Agnideep Das

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

📢 We are excited to welcome our newest Associate Editors Marine Desage-El Murr @unistra.fr and Aurelio Mateo-Alonso @kokelab.bsky.social @polymat.bsky.social on the Editorial Board of #BJOC 💎🔓.

Please join us in welcoming Marine and Aurelio (Koke)!

https://tinyurl.com/2p9ke8xd

Indeed it is huge in terms of time investment and work we have done. pays well as it selected as hot paper @angewandtechemie.bsky.social. Thanks to all the coauthors and special thanks to Aidan @fenicu.bsky.social for effortlessly engaging and sharing advice during this work #chemsky #newpublication

High‐Valent Cobalt‐Difluoride in Oxidative Fluorination of Saturated Hydrocarbons Polyamine-supported CoII complexes catalyzed the oxidative fluorination of saturated hydrocarbons, in some instances selectively, when combined with Selectfluor and CsF, producing fluorinated product...

@agnideep.bsky.social's mega-project on our efforts to develop catalytic fluorination of hydrocarbons is now published. Congrats Agni on an excellent effort!! #chemsky
onlinelibrary.wiley.com/doi/10.1002/...

A good #chemsky week so far, Christmas dinner done, three Senior Sophister theses submitted, and a new group photo (all we need now is for reviewer #3 to be nice!).