Hydrogen Atom Abstraction via Hydride-Coupled Electron Transfer and Its Origin.

ABSTRACT: 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 densit

SUBMITTER: Wojdyla Z 

PROVIDER: S-EPMC12648667 | biostudies-literature | 2025 Nov

REPOSITORIES: biostudies-literature