biostudies-literatureWojdyla ZAkademie Ved Cesk? RepublikyFP7 People: Marie-Curie ActionsMinisterstvo ?kolstv?, Ml?de?e a Telov?chovyGrantov? Agentura Cesk? Republiky22698-22710https://www.ebi.ac.uk/biostudies/studies/S-EPMC12648667biostudies-literatureUnknown64(46)This study explores hydride-coupled electron transfer (HCET) as a fundamentally distinct mechanism alternative to proton-coupled electron transfer (PCET). HCET was identified in the reaction between a Cu^III-OH complex and organic substrates, involving hydride transfer coupled with a reversed electron transfer from Cu^III-OH to the substrate in a single-barrier step. First, we identified the connection between the thermodynamic cycles and reactivity and showed that the mechanism is dictated by the cycle with more favorable off-diagonal thermodynamics. As evidenced by electronic-structure-based descriptors, the transferred hydrogen atom in HCET gains electron density and volume at the transition state, indicating hydride character, while in PCET, it loses electron densitInorganic chemistryHydrogen Atom Abstraction via Hydride-Coupled Electron Transfer and Its Origin.PMC1264866724-11247SCZ.02.01.01/00/ 22_008/0004617101150275Srnec MGopinath JSWojdyla ZfalseHydrogen Atom Abstraction via Hydride-Coupled Electron Transfer and Its Origin.This study explores hydride-coupled electron transfer (HCET) as a fundamentally distinct mechanism alternative to proton-coupled electron transfer (PCET). HCET was identified in the reaction between a Cu^III-OH complex and organic substrates, involving hydride transfer coupled with a reversed electron transfer from Cu^III-OH to the substrate in a single-barrier step. First, we identified the connection between the thermodynamic cycles and reactivity and showed that the mechanism is dictated by the cycle with more favorable off-diagonal thermodynamics. As evidenced by electronic-structure-based descriptors, the transferred hydrogen atom in HCET gains electron density and volume at the transition state, indicating hydride character, while in PCET, it loses electron densit2025-01-01T00:00:00Z2025 Nov2026-06-05T17:54:42.243Z2026-05-19T03:11:57.003ZS-EPMC126486674123115310.1021/acs.inorgchem.5c03613