Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes: Discerning between Electronic and Steric Effects

Takashi Ono; Shuanglin Qu; Carolina Gimbert-Surinach; Michelle A. Johnson; Daniel J. Marell; Jordi Benet-Buchholz; Christopher J. Cramer; Antoni Llobet

doi:10.1021/acscatal.7b00603

Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes: Discerning between Electronic and Steric Effects

Takashi Ono, Shuanglin Qu, Carolina Gimbert-Surinach, Michelle A. Johnson, Daniel J. Marell, Jordi Benet-Buchholz, Christopher J. Cramer, Antoni Llobet

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Abstract

The preparation and isolation of a family of Ru-Cl complexes containing the deprotonated anionic tridentate meridional ligand (1Z,3Z)-N¹,N³-di(pyridin-2-yl)isoindoline-1,3-diimine (Hbid) and 1,3-di(2-pyridyl)benzene) (Hdpb), namely, [Ru(bid)(acac)Cl], 1d, [Ru(bid)(6,6′-Me₂-bpy)Cl], 1e, trans-[Ru(bid)(py)₂Cl], 2, [Ru(dpb)(bpy)Cl], 3a, and [Ru(dpb)(4,4′-(COOEt)₂-bpy)Cl], 3b, are reported. All these complexes have been thoroughly characterized in solution by NMR spectroscopy and for 1d and 1e by single-crystal X-ray diffraction analysis. Furthermore, the redox properties of all complexes have been investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The capacity of the various complexes to catalyze hydrogenative CO₂ reduction was also investigated. Compound 1e is the best catalyst, achieving initial turnover frequencies above 1000 h^-1. Kinetic analysis identifies a relationship between Ru(III/II) couple redox potentials and initial turnover frequencies. Finally, DFT calculations further characterize the catalytic cycle of these complexes and rationalize electronic and steric effects deriving from the auxiliary ligands.

Original language	English (US)
Pages (from-to)	5932-5940
Number of pages	9
Journal	ACS Catalysis
Volume	7
Issue number	9
DOIs	https://doi.org/10.1021/acscatal.7b00603
State	Published - Sep 1 2017

Bibliographical note

Funding Information:
Support was received from MINECO and FEDER (CTQ2016-80058-R, CTQ2015-73028-EXP, SEV 2013-0319, ENE2016-82025-REDT, CTQ2016-81923-REDC), AGAUR (2014-SGR-915), and the U.S. National Science Foundation (CHE-1361595). T.O. thanks MINECO for a predoctoral grant. We also acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper.

Publisher Copyright:
© 2017 American Chemical Society.

Keywords

DFT
catalytic carbon dioxide hydrogenation
catalytic carbon dioxide reduction
ruthenium polypyridyl complexes
transition metal redox properties

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title = "Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes: Discerning between Electronic and Steric Effects",

abstract = "The preparation and isolation of a family of Ru-Cl complexes containing the deprotonated anionic tridentate meridional ligand (1Z,3Z)-N1,N3-di(pyridin-2-yl)isoindoline-1,3-diimine (Hbid) and 1,3-di(2-pyridyl)benzene) (Hdpb), namely, [Ru(bid)(acac)Cl], 1d, [Ru(bid)(6,6′-Me2-bpy)Cl], 1e, trans-[Ru(bid)(py)2Cl], 2, [Ru(dpb)(bpy)Cl], 3a, and [Ru(dpb)(4,4′-(COOEt)2-bpy)Cl], 3b, are reported. All these complexes have been thoroughly characterized in solution by NMR spectroscopy and for 1d and 1e by single-crystal X-ray diffraction analysis. Furthermore, the redox properties of all complexes have been investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The capacity of the various complexes to catalyze hydrogenative CO2 reduction was also investigated. Compound 1e is the best catalyst, achieving initial turnover frequencies above 1000 h-1. Kinetic analysis identifies a relationship between Ru(III/II) couple redox potentials and initial turnover frequencies. Finally, DFT calculations further characterize the catalytic cycle of these complexes and rationalize electronic and steric effects deriving from the auxiliary ligands.",

keywords = "DFT, catalytic carbon dioxide hydrogenation, catalytic carbon dioxide reduction, ruthenium polypyridyl complexes, transition metal redox properties",

author = "Takashi Ono and Shuanglin Qu and Carolina Gimbert-Surinach and Johnson, {Michelle A.} and Marell, {Daniel J.} and Jordi Benet-Buchholz and Cramer, {Christopher J.} and Antoni Llobet",

note = "Funding Information: Support was received from MINECO and FEDER (CTQ2016-80058-R, CTQ2015-73028-EXP, SEV 2013-0319, ENE2016-82025-REDT, CTQ2016-81923-REDC), AGAUR (2014-SGR-915), and the U.S. National Science Foundation (CHE-1361595). T.O. thanks MINECO for a predoctoral grant. We also acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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T2 - Discerning between Electronic and Steric Effects

AU - Ono, Takashi

AU - Qu, Shuanglin

AU - Gimbert-Surinach, Carolina

AU - Johnson, Michelle A.

AU - Marell, Daniel J.

AU - Benet-Buchholz, Jordi

AU - Cramer, Christopher J.

AU - Llobet, Antoni

N1 - Funding Information: Support was received from MINECO and FEDER (CTQ2016-80058-R, CTQ2015-73028-EXP, SEV 2013-0319, ENE2016-82025-REDT, CTQ2016-81923-REDC), AGAUR (2014-SGR-915), and the U.S. National Science Foundation (CHE-1361595). T.O. thanks MINECO for a predoctoral grant. We also acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/9/1

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N2 - The preparation and isolation of a family of Ru-Cl complexes containing the deprotonated anionic tridentate meridional ligand (1Z,3Z)-N1,N3-di(pyridin-2-yl)isoindoline-1,3-diimine (Hbid) and 1,3-di(2-pyridyl)benzene) (Hdpb), namely, [Ru(bid)(acac)Cl], 1d, [Ru(bid)(6,6′-Me2-bpy)Cl], 1e, trans-[Ru(bid)(py)2Cl], 2, [Ru(dpb)(bpy)Cl], 3a, and [Ru(dpb)(4,4′-(COOEt)2-bpy)Cl], 3b, are reported. All these complexes have been thoroughly characterized in solution by NMR spectroscopy and for 1d and 1e by single-crystal X-ray diffraction analysis. Furthermore, the redox properties of all complexes have been investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The capacity of the various complexes to catalyze hydrogenative CO2 reduction was also investigated. Compound 1e is the best catalyst, achieving initial turnover frequencies above 1000 h-1. Kinetic analysis identifies a relationship between Ru(III/II) couple redox potentials and initial turnover frequencies. Finally, DFT calculations further characterize the catalytic cycle of these complexes and rationalize electronic and steric effects deriving from the auxiliary ligands.

AB - The preparation and isolation of a family of Ru-Cl complexes containing the deprotonated anionic tridentate meridional ligand (1Z,3Z)-N1,N3-di(pyridin-2-yl)isoindoline-1,3-diimine (Hbid) and 1,3-di(2-pyridyl)benzene) (Hdpb), namely, [Ru(bid)(acac)Cl], 1d, [Ru(bid)(6,6′-Me2-bpy)Cl], 1e, trans-[Ru(bid)(py)2Cl], 2, [Ru(dpb)(bpy)Cl], 3a, and [Ru(dpb)(4,4′-(COOEt)2-bpy)Cl], 3b, are reported. All these complexes have been thoroughly characterized in solution by NMR spectroscopy and for 1d and 1e by single-crystal X-ray diffraction analysis. Furthermore, the redox properties of all complexes have been investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The capacity of the various complexes to catalyze hydrogenative CO2 reduction was also investigated. Compound 1e is the best catalyst, achieving initial turnover frequencies above 1000 h-1. Kinetic analysis identifies a relationship between Ru(III/II) couple redox potentials and initial turnover frequencies. Finally, DFT calculations further characterize the catalytic cycle of these complexes and rationalize electronic and steric effects deriving from the auxiliary ligands.

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KW - catalytic carbon dioxide hydrogenation

KW - catalytic carbon dioxide reduction

KW - ruthenium polypyridyl complexes

KW - transition metal redox properties

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Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes: Discerning between Electronic and Steric Effects

Abstract

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Keywords

UN SDGs

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