TY - JOUR
T1 - Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes
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 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/9/1
Y1 - 2017/9/1
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.
KW - DFT
KW - catalytic carbon dioxide hydrogenation
KW - catalytic carbon dioxide reduction
KW - ruthenium polypyridyl complexes
KW - transition metal redox properties
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U2 - 10.1021/acscatal.7b00603
DO - 10.1021/acscatal.7b00603
M3 - Article
AN - SCOPUS:85029172819
SN - 2155-5435
VL - 7
SP - 5932
EP - 5940
JO - ACS Catalysis
JF - ACS Catalysis
IS - 9
ER -