrea; Rohde, Jan-Uwe; Que,, Lawrence
  • Journal of the American Chemical Society, Vol. 126, Issue 17
  • DOI: 10.1021/ja0498033

Nonclassical Single-State Reactivity of an Oxo-Iron(IV) Complex Confined to Triplet Pathways
journal, June 2017

  • Kupper, Claudia; Mondal, Bhaskar; Serrano-Plana, Joan
  • Journal of the American Chemical Society, Vol. 139, Issue 26
  • DOI: 10.1021/jacs.7b03255

Generation of a Doubly Bridging CO 2 Ligand and Deoxygenation of CO 2 by an (NHC)Ni(0) Complex
journal, November 2007

  • Lee, Chang Hoon; Laitar, David S.; Mueller, Peter
  • Journal of the American Chemical Society, Vol. 129, Issue 45
  • DOI: 10.1021/ja075630g

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

  • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463096

A Masked Two-Coordinate Cobalt(I) Complex That Activates C–F Bonds
journal, August 2011

  • Dugan, Thomas R.; Sun, Xianru; Rybak-Akimova, Elena V.
  • Journal of the American Chemical Society, Vol. 133, Issue 32
  • DOI: 10.1021/ja2052914

Simultaneous Reduction of CO 2 and Splitting of H 2 O by a Single Immobilized Cobalt Phthalocyanine Electrocatalyst
journal, April 2016

  • Morlanés, Natalia; Takanabe, Kazuhiro; Rodionov, Valentin
  • ACS Catalysis, Vol. 6, Issue 5
  • DOI: 10.1021/acscatal.6b00543

Reduction of CO 2 to CO Using Low-Coordinate Iron:  Formation of a Four-Coordinate Iron Dicarbonyl Complex and a Bridging Carbonate Complex
journal, February 2008

  • Sadique, Azwana R.; Brennessel, William W.; Holland, Patrick L.
  • Inorganic Chemistry, Vol. 47, Issue 3
  • DOI: 10.1021/ic701914m

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Electrochemical Reduction of CO2 to CO Catalyzed by a Bimetallic Palladium Complex
journal, July 2006

  • Raebiger, James W.; Turner, Jeffrey W.; Noll, Bruce C.
  • Organometallics, Vol. 25, Issue 14, p. 3345-3351
  • DOI: 10.1021/om060228g

Electronic Structure and Reactivity of Three-Coordinate Iron Complexes
journal, August 2008

  • Holland, Patrick L.
  • Accounts of Chemical Research, Vol. 41, Issue 8
  • DOI: 10.1021/ar700267b

A diketiminate-bound diiron complex with a bridging carbonate ligand
journal, April 2009

  • Sadique, Azwana R.; Brennessel, William W.; Holland, Patrick L.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 65, Issue 5
  • DOI: 10.1107/S0108270109011275

Binding and Activation of N 2 O at Transition-Metal Centers: Recent Mechanistic Insights
journal, February 2010


Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO 2 Reduction
journal, February 2018


Electrocatalytic water oxidation by a molecular cobalt complex through a high valent cobalt oxo intermediate
journal, January 2016

  • Das, Debasree; Pattanayak, Santanu; Singh, Kundan K.
  • Chemical Communications, Vol. 52, Issue 79
  • DOI: 10.1039/C6CC05773J

Theoretical Studies on the Catalysis of the Reverse Water−Gas Shift Reaction Using First-Row Transition Metal β-Diketiminato Complexes
journal, June 2010

  • Liu, Cong; Munjanja, Lloyd; Cundari, Thomas R.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 21
  • DOI: 10.1021/jp911616y

Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation
journal, September 2015

  • Nguyen, Andy I.; Ziegler, Micah S.; Oña-Burgos, Pascual
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b08396

Mechanistic Studies on the Hydroxylation of Methane by Methane Monooxygenase
journal, June 2003

  • Baik, Mu-Hyun; Newcomb, Martin; Friesner, Richard A.
  • Chemical Reviews, Vol. 103, Issue 6
  • DOI: 10.1021/cr950244f

DFT investigation of C F bond activation by a low-coordinate cobalt(I) complex
journal, April 2017


Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst Determined by in Situ X-ray Spectroscopy
journal, October 2010

  • Kanan, Matthew W.; Yano, Junko; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 132, Issue 39
  • DOI: 10.1021/ja1023767

Density Functional Theory Study on the Mechanism of the Reductive Cleavage of CO 2 by a Bis-β-Diketoiminatediiron Dinitrogen Complex
journal, September 2010

  • Ariafard, Alireza; Brookes, Nigel J.; Stranger, Robert
  • Inorganic Chemistry, Vol. 49, Issue 17
  • DOI: 10.1021/ic1005715

Fe(I)-Mediated Reductive Cleavage and Coupling of CO 2 :  An Fe II (μ-O,μ-CO)Fe II Core
journal, January 2007

  • Lu, Connie C.; Saouma, Caroline T.; Day, Michael W.
  • Journal of the American Chemical Society, Vol. 129, Issue 1
  • DOI: 10.1021/ja065524z

Tuning Reactivity and Mechanism in Oxidation Reactions by Mononuclear Nonheme Iron(IV)-Oxo Complexes
journal, February 2014

  • Nam, Wonwoo; Lee, Yong-Min; Fukuzumi, Shunichi
  • Accounts of Chemical Research, Vol. 47, Issue 4
  • DOI: 10.1021/ar400258p

Nonheme Fe IV O Complexes That Can Oxidize the C−H Bonds of Cyclohexane at Room Temperature
journal, January 2004

  • Kaizer, József; Klinker, Eric J.; Oh, Na Young
  • Journal of the American Chemical Society, Vol. 126, Issue 2
  • DOI: 10.1021/ja037288n

Proteins containing oxo-bridged dinuclear iron centers: a bioinorganic perspective
journal, December 1990

  • Vincent, John B.; Olivier-Lilley, Gay L.; Averill, Bruce A.
  • Chemical Reviews, Vol. 90, Issue 8
  • DOI: 10.1021/cr00106a004

Mechanisms for CO Production from CO 2 Using Reduced Rhenium Tricarbonyl Catalysts
journal, March 2012

  • Agarwal, Jay; Fujita, Etsuko; Schaefer, Henry F.
  • Journal of the American Chemical Society, Vol. 134, Issue 11
  • DOI: 10.1021/ja2105834

Electrocatalytic Reduction of Carbon Dioxide by the Binuclear Copper Complex [Cu2(6-(diphenylphosphino-2,2'-bipyridyl)2(MeCN)2][PF6]2
journal, October 1994

  • Haines, Raymond J.; Wittrig, Rebecca E.; Kubiak, Clifford P.
  • Inorganic Chemistry, Vol. 33, Issue 21
  • DOI: 10.1021/ic00099a024

Nickel(i)-mediated transformations of carbon dioxide in closed synthetic cycles: reductive cleavage and coupling of CO2 generating NiICO, NiIICO3 and NiIIC2O4NiII entities
journal, January 2013

  • Horn, Bettina; Limberg, Christian; Herwig, Christian
  • Chemical Communications, Vol. 49, Issue 93
  • DOI: 10.1039/c3cc45407j

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Reactions of CO 2 and CS 2 with 1,2-Bis(di- tert -butylphosphino)ethane Complexes of Nickel(0) and Nickel(I)
journal, November 2010

  • Anderson, John S.; Iluc, Vlad M.; Hillhouse, Gregory L.
  • Inorganic Chemistry, Vol. 49, Issue 21
  • DOI: 10.1021/ic101652e

CO2 reduction by Fe(i): solvent control of C–O cleavage versus C–C coupling
journal, January 2013

  • Saouma, Caroline T.; Lu, Connie C.; Day, Michael W.
  • Chemical Science, Vol. 4, Issue 10
  • DOI: 10.1039/c3sc51262b

Nitrous Oxide Activation by a Ruthenium Porphyrin
journal, May 1995

  • Groves, John T.; Roman, J. Scott
  • Journal of the American Chemical Society, Vol. 117, Issue 20
  • DOI: 10.1021/ja00125a025

Enhancement of C−H Oxidizing Ability in Co-O 2  Complexes through an Isolated Heterobimetallic Oxo Intermediate
journal, February 2017

  • DeRosha, Daniel E.; Mercado, Brandon Q.; Lukat-Rodgers, Gudrun
  • Angewandte Chemie International Edition, Vol. 56, Issue 12
  • DOI: 10.1002/anie.201612010

Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel
journal, December 2002

  • Holland, Patrick L.; Cundari, Thomas R.; Perez, Lanyn L.
  • Journal of the American Chemical Society, Vol. 124, Issue 48
  • DOI: 10.1021/ja025583m

High-Valent Iron-Oxo and -Nitrido Complexes: Bonding and Reactivity
journal, July 2016

  • Mondal, Bhaskar; Roy, Lisa; Neese, Frank
  • Israel Journal of Chemistry, Vol. 56, Issue 9-10
  • DOI: 10.1002/ijch.201600028

Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts
journal, January 2018


Quantum chemical studies of C–H activation reactions by high-valent nonheme iron centers
journal, February 2009


Reactivity of a Series of Isostructural Cobalt Pincer Complexes with CO 2 , CO, and H +
journal, November 2014

  • Shaffer, David W.; Johnson, Samantha I.; Rheingold, Arnold L.
  • Inorganic Chemistry, Vol. 53, Issue 24
  • DOI: 10.1021/ic5021725

Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts
journal, February 2017


Mechanistic and Kinetic Studies of Cobalt Macrocycles in a Photochemical CO2 Reduction System: Evidence of Co-CO2 Adducts as Intermediates
journal, June 1995

  • Ogata, Tomoyuki; Yanagida, Shozo; Brunschwig, Bruce S.
  • Journal of the American Chemical Society, Vol. 117, Issue 25
  • DOI: 10.1021/ja00130a009

Covalent Attachment of Catalyst Molecules to Conductive Diamond: CO 2 Reduction Using “Smart” Electrodes
journal, September 2012

  • Yao, Shu A.; Ruther, Rose E.; Zhang, Linghong
  • Journal of the American Chemical Society, Vol. 134, Issue 38
  • DOI: 10.1021/ja304783j

Cobalt–phosphate oxygen-evolving compound
journal, January 2009

  • Kanan, Matthew W.; Surendranath, Yogesh; Nocera, Daniel G.
  • Chemical Society Reviews, Vol. 38, Issue 1, p. 109-114
  • DOI: 10.1039/B802885K

Reactivity comparison of high-valent iron(iv)-oxo complexes bearing N-tetramethylated cyclam ligands with different ring size
journal, January 2013

  • Hong, Seungwoo; So, Hee; Yoon, Heejung
  • Dalton Transactions, Vol. 42, Issue 22
  • DOI: 10.1039/c3dt50750e

Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical–Co(II)–Superoxide Complex with Divergent Catalytic Reactivity
journal, February 2016

  • Corcos, Amanda R.; Villanueva, Omar; Walroth, Richard C.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b12643

Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt
journal, September 1980

  • Fisher, Barbara J.; Eisenberg, Richard
  • Journal of the American Chemical Society, Vol. 102, Issue 24, p. 7361-7363
  • DOI: 10.1021/ja00544a035

Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation
journal, December 2009

  • Rakowski Dubois, M.; Dubois, Daniel L.
  • Accounts of Chemical Research, Vol. 42, Issue 12, p. 1974-1982
  • DOI: 10.1021/ar900110c

Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels
journal, January 2009

  • Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.
  • Chem. Soc. Rev., Vol. 38, Issue 1
  • DOI: 10.1039/B804323J

Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
journal, April 1994

  • Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 100, Issue 8
  • DOI: 10.1063/1.467146

Synthesis, Structure, and Spectroscopy of an Oxodiiron(II) Complex
journal, July 2005

  • Eckert, Nathan A.; Stoian, Sebastian; Smith, Jeremy M.
  • Journal of the American Chemical Society, Vol. 127, Issue 26
  • DOI: 10.1021/ja0436704

Bioinspired Nonheme Iron Catalysts for C–H and C═C Bond Oxidation: Insights into the Nature of the Metal-Based Oxidants
journal, August 2015


Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013

  • Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
  • Chemical Reviews, Vol. 113, Issue 8
  • DOI: 10.1021/cr300463y

Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO 2 Reduction
journal, November 2016


Inhibition of mitochondrial calcium ion transport by an oxo-bridged dinuclear ruthenium ammine complex
journal, May 1991

  • Ying, Wen Long; Emerson, Jeffrey; Clarke, Michael J.
  • Biochemistry, Vol. 30, Issue 20
  • DOI: 10.1021/bi00234a016

Formation of a Unique Zinc Carbamate by CO 2 Fixation: Implications for the Reactivity of Tetra-Azamacrocycle Ligated Zn(II) Complexes
journal, February 2008

  • Notni, Johannes; Schenk, Stephan; Görls, Helmar
  • Inorganic Chemistry, Vol. 47, Issue 4
  • DOI: 10.1021/ic701899u

Catalytic Degenerate and Nondegenerate Oxygen Atom Transfers Employing N2O and CO2 and a MII/MIV Cycle Mediated by Group 6 MIV Terminal Oxo Complexes
journal, October 2011

  • Yonke, Brendan L.; Reeds, Jonathan P.; Zavalij, Peter Y.
  • Angewandte Chemie, Vol. 123, Issue 51
  • DOI: 10.1002/ange.201106074

    Works referencing / citing this record:

    A bis ‐Pyrazolate Pincer on Reduced Cr Deoxygenates CO 2 : Selective Capture of the Derived Oxide by Cr II
    journal, April 2019

    • Labrum, Nicholas S.; Chen, Chun‐Hsing; Caulton, Kenneth G.
    • Chemistry – A European Journal, Vol. 25, Issue 33
    • DOI: 10.1002/chem.201901134

    CO 2 fixation and transformation on a thiolate-bridged dicobalt scaffold under oxidising conditions
    journal, January 2019

    • Wu, Hui; Li, Jianzhe; Yang, Dawei
    • Inorganic Chemistry Frontiers, Vol. 6, Issue 8
    • DOI: 10.1039/c9qi00423h