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Title: Mechanism of photocatalytic reduction of CO2 by Re(bpy)(CO)3Cl from differences in carbon isotope discrimination

Abstract

The rhenium complex Re(bpy)(CO)3Cl (1, bpy = 2,2'-bipyridine) catalyzes CO2 reduction to CO in mixtures containing triethanolamine (TEOA) as a sacrificial reductant. The mechanism of this reaction under photocatalytic conditions remains to be fully characterized. Here, we report the competitive carbon kinetic isotope effects (13C KIEs) on photocatalytic CO2 reduction by 1 and analyze the results of experimental measurements by comparing with computed KIEs via density functional theory (DFT) calculations as a means of formulating a chemical mechanism and illustrating the utility of this approach. The 13C KIEs, k(12C)/k(13C), in acetonitrile (ACN) and dimethylformamide (DMF) were determined to be 1.0718 ± 0.0036 and 1.0685 ± 0.0075, respectively. When [Ru(bpy)3]Cl2 is added to the reaction mixture in acetonitrile as a photosensitizer, the reduction of CO2 exhibited a 13C KIE = 1.0703 ± 0.0043. These values are consistent with the calculated isotope effect of CO2 binding to the one-electron reduced [ReI(bpy•)(CO)3] species. The findings reported here provide strong evidence that the reactions in the two different solvents have the same first irreversible step and proceed with similar reactive intermediates upon reduction. Theoretically, we found that the major contribution for the large 13C isotope effects comes from a dominant zero-point energy (ZPE) term.more » Lastly, these results lay the groundwork for combined experimental and theoretical approaches for analysis of competitive isotope effects toward understanding CO2 reduction catalyzed by other complexes.« less

Authors:
 [1];  [2];  [2];  [1]
  1. Univ. of Connecticut, Storrs, CT (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1331074
Report Number(s):
BNL-113175-2016-JA
Journal ID: ISSN 2155-5435; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 8; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schneider, Taylor W., Ertem, Mehmed Z., Muckerman, James T., and Angeles-Boza, Alfredo M. Mechanism of photocatalytic reduction of CO2 by Re(bpy)(CO)3Cl from differences in carbon isotope discrimination. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b01208.
Schneider, Taylor W., Ertem, Mehmed Z., Muckerman, James T., & Angeles-Boza, Alfredo M. Mechanism of photocatalytic reduction of CO2 by Re(bpy)(CO)3Cl from differences in carbon isotope discrimination. United States. https://doi.org/10.1021/acscatal.6b01208
Schneider, Taylor W., Ertem, Mehmed Z., Muckerman, James T., and Angeles-Boza, Alfredo M. Mon . "Mechanism of photocatalytic reduction of CO2 by Re(bpy)(CO)3Cl from differences in carbon isotope discrimination". United States. https://doi.org/10.1021/acscatal.6b01208. https://www.osti.gov/servlets/purl/1331074.
@article{osti_1331074,
title = {Mechanism of photocatalytic reduction of CO2 by Re(bpy)(CO)3Cl from differences in carbon isotope discrimination},
author = {Schneider, Taylor W. and Ertem, Mehmed Z. and Muckerman, James T. and Angeles-Boza, Alfredo M.},
abstractNote = {The rhenium complex Re(bpy)(CO)3Cl (1, bpy = 2,2'-bipyridine) catalyzes CO2 reduction to CO in mixtures containing triethanolamine (TEOA) as a sacrificial reductant. The mechanism of this reaction under photocatalytic conditions remains to be fully characterized. Here, we report the competitive carbon kinetic isotope effects (13C KIEs) on photocatalytic CO2 reduction by 1 and analyze the results of experimental measurements by comparing with computed KIEs via density functional theory (DFT) calculations as a means of formulating a chemical mechanism and illustrating the utility of this approach. The 13C KIEs, k(12C)/k(13C), in acetonitrile (ACN) and dimethylformamide (DMF) were determined to be 1.0718 ± 0.0036 and 1.0685 ± 0.0075, respectively. When [Ru(bpy)3]Cl2 is added to the reaction mixture in acetonitrile as a photosensitizer, the reduction of CO2 exhibited a 13C KIE = 1.0703 ± 0.0043. These values are consistent with the calculated isotope effect of CO2 binding to the one-electron reduced [ReI(bpy•–)(CO)3] species. The findings reported here provide strong evidence that the reactions in the two different solvents have the same first irreversible step and proceed with similar reactive intermediates upon reduction. Theoretically, we found that the major contribution for the large 13C isotope effects comes from a dominant zero-point energy (ZPE) term. Lastly, these results lay the groundwork for combined experimental and theoretical approaches for analysis of competitive isotope effects toward understanding CO2 reduction catalyzed by other complexes.},
doi = {10.1021/acscatal.6b01208},
journal = {ACS Catalysis},
number = 8,
volume = 6,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

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

Photocatalytic CO 2 Reduction and Surface Immobilization of a Tricarbonyl Re(I) Compound Modified with Amide Groups
journal, February 2013

  • Liu, Chao; Dubois, Kevin D.; Louis, Michael E.
  • ACS Catalysis, Vol. 3, Issue 4
  • DOI: 10.1021/cs300796e

NHC-Containing Manganese(I) Electrocatalysts for the Two-Electron Reduction of CO 2
journal, April 2014

  • Agarwal, Jay; Shaw, Travis W.; Stanton, Charles J.
  • Angewandte Chemie International Edition
  • DOI: 10.1002/anie.201311099

Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis
journal, February 2014

  • Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A.
  • Journal of the American Chemical Society, Vol. 136, Issue 14
  • DOI: 10.1021/ja501252f

Mechanistic insights into electrocatalytic CO 2 reduction within [Ru II (tpy)(NN)X] n+ architectures
journal, January 2014

  • White, Travis A.; Maji, Somnath; Ott, Sascha
  • Dalton Trans., Vol. 43, Issue 40
  • DOI: 10.1039/C4DT01591F

Bio-inspired CO 2 conversion by iron sulfide catalysts under sustainable conditions
journal, January 2015

  • Roldan, A.; Hollingsworth, N.; Roffey, A.
  • Chemical Communications, Vol. 51, Issue 35
  • DOI: 10.1039/C5CC02078F

Efficient Reduction of CO 2 to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials
journal, May 2014

  • Medina-Ramos, Jonnathan; DiMeglio, John L.; Rosenthal, Joel
  • Journal of the American Chemical Society, Vol. 136, Issue 23
  • DOI: 10.1021/ja501923g

Photocatalytic CO 2 reduction using a Mn complex as a catalyst
journal, January 2014

  • Takeda, Hiroyuki; Koizumi, Hiroki; Okamoto, Kouhei
  • Chem. Commun., Vol. 50, Issue 12
  • DOI: 10.1039/C3CC48122K

A robust and efficient cobalt molecular catalyst for CO 2 reduction
journal, January 2015

  • Chan, Sharon Lai-Fung; Lam, Tsz Lung; Yang, Chen
  • Chemical Communications, Vol. 51, Issue 37
  • DOI: 10.1039/C5CC00566C

Photocatalytic CO 2 Reduction to Formate Using a Mn(I) Molecular Catalyst in a Robust Metal–Organic Framework
journal, July 2015


Push or Pull? Proton Responsive Ligand Effects in Rhenium Tricarbonyl CO 2 Reduction Catalysts
journal, December 2014

  • Manbeck, Gerald F.; Muckerman, James T.; Szalda, David J.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 24
  • DOI: 10.1021/jp511131x

Photochemical CO 2 Reduction Catalyzed by Phenanthroline Extended Tetramesityl Porphyrin Complexes Linked with a Rhenium(I) Tricarbonyl Unit
journal, October 2015


Efficient electrocatalytic CO 2 reduction with a molecular cofacial iron porphyrin dimer
journal, January 2015

  • Mohamed, Eman A.; Zahran, Zaki N.; Naruta, Yoshinori
  • Chemical Communications, Vol. 51, Issue 95
  • DOI: 10.1039/C5CC04273A

Polyannulated Bis(N-heterocyclic carbene)palladium Pincer Complexes for Electrocatalytic CO 2 Reduction
journal, December 2015


Unique Solvent Effects on Visible-Light CO 2 Reduction over Ruthenium(II)-Complex/Carbon Nitride Hybrid Photocatalysts
journal, February 2016

  • Kuriki, Ryo; Ishitani, Osamu; Maeda, Kazuhiko
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 9
  • DOI: 10.1021/acsami.5b11836

A highly active nickel electrocatalyst shows excellent selectivity for CO 2 reduction in acidic media
journal, January 2016

  • Neri, Gaia; Aldous, Iain M.; Walsh, James J.
  • Chemical Science, Vol. 7, Issue 2
  • DOI: 10.1039/C5SC03225C

Covalent Immobilization of a Molecular Catalyst on Cu 2 O Photocathodes for CO 2 Reduction
journal, February 2016

  • Schreier, Marcel; Luo, Jingshan; Gao, Peng
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b12157

Photocatalytic Reduction of CO 2 with Re-Pyridyl-NHCs
journal, November 2015


CO 2 Capture by a Rhenium(I) Complex with the Aid of Triethanolamine
journal, October 2013

  • Morimoto, Tatsuki; Nakajima, Takuya; Sawa, Shuhei
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja409271s

Direct Detection of Key Reaction Intermediates in Photochemical CO 2 Reduction Sensitized by a Rhenium Bipyridine Complex
journal, April 2014

  • Kou, Youki; Nabetani, Yu; Masui, Dai
  • Journal of the American Chemical Society, Vol. 136, Issue 16
  • DOI: 10.1021/ja500403e

Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO 2 Reduction using Infrared Spectroelectrochemistry
journal, April 2014

  • Machan, Charles W.; Sampson, Matthew D.; Chabolla, Steven A.
  • Organometallics, Vol. 33, Issue 18
  • DOI: 10.1021/om500044a

Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide
journal, November 2014

  • Riplinger, Christoph; Sampson, Matthew D.; Ritzmann, Andrew M.
  • Journal of the American Chemical Society, Vol. 136, Issue 46
  • DOI: 10.1021/ja508192y

Influence of Weak Brønsted Acids on Electrocatalytic CO 2 Reduction by Manganese and Rhenium Bipyridine Catalysts
journal, January 2015

  • Riplinger, Christoph; Carter, Emily A.
  • ACS Catalysis, Vol. 5, Issue 2
  • DOI: 10.1021/cs501687n

One- and two-electron pathways in the electrocatalytic reduction of CO 2 by fac-Re(bpy)(CO) 3 Cl (bpy = 2,2′-bipyridine)
journal, January 1985

  • Sullivan, B. Patrick; Bolinger, C. Mark; Conrad, David
  • J. Chem. Soc., Chem. Commun., Issue 20
  • DOI: 10.1039/C39850001414

Direct observation of the reduction of carbon dioxide by rhenium bipyridine catalysts
journal, January 2013

  • Sampson, Matthew D.; Froehlich, Jesse D.; Smieja, Jonathan M.
  • Energy & Environmental Science, Vol. 6, Issue 12
  • DOI: 10.1039/c3ee42186d

Efficient photocatalytic CO2 reduction using [Re(bpy) (CO)3{P(OEt)3}]+
journal, May 1996

  • Hori, Hisao; Johnson, Frank P. A.; Koike, Kazuhide
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 96, Issue 1-3
  • DOI: 10.1016/1010-6030(95)04298-9

The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO 2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry
journal, March 2013

  • Benson, Eric E.; Sampson, Matthew D.; Grice, Kyle A.
  • Angewandte Chemie International Edition, Vol. 52, Issue 18
  • DOI: 10.1002/anie.201209911

Development of an Efficient Photocatalytic System for CO 2 Reduction Using Rhenium(I) Complexes Based on Mechanistic Studies
journal, February 2008

  • Takeda, Hiroyuki; Koike, Kazuhide; Inoue, Haruo
  • Journal of the American Chemical Society, Vol. 130, Issue 6
  • DOI: 10.1021/ja077752e

A mechanistic investigation of the photoinduced reduction of carbon dioxide mediated by tricarbonylbromo(2,2'-bipyridine)rhenium(I)
journal, December 1985

  • Kutal, Charles.; Weber, Michael A.; Ferraudi, Guillermo.
  • Organometallics, Vol. 4, Issue 12
  • DOI: 10.1021/om00131a016

Further studies of the photoinduced reduction of carbon dioxide mediated by tricarbonylbromo(2,2'-bipyridine)rhenium(I)
journal, March 1987

  • Kutal, Charles.; Corbin, A. Joan.; Ferraudi, Guillermo.
  • Organometallics, Vol. 6, Issue 3
  • DOI: 10.1021/om00146a020

Luminescence and redox reactions of the metal-to-ligand charge-transfer excited state of tricarbonylchloro-(polypyridyl)rhenium(I) complexes
journal, January 1986

  • Kalyanasundaram, Kuppuswamy
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 82, Issue 12
  • DOI: 10.1039/f29868202401

Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
journal, December 2009

  • Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar9001679

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

Kinetic Isotope Effects (KIE) and Density Functional Theory (DFT): A Match Made in Heaven?
journal, February 2015


The power of integrating kinetic isotope effects into the formalism of the Michaelis-Menten equation
journal, September 2013


Oxygen Kinetic Isotope Effects upon Catalytic Water Oxidation by a Monomeric Ruthenium Complex
journal, March 2012

  • Angeles-Boza, Alfredo M.; Roth, Justine P.
  • Inorganic Chemistry, Vol. 51, Issue 8
  • DOI: 10.1021/ic202745n

Studies of the Di-iron(VI) Intermediate in Ferrate-Dependent Oxygen Evolution from Water
journal, September 2012

  • Sarma, Rupam; Angeles-Boza, Alfredo M.; Brinkley, David W.
  • Journal of the American Chemical Society, Vol. 134, Issue 37
  • DOI: 10.1021/ja304786s

Competitive oxygen-18 kinetic isotope effects expose O–O bond formation in water oxidation catalysis by monomeric and dimeric ruthenium complexes
journal, January 2014

  • Angeles-Boza, Alfredo M.; Ertem, Mehmed Z.; Sarma, Rupam
  • Chem. Sci., Vol. 5, Issue 3
  • DOI: 10.1039/c3sc51919h

Mechanism of Manganese-Catalyzed Oxygen Evolution from Experimental and Theoretical Analyses of 18 O Kinetic Isotope Effects
journal, November 2015


The use of isotope effects to determine enzyme mechanisms
journal, January 2005


Interpretation of V/K isotope effects for enzymatic reactions exhibiting multiple isotopically sensitive steps
journal, December 2006


Competitive 13 C and 18 O kinetic isotope effects on CO 2 reduction catalyzed by Re(bpy)(CO) 3 Cl
journal, January 2015

  • Schneider, Taylor W.; Angeles-Boza, Alfredo M.
  • Dalton Transactions, Vol. 44, Issue 19
  • DOI: 10.1039/C4DT03977G

Architecture of Supramolecular Metal Complexes for Photocatalytic CO 2 Reduction:  Ruthenium−Rhenium Bi- and Tetranuclear Complexes
journal, April 2005

  • Gholamkhass, Bobak; Mametsuka, Hiroaki; Koike, Kazuhide
  • Inorganic Chemistry, Vol. 44, Issue 7
  • DOI: 10.1021/ic048779r

Oxygen-18 kinetic isotope effects in the dopamine .beta.-monooxygenase reaction: Evidence for a new chemical mechanism in non-heme, metallomonooxygenase
journal, January 1994

  • Tian, Gaochao; Berry, Joseph A.; Klinman, Judith P.
  • Biochemistry, Vol. 33, Issue 1
  • DOI: 10.1021/bi00167a030

Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
journal, May 2012

  • Smieja, J. M.; Benson, E. E.; Kumar, B.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1119863109

Calculation of Equilibrium Constants for Isotopic Exchange Reactions
journal, May 1947

  • Bigeleisen, Jacob; Mayer, Maria Goeppert
  • The Journal of Chemical Physics, Vol. 15, Issue 5
  • DOI: 10.1063/1.1746492

Quantum mechanical effects in inorganic and bioinorganic electron transfer
journal, December 1985


Secondary carbon-13 isotope effect on the ionization of benzoic acid
journal, January 1976

  • Bayles, John W.; Bron, Jan; Paul, Sylvia O.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0
  • DOI: 10.1039/f19767201546

Carbon-13 Isotope Effects in Systems Containing Carbon Dioxide, Bicarbonate, Carbonate, and Metal ions
journal, March 1965

  • Thode, H. G.; Shima, M.; Rees, C. E.
  • Canadian Journal of Chemistry, Vol. 43, Issue 3
  • DOI: 10.1139/v65-076

Mechanism of the Photochemical Ligand Substitution Reactions of f ac -[Re(bpy)(CO) 3 (PR 3 )] + Complexes and the Properties of Their Triplet Ligand-Field Excited States
journal, August 2002

  • Koike, Kazuhide; Okoshi, Nobuaki; Hori, Hisao
  • Journal of the American Chemical Society, Vol. 124, Issue 38
  • DOI: 10.1021/ja017032m

Oxygen Isotopic Effect on the Reduction of Aquo- and Hydroxopentaamminecobalt(III)
journal, October 1966

  • Diebler, Hartmut; Dodel, Peter H.; Taube, Henry
  • Inorganic Chemistry, Vol. 5, Issue 10
  • DOI: 10.1021/ic50044a011

Re(bipy-tBu)(CO) 3 Cl−improved Catalytic Activity for Reduction of Carbon Dioxide: IR-Spectroelectrochemical and Mechanistic Studies
journal, October 2010

  • Smieja, Jonathan M.; Kubiak, Clifford P.
  • Inorganic Chemistry, Vol. 49, Issue 20
  • DOI: 10.1021/ic1008363

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Energy-adjustedab initio pseudopotentials for the second and third row transition elements
journal, January 1990

  • Andrae, D.; H�u�ermann, U.; Dolg, M.
  • Theoretica Chimica Acta, Vol. 77, Issue 2
  • DOI: 10.1007/BF01114537

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journal, August 2017


[Ru II (tpy)(bpy)Cl] + -Catalyzed reduction of carbon dioxide. Mechanistic insights by carbon-13 kinetic isotope effects
journal, January 2018

  • Schneider, T. W.; Hren, M. T.; Ertem, M. Z.
  • Chemical Communications, Vol. 54, Issue 61
  • DOI: 10.1039/c8cc03009j

Mechanisms of catalytic reduction of CO 2 with heme and nonheme metal complexes
journal, January 2018

  • Fukuzumi, Shunichi; Lee, Yong-Min; Ahn, Hyun S.
  • Chemical Science, Vol. 9, Issue 28
  • DOI: 10.1039/c8sc02220h

Addition of Re-Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization: Addition of Re-Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization
journal, January 2020

  • Álvarez, Daniel; Díaz, Jesús; Menéndez, M. Isabel
  • European Journal of Inorganic Chemistry, Vol. 2020, Issue 3
  • DOI: 10.1002/ejic.201901196

A stable covalent organic framework for photocatalytic carbon dioxide reduction
journal, January 2020

  • Fu, Zhiwei; Wang, Xiaoyan; Gardner, Adrian M.
  • Chemical Science, Vol. 11, Issue 2
  • DOI: 10.1039/c9sc03800k

Immobilizing Re(CO) 3 Br(dcbpy) Complex on CsPbBr 3 Nanocrystal for Boosted Charge Separation and Photocatalytic CO 2 Reduction
journal, September 2019


A highly active, robust photocatalyst heterogenized in discrete cages of metal–organic polyhedra for CO 2 reduction
journal, January 2020

  • Lee, Hyeon Shin; Jee, Seohyeon; Kim, Raekyung
  • Energy & Environmental Science, Vol. 13, Issue 2
  • DOI: 10.1039/c9ee02619c