Proton-coupled electron transfer (PCET) mediated by hydroquinone and related molecules is key to natural and artificial energy conversion. The reactivity of these molecules depends on their bond disso...

New research from Carnegie Mellon University’s Mellon College of Science aims to understand how forever chemichals build up in the body.

FeIV=O units found in the active sites of nonheme iron oxygenases and related synthetic analogs are intriguing inter-mediates capable of performing challenging oxygenation reactions. The first crystal...

Reactions that alter organic scaffolds by a single atom are already proving useful, but time will tell if they’ll fundamentally change how molecules are made

Herein, we show for the first time that thiolate ligands can play an important role in promoting 2e- oxo atom transfer with nonheme iron. We examine the mechanism of oxo atom transfer to a cis thiolate sulfur for two structurally related iron complexes using low-temperature kinetics, spectroscopic, and computational methods. Intermediate oxo atom donor adducts, FeOIAr, are spectroscopically characterized and shown to have electronic spectral, EPR, and Mössbauer parameters, and kinetic barriers dependent on the nature of the oxo atom donor. More stable adducts containing pyridine N-oxide (PNO) were crystallographically characterized and computationally optimized to establish optimum functionals and basis sets. Oxo atom transfer is shown both experimentally and computationally to involve a stepwise, as opposed to a concerted, mechanism. A new metastable intermediate is observed by low-temperature Mössbauer and ⊥-mode EPR after the Fe–OxIPh intermediate and prior to the final sulfenate Fe-OSR product. The DFT calculated minimum energy pathway is shown to contain a local minimum between the Fe–O2IPh adduct and Fe–S(R)O product. The DFT optimized geometric and electronic structure of this intermediate is shown to be consistent with an S = 1 Fe(IV)═O that is antiferromagnetically coupled to an S = 1/2 radical delocalized over the two cis thiolate-sulfurs, analogous to the electronic configuration of P450 Cmpd I. Radical character on the thiolate sulfur adjacent to the oxo is shown to facilitate trapping of the high-valent Fe-oxo as a η2-SO-Fe sulfenate complex.

New compounds are 'among the most complex organosilanes ever synthesised'

Carnegie Mellon University’s Yisong (Alex) Guo and collaborators at the University of Minnesota and the Universitat de Girona have unlocked new understanding of how to design synthetic model systems t...

In this research article, we report the synthesis, characterization, and reactivity of a family of Cu complexes bearing a tridentate iminosemiquinone ligand and ancillary amine ligands ((sqONO)CuII(L)...

Wastewater produced from hydraulic fracturing of unconventional oil and gas wells is a complex mixture of high levels of salts and variable levels of organics, naturally occurring radioactive material...

Three intermediates in the formylglycine-generating enzyme are characterized at the molecular level.

SCS undergrads Sheng Shu and Hyojae Park have received 2025 Goldwater Scholarships.

Already-approved grants were sent back for review, while 200 active ones may face termination

Unclear how many chemistry students have been affected by ‘brand-new . . . scary era’

Some say their visas were revoked this week; Beijing warns other nationals to reconsider study plans in America.