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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2025

Confidentiality

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

Name of the periodical

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Volume of the periodical

64

Issue of the periodical within the volume

46

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

22698-22710

UT code for WoS article

001614136700001

EID of the result in the Scopus database

2-s2.0-105022632637