#PCET

@agnideep.bsky.social

5 months ago

Probing Proton Coupled Electron Transfer and Fluorine Atom Transfer in CoII–Catalyzed Oxidative Hydrocarbon Fluorination In exploring CoII-catalyzed oxidative fluorination, we have synthesized a family of CoII complexes supported by linear tetradentate ligands. Nuclear magnetic resonance and infrared spectroscopies, mass spectrometry, and X-ray crystallography provided insights into the structural and electronic properties of the catalysts. All complexes displayed a cis-α geometry at Co, while displaying variable CoII/III E1/2 values. Certain catalysts delivered near quantitative yields of fluorinated product in the selectfluor-mediated fluorination of 1-adamantanol. The rate of fluorination was impacted by the nature of the supporting ligands, with more electron-rich Co sites displaying faster rates of fluorination, but lower yields of fluorinated product. Kinetic analysis suggested that proton coupled electron transfer (PCET) C–H activation was rate-limiting (substrate kinetic isotope effects = 2). We concluded that a CoIV(F)2 entity was the likely PCET oxidant producing an alkyl radical, HF, and CoIII–F. In order to explore how the alkyl radical and CoIII–F reacted through fluorine atom transfer (FAT), we probed a series of radical clock bicyclic substrates in the CoII-catalyzed reaction. Product analysis supported the occurrence of a fast FAT rebound, consistent with the alkyl radical being in close proximity to the fluorine donor.

💡Published 💡
Excited to share our new paper in Inorg. Chem 🧪
We show that Co(II)-catalyzed hydrocarbon fluorination proceeds via rate-limiting PCET and a fast fluorine atom rebound mechanism. 🔗 pubs.acs.org/doi/10.1021/...
#Chemistry #PCET #Fluorination #Catalysis #TCD
@acs.org @fenicu.bsky.social

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Ken Lo

@bhkenlo.bsky.social

5 months ago

Probing Proton Coupled Electron Transfer and Fluorine Atom Transfer in CoII–Catalyzed Oxidative Hydrocarbon Fluorination | Inorganic Chemistry pubs.acs.org/doi/10.1021/... McDonald and co-workers @InorgChem #cobalt #II #PCET #FAT #fluorination

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Tim Schramm

@tkschramm.bsky.social

7 months ago

Expanding the PCET Thermochemistry of CpN3: N–H Bond Strengths of Metal-Free CpN3 Molecules and the Influence of Fe(CO)3 Coordination Amine rich cyclopentadienyl (CpN3) ligands are electronically distinct from classical Cp ligand architectures, as they exhibit fascinating proton-coupled electron transfer (PCET) chemistry under acidi...

Happy to share my first PhD contribution from the @grimmelab.bsky.social! 🎓 We explored the N-H bond thermochemistry of an amine-rich cyclopentadienyl ligand motif that shows no change in N-H bond acidity when coordinated to iron - surprising!
#compchem #PCET #catalysis #ORCA
doi.org/10.1021/acso...

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Ken Lo

@bhkenlo.bsky.social

8 months ago

Mechanistic Studies of the Proton-Coupled Electron Transfer Reactivity of a Cobalt Complex with a Proton-Responsive PNP Pincer-Type Ligand | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Podewitz, Siewert, and co-workers @InorgChem #cobalt #PNP #pincer #PCET #DFT #BDFE

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Ken Lo

@bhkenlo.bsky.social

9 months ago

Direct Evidence for Buffer-Enhanced Proton-Coupled Electron Transfer Generation of a High-Valent Metal-Oxo Complex | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Meyer and co-workers @InorgChem #ruthenium #PCET #oxo #buffer_enanced #concerted #ITO #catalysis

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Sven T. Stripp

@stripplab.bsky.social

9 months ago

Looking forward!! #PCET #FTW

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Ken Lo

@bhkenlo.bsky.social

10 months ago

Impact of Pendant Amine Basicity on Electrochemically-Promoted Cobalt Hydride Formation: Kinetic and Mechanistic Analysis | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Dempsey and co-workers @InorgChem #cobalt #hydride #amine #CO2 #PCET #H2

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LMU München

@lmu.de

11 months ago

Ivana Ivanović-Burmazović works with high pressure to investigate reaction rates.

Under pressure: #LMU Researchers decode #PCET mechanisms 🔄 – offering insights that could drive advances in energy conversion and storage technologies.🧪 Read more: www.lmu.de/en/newsroom/... #Chemistry #ReactionMechanisms #HighPressure #PhotoinducedReactions #ExcitedStateReactions #ElectronTransfer

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Adam Weingarten

@adamsweingarten.bsky.social

11 months ago

High-pressure pump–probe experiments reveal the mechanism of excited-state proton-coupled electron transfer and a shift from stepwise to concerted pathways - Nature Chemistry Chemical energy conversion and storage rely on the selective movement of protons and electrons, thus understanding these processes is important for applications. Now experiments at elevated pressures ...

We behave differently under pressure, and so do photocatalysts! Congrats to Ivanović-Burmazović, Guldi & team for their latest work @naturechemistry.bsky.social www.nature.com/articles/s41...
#Chemistry
#PCET
#ReactionMechanisms
#PhotoinducedReactions
#ExcitedStateReactions
#HighPressure

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Ken Lo

@bhkenlo.bsky.social

1 year ago

Electron-Donating para-Substituent (X) Enhances the Water Oxidation Activity of the Catalyst Ru(4′-X-terpyridine)(phenanthroline-SO3)+ | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Musaev, Grotjahn, and co-workers @InorgChem #ruthenium #phenSO3 #X_terpy #WOC #PCET #ETPTs

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Ken Lo

@bhkenlo.bsky.social

1 year ago

Harnessing the Cobalt-Catalyzed Hydrogen Evolution Reaction through a Data-Driven Approach | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Liang and Zhang @InorgChem #cobalt #SMADP #PCET #HER

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Ken Lo

@bhkenlo.bsky.social

1 year ago

The Catalytic Mechanism of a Highly Active Cobalt Chlorin Complex for Photocatalytic Water Oxidation | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Yamada and co-workers @InorgChem #cobalt #chlorin #electrocatalysis #photocatalysis #spectroEC #water_oxidation #PCET

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Ken Lo

@bhkenlo.bsky.social

1 year ago

nhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Iwano and Uchida @InorgChem #POMs #Keplerate #Keggin #core_shell #proton_conduction #PCET

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Magda Pascual-Borràs

@mpascualb.bsky.social

1 year ago

Vanadium Substitution Dictates H Atom Uptake at Lindqvist-type Polyoxotungstates Understanding how modification of molecular structures changes the thermochemistry of H atom uptake can provide design criteria for the formation of highly active catalysts for reductive transformatio...

Our collaboration with @matsonlab.bsky.social looking at #PCET at the surface of vanadium-doped Polyoxotungstates is just out in Inorg. Chem.! pubs.acs.org/doi/10.1021/... #POMs #POMspapers

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Ken Lo

@bhkenlo.bsky.social

1 year ago

Vanadium Substitution Dictates H Atom Uptake at Lindqvist-type Polyoxotungstates | Inorganic Chemistry pubs.acs.org/doi/10.1021/... Errington, @MatsonLab and co-workers @InorgChem #polyoxotungstates #PCET #vanadium #BDFE

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