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

Research output: Contribution to journalArticle

6 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)5932-5940
Number of pages9
JournalACS Catalysis
Volume7
Issue number9
DOIs
StatePublished - Sep 1 2017

Fingerprint

Ruthenium
Carbon Dioxide
Carbon dioxide
Ligands
Voltammetry
Benzene
Discrete Fourier transforms
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry
Single crystals
Catalysts
Kinetics
Oxidation-Reduction
dichlorotetrakis(dimethyl sulfoxide)ruthenium II

Keywords

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

Cite this

Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes : Discerning between Electronic and Steric Effects. / Ono, Takashi; Qu, Shuanglin; Gimbert-Surinach, Carolina; Johnson, Michelle A.; Marell, Daniel J.; Benet-Buchholz, Jordi; Cramer, Christopher J.; Llobet, Antoni.

In: ACS Catalysis, Vol. 7, No. 9, 01.09.2017, p. 5932-5940.

Research output: Contribution to journalArticle

Ono, Takashi ; Qu, Shuanglin ; Gimbert-Surinach, Carolina ; Johnson, Michelle A. ; Marell, Daniel J. ; Benet-Buchholz, Jordi ; Cramer, Christopher J. ; Llobet, Antoni. / Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes : Discerning between Electronic and Steric Effects. In: ACS Catalysis. 2017 ; Vol. 7, No. 9. pp. 5932-5940.
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