Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer

Loipersberger, Matthias; Zee, David Z.; Panetier, Julien A.; Chang, Christopher J.; Long, Jeffrey R.; Head-Gordon, Martin

doi:10.1021/acs.inorgchem.0c00454

Title: Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO₂ Reduction: Key Roles for Intramolecular Interactions in CO₂ Binding and Proton Transfer

Journal Article · Wed May 27 00:00:00 EDT 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c00454· OSTI ID:1737618

^[1]; Zee, David Z. ^[1];

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); State Univ. of New York (SUNY), Binghamton, NY (United States)

A solar-driven conversion of CO₂ into fuels by artificial photosynthesis would not only mitigate the greenhouse effect but also provide an alternative to obtain fuels in a renewable fashion. To this end, the new iron polypyridine catalyst [Fe(bpy^NHEtPY2Me)L₂]²⁺ (L = H₂O, CH₃CN) was recently developed for the electrochemical reduction of CO₂ to CO. Here, we performed density functional theory (DFT) electronic structure calculations to shed light on a possible pathway for CO₂ reduction and the origin of the selectivity between CO₂ reduction versus the hydrogen evolution reaction. The metal center remains Lewis acidic throughout the reduction process due to ligand loss and mainly ligand-based reduction stabilized by antiferromagnetic coupling to a high-spin Fe(II) center. This results in a high barrier for hydride formation but a facile addition and activation of CO₂ via an η² coordination and stabilizing hydrogen bonding by the amine group. The second unoccupied equatorial coordination site opens up the possibility for an intramolecular protonation with a coordinated water ligand. This facilitates protonation because not only CO₂ but also the proton source H₂O is activated and properly aligned for a proton transfer due to the Fe-OH₂ bond; consequently, both protonation steps are facile. The moderate ligand field allows a rapid ligand exchange for a second intramolecular protonation step and facilitates an exergonic CO release. The lower selectivity of the related [Fe(bpy^OHPY2Me)L₂]²⁺ complex can be related to its more acidic second coordination sphere, which enables an intramolecular proton transfer that is kinetically competitive with CO₂ addition.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0004993; 101528-002

OSTI ID:: 1737618

Journal Information:: Inorganic Chemistry, Vol. 59, Issue 12; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (112)

Chemical approaches to artificial photosynthesis Concepcion, J. J.; House, R. L.; Papanikolas, J. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1212254109	journal	September 2012
Chemical Approaches to Artificial Photosynthesis. 2 Alstrum-Acevedo, James H.; Brennaman, M. Kyle; Meyer, Thomas J. Inorganic Chemistry, Vol. 44, Issue 20 https://doi.org/10.1021/ic050904r	journal	October 2005
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B. Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr300463y	journal	June 2013
Direct and Reversible Hydrogenation of CO2 to Formate by a Bacterial Carbon Dioxide Reductase Schuchmann, K.; Muller, V. Science, Vol. 342, Issue 6164 https://doi.org/10.1126/science.1244758	journal	December 2013
Recent advances in catalytic hydrogenation of carbon dioxide Wang, Wei; Wang, Shengping; Ma, Xinbin Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c1cs15008a	journal	January 2011
Photocatalytic Reduction of CO ₂ on TiO ₂ and Other Semiconductors Habisreutinger, Severin N.; Schmidt-Mende, Lukas; Stolarczyk, Jacek K. Angewandte Chemie International Edition, Vol. 52, Issue 29 https://doi.org/10.1002/anie.201207199	journal	June 2013
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels Qiao, Jinli; Liu, Yuyu; Hong, Feng Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60323G	journal	January 2014
Progress in catalyst exploration for heterogeneous CO ₂ reduction and utilization: a critical review Zhao, Guixia; Huang, Xiubing; Wang, Xiangxue J. Mater. Chem. A, Vol. 5, Issue 41 https://doi.org/10.1039/C7TA07290B	journal	January 2017
A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO ₂ Verma, Sumit; Kim, Byoungsu; Jhong, Huei-Ru “Molly” ChemSusChem, Vol. 9, Issue 15 https://doi.org/10.1002/cssc.201600394	journal	June 2016
“Catalysis in the Refining of Fischer-Tropsch Syncrude” Brown, Stewart Platinum Metals Review, Vol. 55, Issue 4 https://doi.org/10.1595/147106711X593717	journal	October 2011
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
Controlling H ⁺ vs CO ₂ Reduction Selectivity on Pb Electrodes Lee, Chang Hoon; Kanan, Matthew W. ACS Catalysis, Vol. 5, Issue 1 https://doi.org/10.1021/cs5017672	journal	November 2014
Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO ₂ : New Theoretical Insights from an Improved Electrochemical Model Goodpaster, Jason D.; Bell, Alexis T.; Head-Gordon, Martin The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00358	journal	April 2016
Efficient Conversion of CO ₂ to CO Using Tin and Other Inexpensive and Easily Prepared Post-Transition Metal Catalysts Medina-Ramos, Jonnathan; Pupillo, Rachel C.; Keane, Thomas P. Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/ja5121088	journal	April 2015
Mechanism of CO ₂ Reduction at Copper Surfaces: Pathways to C ₂ Products Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03477	journal	January 2018
Manganese as a Substitute for Rhenium in CO ₂ Reduction Catalysts: The Importance of Acids Smieja, Jonathan M.; Sampson, Matthew D.; Grice, Kyle A. Inorganic Chemistry, Vol. 52, Issue 5 https://doi.org/10.1021/ic302391u	journal	February 2013
Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO ₂ with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center Chen, Lingjing; Guo, Zhenguo; Wei, Xi-Guang Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b06535	journal	August 2015
Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.6b11474	journal	March 2017
CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine Wang, Min; Torbensen, Kristian; Salvatore, Danielle Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11542-w	journal	August 2019
A Local Proton Source Enhances CO ₂ Electroreduction to CO by a Molecular Fe Catalyst Costentin, Cyrille; Drouet, Samuel; Robert, Marc Science, Vol. 338, Issue 6103 https://doi.org/10.1126/science.1224581	journal	October 2012
Electrocatalytic reduction of carbon dioxide by nickel cyclam2+ in water: study of the factors affecting the efficiency and the selectivity of the process Beley, Marc.; Collin, Jean Paul.; Ruppert, Romain. Journal of the American Chemical Society, Vol. 108, Issue 24 https://doi.org/10.1021/ja00284a003	journal	November 1986
Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO ₂ Reduction Takeda, Hiroyuki; Cometto, Claudio; Ishitani, Osamu ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02181	journal	November 2016
Electroreduction of CO ₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center Wu, Yueshen; Jiang, Jianbing; Weng, Zhe ACS Central Science, Vol. 3, Issue 8 https://doi.org/10.1021/acscentsci.7b00160	journal	July 2017
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO ₂ reduction in water Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao Science, Vol. 349, Issue 6253 https://doi.org/10.1126/science.aac8343	journal	August 2015
Fe-Porphyrin-Based Metal–Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO ₂ Hod, Idan; Sampson, Matthew D.; Deria, Pravas ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01767	journal	September 2015
Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide Kornienko, Nikolay; Zhao, Yingbo; Kley, Christopher S. Journal of the American Chemical Society, Vol. 137, Issue 44 https://doi.org/10.1021/jacs.5b08212	journal	October 2015
Versatile functionalization of carbon electrodes with a polypyridine ligand: metallation and electrocatalytic H ⁺ and CO ₂ reduction Elgrishi, Noémie; Griveau, Sophie; Chambers, Matthew B. Chemical Communications, Vol. 51, Issue 14 https://doi.org/10.1039/C4CC10027A	journal	January 2015
Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction Oh, Seokjoon; Gallagher, James R.; Miller, Jeffrey T. Journal of the American Chemical Society, Vol. 138, Issue 6 https://doi.org/10.1021/jacs.5b13080	journal	February 2016
Molecular electrocatalysts can mediate fast, selective CO ₂ reduction in a flow cell Ren, Shaoxuan; Joulié, Dorian; Salvatore, Danielle Science, Vol. 365, Issue 6451 https://doi.org/10.1126/science.aax4608	journal	July 2019
Photochemical and Photoelectrochemical Reduction of CO ₂ Kumar, Bhupendra; Llorente, Mark; Froehlich, Jesse Annual Review of Physical Chemistry, Vol. 63, Issue 1 https://doi.org/10.1146/annurev-physchem-032511-143759	journal	May 2012
Re(bipy-tBu)(CO) ₃ Cl−improved Catalytic Activity for Reduction of Carbon Dioxide: IR-Spectroelectrochemical and Mechanistic Studies Smieja, Jonathan M.; Kubiak, Clifford P. Inorganic Chemistry, Vol. 49, Issue 20 https://doi.org/10.1021/ic1008363	journal	October 2010
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO Smieja, J. M.; Benson, E. E.; Kumar, B. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1119863109	journal	May 2012
The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO ₂ Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry Benson, Eric E.; Sampson, Matthew D.; Grice, Kyle A. Angewandte Chemie International Edition, Vol. 52, Issue 18 https://doi.org/10.1002/anie.201209911	journal	March 2013
Direct observation of the reduction of carbon dioxide by rhenium bipyridine catalysts Sampson, Matthew D.; Froehlich, Jesse D.; Smieja, Jonathan M. Energy & Environmental Science, Vol. 6, Issue 12 https://doi.org/10.1039/c3ee42186d	journal	January 2013
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A. Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja501252f	journal	February 2014
Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO ₂ Reduction using Infrared Spectroelectrochemistry Machan, Charles W.; Sampson, Matthew D.; Chabolla, Steven A. Organometallics, Vol. 33, Issue 18 https://doi.org/10.1021/om500044a	journal	April 2014
Electrocatalytic Reduction of Carbon Dioxide by Mn(CN)(2,2′-bipyridine)(CO) ₃ : CN Coordination Alters Mechanism Machan, Charles W.; Stanton, Charles J.; Vandezande, Jonathon E. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01715	journal	August 2015
Synergistic Effects of Imidazolium-Functionalization on fac -Mn(CO) ₃ Bipyridine Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction Sung, Siyoung; Li, Xiaohui; Wolf, Lucienna M. Journal of the American Chemical Society, Vol. 141, Issue 16 https://doi.org/10.1021/jacs.8b13657	journal	March 2019
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO ₂ Reduction by fac -Re(bpy)(CO) ₃ Cl Keith, John A.; Grice, Kyle A.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja406456g	journal	October 2013
Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide Riplinger, Christoph; Sampson, Matthew D.; Ritzmann, Andrew M. Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja508192y	journal	November 2014
Influence of Weak Brønsted Acids on Electrocatalytic CO ₂ Reduction by Manganese and Rhenium Bipyridine Catalysts Riplinger, Christoph; Carter, Emily A. ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501687n	journal	January 2015
The Mechanism of Homogeneous CO ₂ Reduction by Ni(cyclam): Product Selectivity, Concerted Proton–Electron Transfer and C–O Bond Cleavage Song, Jinshuai; Klein, Eric L.; Neese, Frank Inorganic Chemistry, Vol. 53, Issue 14 https://doi.org/10.1021/ic500829p	journal	June 2014
Kinetics of CO Addition to Ni(cyclam) ⁺ in Aqueous Solution Kelly, Craig A.; Mulazzani, Quinto G.; Blinn, Elliott L. Inorganic Chemistry, Vol. 35, Issue 18 https://doi.org/10.1021/ic951527t	journal	January 1996
The Homogeneous Reduction of CO ₂ by [Ni(cyclam)] ⁺ : Increased Catalytic Rates with the Addition of a CO Scavenger Froehlich, Jesse D.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/ja512575v	journal	March 2015
Ultraefficient homogeneous catalyst for the CO ₂ -to-CO electrochemical conversion Costentin, Cyrille; Passard, Guillaume; Robert, Marc Proceedings of the National Academy of Sciences, Vol. 111, Issue 42 https://doi.org/10.1073/pnas.1416697111	journal	October 2014
Electronic Structure of a Formal Iron(0) Porphyrin Complex Relevant to CO ₂ Reduction Römelt, Christina; Song, Jinshuai; Tarrago, Maxime Inorganic Chemistry, Vol. 56, Issue 8 https://doi.org/10.1021/acs.inorgchem.7b00401	journal	April 2017
Molecular catalysis of the electrochemical and photochemical reduction of CO2 with Fe and Co metal based complexes. Recent advances Bonin, Julien; Maurin, Antoine; Robert, Marc Coordination Chemistry Reviews, Vol. 334 https://doi.org/10.1016/j.ccr.2016.09.005	journal	March 2017
Mechanisms of catalytic reduction of CO 2 with heme and nonheme metal complexes Fukuzumi, Shunichi; Lee, Yong-Min; Ahn, Hyun S. Chemical Science, Vol. 9, Issue 28 https://doi.org/10.1039/C8SC02220H	journal	January 2018
CO ₂ Reduction on an Iron-Porphyrin Center: A Computational Study Davethu, Paul A.; de Visser, Sam P. The Journal of Physical Chemistry A, Vol. 123, Issue 30 https://doi.org/10.1021/acs.jpca.9b05102	journal	July 2019
Pendant Acid–Base Groups in Molecular Catalysts: H-Bond Promoters or Proton Relays? Mechanisms of the Conversion of CO ₂ to CO by Electrogenerated Iron(0)Porphyrins Bearing Prepositioned Phenol Functionalities Costentin, Cyrille; Passard, Guillaume; Robert, Marc Journal of the American Chemical Society, Vol. 136, Issue 33 https://doi.org/10.1021/ja506193v	journal	August 2014
Proton-Coupled Electron Transfer Cleavage of Heavy-Atom Bonds in Electrocatalytic Processes. Cleavage of a C–O Bond in the Catalyzed Electrochemical Reduction of CO ₂ Costentin, Cyrille; Drouet, Samuel; Passard, Guillaume Journal of the American Chemical Society, Vol. 135, Issue 24 https://doi.org/10.1021/ja4030148	journal	June 2013
Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction Nichols, Asa W.; Machan, Charles W. Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00397	journal	June 2019
A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO ₂ and a Proton Donor Promotes the Electrochemical Reduction of CO ₂ to CO Catalyzed by a Rhenium Bipyridine-Type Complex Haviv, Eynat; Azaiza-Dabbah, Dima; Carmieli, Raanan Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b05658	journal	September 2018
Visible-Light-Driven Photocatalytic CO ₂ Reduction by a Ni(II) Complex Bearing a Bioinspired Tetradentate Ligand for Selective CO Production Hong, Dachao; Tsukakoshi, Yuto; Kotani, Hiroaki Journal of the American Chemical Society, Vol. 139, Issue 19 https://doi.org/10.1021/jacs.7b01956	journal	May 2017
Bio-Inspired Mn(I) Complexes for the Hydrogenation of CO ₂ to Formate and Formamide Dubey, Abhishek; Nencini, Luca; Fayzullin, Robert R. ACS Catalysis, Vol. 7, Issue 6 https://doi.org/10.1021/acscatal.7b00943	journal	May 2017
Minimal Proton Channel Enables H ₂ Oxidation and Production with a Water-Soluble Nickel-Based Catalyst Dutta, Arnab; Lense, Sheri; Hou, Jianbo Journal of the American Chemical Society, Vol. 135, Issue 49 https://doi.org/10.1021/ja407826d	journal	November 2013
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO ₂ Reduction Catalyst Schmeier, Timothy J.; Dobereiner, Graham E.; Crabtree, Robert H. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja2035514	journal	June 2011
Turning on the Protonation-First Pathway for Electrocatalytic CO ₂ Reduction by Manganese Bipyridyl Tricarbonyl Complexes Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b08776	journal	February 2017
Development of Molecular Electrocatalysts for Energy Storage DuBois, Daniel L. Inorganic Chemistry, Vol. 53, Issue 8 https://doi.org/10.1021/ic4026969	journal	February 2014
Positional effects of second-sphere amide pendants on electrochemical CO ₂ reduction catalyzed by iron porphyrins Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K. Chemical Science, Vol. 9, Issue 11 https://doi.org/10.1039/C7SC04682K	journal	January 2018
Tuning Second Coordination Sphere Interactions in Polypyridyl–Iron Complexes to Achieve Selective Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide Zee, David Z.; Nippe, Michael; King, Amanda E. Inorganic Chemistry, Vol. 59, Issue 7 https://doi.org/10.1021/acs.inorgchem.0c00455	journal	March 2020
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008
ω B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation Mardirossian, Narbe; Head-Gordon, Martin The Journal of Chemical Physics, Vol. 144, Issue 21 https://doi.org/10.1063/1.4952647	journal	June 2016
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals Mardirossian, Narbe; Head-Gordon, Martin Molecular Physics, Vol. 115, Issue 19 https://doi.org/10.1080/00268976.2017.1333644	journal	April 2017
Assessment of DFT Methods for Transition Metals with the TMC151 Compilation of Data Sets and Comparison with Accuracies for Main-Group Chemistry Chan, Bun; Gill, Peter M. W.; Kimura, Masanari Journal of Chemical Theory and Computation, Vol. 15, Issue 6 https://doi.org/10.1021/acs.jctc.9b00239	journal	April 2019
A new method for incorporating solvent effect into the classical, ab initio molecular orbital and density functional theory frameworks for arbitrary shape cavity Truong, Thanh N.; Stefanovich, Eugene V. Chemical Physics Letters, Vol. 240, Issue 4 https://doi.org/10.1016/0009-2614(95)00541-B	journal	June 1995
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn Hellweg, Arnim; Hättig, Christof; Höfener, Sebastian Theoretical Chemistry Accounts, Vol. 117, Issue 4 https://doi.org/10.1007/s00214-007-0250-5	journal	January 2007
Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 111, Issue 2 https://doi.org/10.1021/jp065403l	journal	January 2007
Reduction of Systematic Uncertainty in DFT Redox Potentials of Transition-Metal Complexes Konezny, Steven J.; Doherty, Mark D.; Luca, Oana R. The Journal of Physical Chemistry C, Vol. 116, Issue 10 https://doi.org/10.1021/jp300485t	journal	March 2012
Accurate p K _a Calculations for Carboxylic Acids Using Complete Basis Set and Gaussian-n Models Combined with CPCM Continuum Solvation Methods Liptak, Matthew D.; Shields, George C. Journal of the American Chemical Society, Vol. 123, Issue 30 https://doi.org/10.1021/ja010534f	journal	August 2001
A Computational Study of the Mechanism of Hydrogen Evolution by Cobalt(Diimine-Dioxime) Catalysts Bhattacharjee, Anirban; Andreiadis, Eugen S.; Chavarot-Kerlidou, Murielle Chemistry - A European Journal, Vol. 19, Issue 45 https://doi.org/10.1002/chem.201301860	journal	September 2013
Acidities of strong neutral Brønsted acids in different media: ACIDITIES OF STRONG NEUTRAL BRØNSTED ACIDS Raamat, Elin; Kaupmees, Karl; Ovsjannikov, Gea Journal of Physical Organic Chemistry, Vol. 26, Issue 2 https://doi.org/10.1002/poc.2946	journal	May 2012
Unified Benchmarking of Electrocatalysts in Noninnocent Second Coordination Spheres for CO ₂ Reduction Matsubara, Yasuo ACS Energy Letters, Vol. 4, Issue 8 https://doi.org/10.1021/acsenergylett.9b01180	journal	July 2019
Quantum-Chemical Predictions of Absolute Standard Redox Potentials of Diverse Organic Molecules and Free Radicals in Acetonitrile Fu, Yao; Liu, Lei; Yu, Hai-Zhu Journal of the American Chemical Society, Vol. 127, Issue 19 https://doi.org/10.1021/ja0421856	journal	May 2005
Calculation of One-Electron Redox Potentials Revisited. Is It Possible to Calculate Accurate Potentials with Density Functional Methods? Roy, Lindsay E.; Jakubikova, Elena; Guthrie, M. Graham The Journal of Physical Chemistry A, Vol. 113, Issue 24 https://doi.org/10.1021/jp811388w	journal	June 2009
Theoretical Studies on the Redox Potentials of Fe Dinuclear Complexes as Models for Hydrogenase Roy, Lindsay E.; Batista, Enrique R.; Hay, P. Jeffrey Inorganic Chemistry, Vol. 47, Issue 20 https://doi.org/10.1021/ic800541w	journal	October 2008
Catalytic hydrogen production by a Ni–Ru mimic of NiFe hydrogenases involves a proton-coupled electron transfer step Canaguier, Sigolène; Fourmond, Vincent; Perotto, Carlo U. Chemical Communications, Vol. 49, Issue 44 https://doi.org/10.1039/c3cc40987b	journal	January 2013
Assertion and validation of the performance of the B3LYP⋆ functional for the first transition metal row and the G2 test set Salomon, Oliver; Reiher, Markus; Hess, Bernd Artur The Journal of Chemical Physics, Vol. 117, Issue 10 https://doi.org/10.1063/1.1493179	journal	September 2002
Accurate Spin-State Energies for Iron Complexes Swart, Marcel Journal of Chemical Theory and Computation, Vol. 4, Issue 12 https://doi.org/10.1021/ct800277a	journal	November 2008
Towards quantifying the role of exact exchange in predictions of transition metal complex properties Ioannidis, Efthymios I.; Kulik, Heather J. The Journal of Chemical Physics, Vol. 143, Issue 3 https://doi.org/10.1063/1.4926836	journal	July 2015
Theoretical Study of Spin Crossover in 30 Iron Complexes Kepp, Kasper P. Inorganic Chemistry, Vol. 55, Issue 6 https://doi.org/10.1021/acs.inorgchem.5b02371	journal	February 2016
Assessment of density functional theory for iron(II) molecules across the spin-crossover transition Droghetti, A.; Alfè, D.; Sanvito, S. The Journal of Chemical Physics, Vol. 137, Issue 12 https://doi.org/10.1063/1.4752411	journal	September 2012
Assessment of electronic structure methods for the determination of the ground spin states of Fe( ii ), Fe( iii ) and Fe( iv ) complexes Verma, Pragya; Varga, Zoltan; Klein, Johannes E. M. N. Physical Chemistry Chemical Physics, Vol. 19, Issue 20 https://doi.org/10.1039/C7CP01263B	journal	January 2017
Highly Selective Molecular Catalysts for the CO ₂ -to-CO Electrochemical Conversion at Very Low Overpotential. Contrasting Fe vs Co Quaterpyridine Complexes upon Mechanistic Studies Cometto, Claudio; Chen, Lingjing; Lo, Po-Kam ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b04412	journal	March 2018
(η ² -Acetonitrile)bis(η ⁵ -cyclopentadienyl)molybdenum( II ):the first structurally characterized complex containing an η ² -nitrile ligand Wright, Thomas C.; Wilkinson, Geoffrey; Motevalli, Majid J. Chem. Soc., Dalton Trans., Issue 9 https://doi.org/10.1039/DT9860002017	journal	January 1986
Crystal structure of an .eta.2-acetonitrile complex of tungsten(II): acetonitrile as a four-electron donor Barrera, Joseph; Sabat, Michal; Harman, W. Dean Journal of the American Chemical Society, Vol. 113, Issue 21 https://doi.org/10.1021/ja00021a060	journal	October 1991
Reversible Cleavage of Carbon−Carbon Bonds in Benzonitrile Using Nickel(0) Garcia, Juventino J.; Jones, William D. Organometallics, Vol. 19, Issue 26 https://doi.org/10.1021/om0008474	journal	December 2000
Formation of .eta.2-side-bonded aryl nitrile complexes from 4-metallaisoxazolin-5-one species and their application in the thermal and photochemical activation of carbon-hydrogen bonds Chetcuti, Peter A.; Knobler, Carolyn B.; Hawthorne, M. Frederick Organometallics, Vol. 7, Issue 3 https://doi.org/10.1021/om00093a013	journal	March 1988
Alkyne and Nitrile as η ² (3e) Ligands in [Tris(pyrazolyl)borato]niobium(I) Complexes. Synthesis, Structure, and Coupling Reaction Lorente, Philippe; Carfagna, Carla; Etienne, Michel Organometallics, Vol. 15, Issue 4 https://doi.org/10.1021/om9508952	journal	January 1996
How Innocent are Potentially Redox Non-Innocent Ligands? Electronic Structure and Metal Oxidation States in Iron-PNN Complexes as a Representative Case Study Butschke, Burkhard; Fillman, Kathlyn L.; Bendikov, Tatyana Inorganic Chemistry, Vol. 54, Issue 10 https://doi.org/10.1021/acs.inorgchem.5b00509	journal	April 2015
On the Innocence of Bipyridine Ligands: How Well Do DFT Functionals Fare for These Challenging Spin Systems? Milko, Petr; Iron, Mark A. Journal of Chemical Theory and Computation, Vol. 10, Issue 1 https://doi.org/10.1021/ct400913z	journal	November 2013
Entangled Electrons Foil Synthesis of Elusive Low-Valent Vanadium Oxo Complex Schlimgen, Anthony W.; Heaps, Charles W.; Mazziotti, David A. The Journal of Physical Chemistry Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acs.jpclett.5b02547	journal	January 2016
Multireference Electronic Structures of Fe–Pyridine(diimine) Complexes over Multiple Oxidation States Ortuño, Manuel A.; Cramer, Christopher J. The Journal of Physical Chemistry A, Vol. 121, Issue 31 https://doi.org/10.1021/acs.jpca.7b06032	journal	July 2017
Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals Sayfutyarova, Elvira R.; Sun, Qiming; Chan, Garnet Kin-Lic Journal of Chemical Theory and Computation, Vol. 13, Issue 9 https://doi.org/10.1021/acs.jctc.7b00128	journal	August 2017
Active Space Selection Based on Natural Orbital Occupation Numbers from n -Electron Valence Perturbation Theory Khedkar, Abhishek; Roemelt, Michael Journal of Chemical Theory and Computation, Vol. 15, Issue 6 https://doi.org/10.1021/acs.jctc.8b01293	journal	April 2019
Automated Selection of Active Orbital Spaces Stein, Christopher J.; Reiher, Markus Journal of Chemical Theory and Computation, Vol. 12, Issue 4 https://doi.org/10.1021/acs.jctc.6b00156	journal	March 2016
Automated Identification of Relevant Frontier Orbitals for Chemical Compounds and Processes Stein, ChristopherJ.; Reiher, Markus CHIMIA International Journal for Chemistry, Vol. 71, Issue 4 https://doi.org/10.2533/chimia.2017.170	journal	April 2017
autoCAS : A Program for Fully Automated Multiconfigurational Calculations Stein, Christopher J.; Reiher, Markus Journal of Computational Chemistry https://doi.org/10.1002/jcc.25869	journal	June 2019
A New Mode of Activation of CO2 by Metal-Ligand Cooperation with Reversible CC and MO Bond Formation at Ambient Temperature Vogt, Matthias; Gargir, Moti; Iron, Mark A. Chemistry - A European Journal, Vol. 18, Issue 30 https://doi.org/10.1002/chem.201201730	journal	June 2012
Reversible CO ₂ binding triggered by metal–ligand cooperation in a rhenium( i ) PNP pincer-type complex and the reaction with dihydrogen Vogt, Matthias; Nerush, Alexander; Diskin-Posner, Yael Chem. Sci., Vol. 5, Issue 5 https://doi.org/10.1039/C4SC00130C	journal	January 2014
Rhenium(I) Triscarbonyl Complexes with Redox-Active Amino- and Iminopyridine Ligands: Metal–Ligand Cooperation as Trigger for the Reversible Binding of CO ₂ via a Dearmomatization/Rearomatization Reaction Sequence Stichauer, Rasmus; Helmers, Arne; Bremer, Jennifer Organometallics, Vol. 36, Issue 4 https://doi.org/10.1021/acs.organomet.6b00897	journal	February 2017
Transition Metal Frustrated Lewis Pairs Flynn, Stephanie R.; Wass, Duncan F. ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs400754w	journal	October 2013
Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1089	journal	July 2011
Reduction of CO ₂ by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal-Ligand Binding of CO ₂ Sieh, Daniel; Lacy, David C.; Peters, Jonas C. Chemistry - A European Journal, Vol. 21, Issue 23 https://doi.org/10.1002/chem.201500463	journal	April 2015

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