Our CO2 reduction catalyst featured in Chemistry Views
Ben's paper on a Ruthenium CO2 reduction catalyst was featured by Chemistry Views.
Ben A. Johnson, Hemlata Agarwala, Travis A. White, Edgar Mijangos, Somnath Maji, Sascha Ott,
Chem. Eur. J. 2016.
Judicious Ligand Design in Ruthenium Polypyridyl CO2 Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects
A series of RuII polypyridyl complexes of the structural design [RuII(R−tpy)(NN)(CH3CN)]2+ (R−tpy=2,2′:6′,2′′-terpyridine (R=H) or 4,4′,4′′-tri-tert-butyl-2,2′:6′,2′′-terpyridine (R=tBu); NN=2,2′-bipyridine with methyl substituents in various positions) have been synthesized and analyzed for their ability to function as electrocatalysts for the reduction of CO2 to CO. Detailed electrochemical analyses establish how substitutions at different ring positions of the bipyridine and terpyridine ligands can have profound electronic and, even more importantly, steric effects that determine the complexes’ reactivities. Whereas electron-donating groups para to the heteroatoms exhibit the expected electronic effect, with an increase in turnover frequencies at increased overpotential, the introduction of a methyl group at the ortho position of NN imposes drastic steric effects. Two complexes, [RuII(tpy)(6-mbpy)(CH3CN)]2+ (trans-2+; 6-mbpy=6-methyl-2,2′-bipyridine) and [RuII(tBu−tpy)(6-mbpy)(CH3CN)]2+ (trans-2+), in which the methyl group of the 6-mbpy ligand is trans to the CH3CN ligand, show electrocatalytic CO2 reduction at a previously unreactive oxidation state of the complex. This low overpotential pathway follows an ECE mechanism (electron transfer–chemical reaction–electron transfer), and is a direct result of steric interactions that facilitate CH3CN ligand dissociation, CO2 coordination, and ultimately catalytic turnover at the first reduction potential of the complexes. All experimental observations are rigorously corroborated by DFT calculations.
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Seminar: Martin Oestreich, Wed, 30th March. 13:15
Seminar by Prof. Martin Oestreich.
The seminar will be held at 15:15 in the seminar room, Floor 1, House 7 at Ångström.
Heavier pnictogens – treasures for optical electronic and reactivity tuning
The Orthaber group has boarded the front cover of this week’s issue of Dalton Transactions, with a Hot invited Frontier article on the Treasures of the Heavier Pnictogens (DOI: 10.1039/C9DT00574A).
Ulrike's paper in Chem Comm
The article presents the first application of Rutherford Backscattering Spectroscopy to study post-synthetic ligand exchange in metal-organic frameworks.
Bis' paper in ChemSusChem: CONGRATS!
Iron Pentapyridyl Complexes as Molecular Water Oxidation Catalysts: Strong Influence of a Chloride Ligand and pH in Altering the Mechanism
New publications from the Orthaber group
Silver coordination polymers using the tetratopic BDF-H2 ligand (Eur. J. I. C.) and unexpected chloroarsine chemistry (P, S, Si and rel. El.).
Design av guld nanopartiklar för molekylär elektronik
Våra nydesignade guld nanopartiklar och deras tillämpning i molekylär elektronik har accepterats i Mol. Sys. Des. Eng. Stort tack till våra kollaborationspartners från Engineering (Leifer-gruppen) och Montpellier (Serein-Spirau-gruppen).