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Title: Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes

Abstract

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO 2 reduction ability. We reported complexes are of the type Re(N-N)(CO) 3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO 2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO 2 reduction by 1 in acetonitrile using density functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG = 27.2 kcal mol –1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO) 3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reductionmore » potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (i cat/i p) 2, up to 7 times larger than that of I.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [4];  [3];  [5]; ORCiD logo [1]
  1. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry
  2. Vassar College, Poughkeepsie, NY (United States). Dept. of Chemistry
  3. DePaul Univ., Chicago, IL (United States). Dept. of Chemistry
  4. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
  5. Yale Univ., New Haven, CT (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1349563
Report Number(s):
BNL-113673-2017-JA
Journal ID: ISSN 0020-1669; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704; SC0001059
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nganga, John K., Samanamu, Christian R., Tanski, Joseph M., Pacheco, Carlos, Saucedo, Cesar, Batista, Victor S., Grice, Kyle A., Ertem, Mehmed Z., and Angeles-Boza, Alfredo M. Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.6b02384.
Nganga, John K., Samanamu, Christian R., Tanski, Joseph M., Pacheco, Carlos, Saucedo, Cesar, Batista, Victor S., Grice, Kyle A., Ertem, Mehmed Z., & Angeles-Boza, Alfredo M. Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes. United States. doi:10.1021/acs.inorgchem.6b02384.
Nganga, John K., Samanamu, Christian R., Tanski, Joseph M., Pacheco, Carlos, Saucedo, Cesar, Batista, Victor S., Grice, Kyle A., Ertem, Mehmed Z., and Angeles-Boza, Alfredo M. Thu . "Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes". United States. doi:10.1021/acs.inorgchem.6b02384. https://www.osti.gov/servlets/purl/1349563.
@article{osti_1349563,
title = {Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes},
author = {Nganga, John K. and Samanamu, Christian R. and Tanski, Joseph M. and Pacheco, Carlos and Saucedo, Cesar and Batista, Victor S. and Grice, Kyle A. and Ertem, Mehmed Z. and Angeles-Boza, Alfredo M.},
abstractNote = {In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO2 reduction ability. We reported complexes are of the type Re(N-N)(CO)3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO2 reduction by 1 in acetonitrile using density functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG‡ = 27.2 kcal mol–1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO)3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (icat/ip)2, up to 7 times larger than that of I.},
doi = {10.1021/acs.inorgchem.6b02384},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 6,
volume = 56,
place = {United States},
year = {2017},
month = {3}
}

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