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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00641718" target="_blank" >RIV/61388955:_____/25:00641718 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0371766" target="_blank" >https://hdl.handle.net/11104/0371766</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5c03613" target="_blank" >10.1021/acs.inorgchem.5c03613</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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 CuIII–OH complex and organic substrates, involving hydride transfer coupled with a reversed electron transfer from CuIII–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 density and volume, signaling proton character. Second, intrinsic bond orbital analysis confirmed that HCET is a two-electron process: it involves the complete transfer of the proton and the C–H α-electron from the substrate to the Cu ion, while the β-electron undergoes a transient exchange, initially migrating alongside the α-electron to the Cu center before returning to substrate. An analogous HCET mechanism was identified in the reaction between a NiII–OH complex and TEMPOH, where two β-electrons are engaged in the process: one transiently and one completely transferred to a NiII-coordinating ligand.

Název v anglickém jazyce

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

Popis výsledku anglicky

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 CuIII–OH complex and organic substrates, involving hydride transfer coupled with a reversed electron transfer from CuIII–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 density and volume, signaling proton character. Second, intrinsic bond orbital analysis confirmed that HCET is a two-electron process: it involves the complete transfer of the proton and the C–H α-electron from the substrate to the Cu ion, while the β-electron undergoes a transient exchange, initially migrating alongside the α-electron to the Cu center before returning to substrate. An analogous HCET mechanism was identified in the reaction between a NiII–OH complex and TEMPOH, where two β-electrons are engaged in the process: one transiently and one completely transferred to a NiII-coordinating ligand.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

46

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

22698-22710

Kód UT WoS článku

001614136700001

EID výsledku v databázi Scopus

2-s2.0-105022632637