FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2893669076> ?p ?o ?g. }

• W2893669076 abstract "Hydrogen atom abstraction (HAA) reactions are cornerstones of chemistry. Various (metallo)enzymes performing the HAA catalysis evolved in nature and inspired the rational development of multiple synthetic catalysts. Still, the factors determining their catalytic efficiency are not fully understood. Herein, we define the simple thermodynamic factor η by employing two thermodynamic cycles: one for an oxidant (catalyst), along with its reduced, protonated, and hydrogenated form; and one for the substrate, along with its oxidized, deprotonated, and dehydrogenated form. It is demonstrated that η reflects the propensity of the substrate and catalyst for (a)synchronicity in concerted H+/e- transfers. As such, it significantly contributes to the activation energies of the HAA reactions, in addition to a classical thermodynamic (Bell-Evans-Polanyi) effect. In an attempt to understand the physicochemical interpretation of η, we discovered an elegant link between η and reorganization energy λ from Marcus theory. We discovered computationally that for a homologous set of HAA reactions, λ reaches its maximum for the lowest |η|, which then corresponds to the most synchronous HAA mechanism. This immediately implies that among HAA processes with the same reaction free energy, ΔG0, the highest barrier (≡ΔG≠) is expected for the most synchronous proton-coupled electron (i.e., hydrogen) transfer. As proof of concept, redox and acidobasic properties of nonheme FeIVO complexes are correlated with activation free energies for HAA from C-H and O-H bonds. We believe that the reported findings may represent a powerful concept in designing new HAA catalysts." @default.
• W2893669076 created "2018-10-05" @default.
• W2893669076 creator A5020419269 @default.
• W2893669076 creator A5076147652 @default.
• W2893669076 creator A5083427846 @default.
• W2893669076 creator A5087245272 @default.
• W2893669076 date "2018-09-25" @default.
• W2893669076 modified "2023-10-18" @default.
• W2893669076 title "Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity" @default.
• W2893669076 cites W1968963012 @default.
• W2893669076 cites W1976205221 @default.
• W2893669076 cites W1978607450 @default.
• W2893669076 cites W2013596909 @default.
• W2893669076 cites W2019692171 @default.
• W2893669076 cites W2029784659 @default.
• W2893669076 cites W2041930594 @default.
• W2893669076 cites W2062244899 @default.
• W2893669076 cites W2071070420 @default.
• W2893669076 cites W2071982166 @default.
• W2893669076 cites W2076587517 @default.
• W2893669076 cites W2078899588 @default.
• W2893669076 cites W2081482983 @default.
• W2893669076 cites W2081643670 @default.
• W2893669076 cites W2089275038 @default.
• W2893669076 cites W2105067416 @default.
• W2893669076 cites W2112542406 @default.
• W2893669076 cites W2134994080 @default.
• W2893669076 cites W2142419145 @default.
• W2893669076 cites W2155860547 @default.
• W2893669076 cites W2156416251 @default.
• W2893669076 cites W2313309178 @default.
• W2893669076 cites W2314123842 @default.
• W2893669076 cites W2315008872 @default.
• W2893669076 cites W2332562347 @default.
• W2893669076 cites W2335441010 @default.
• W2893669076 cites W2398174906 @default.
• W2893669076 cites W2547884128 @default.
• W2893669076 cites W2594081393 @default.
• W2893669076 cites W2594815952 @default.
• W2893669076 cites W2628771438 @default.
• W2893669076 cites W2781813451 @default.
• W2893669076 cites W2799530527 @default.
• W2893669076 cites W4211091797 @default.
• W2893669076 doi "https://doi.org/10.1073/pnas.1806399115" @default.
• W2893669076 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/6217389" @default.
• W2893669076 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/30254163" @default.
• W2893669076 hasPublicationYear "2018" @default.
• W2893669076 type Work @default.
• W2893669076 sameAs 2893669076 @default.
• W2893669076 citedByCount "58" @default.
• W2893669076 countsByYear W28936690762019 @default.
• W2893669076 countsByYear W28936690762020 @default.
• W2893669076 countsByYear W28936690762021 @default.
• W2893669076 countsByYear W28936690762022 @default.
• W2893669076 countsByYear W28936690762023 @default.
• W2893669076 crossrefType "journal-article" @default.
• W2893669076 hasAuthorship W2893669076A5020419269 @default.
• W2893669076 hasAuthorship W2893669076A5076147652 @default.
• W2893669076 hasAuthorship W2893669076A5083427846 @default.
• W2893669076 hasAuthorship W2893669076A5087245272 @default.
• W2893669076 hasBestOaLocation W28936690761 @default.
• W2893669076 hasConcept C118629725 @default.
• W2893669076 hasConcept C121332964 @default.
• W2893669076 hasConcept C142724271 @default.
• W2893669076 hasConcept C145148216 @default.
• W2893669076 hasConcept C147597530 @default.
• W2893669076 hasConcept C161790260 @default.
• W2893669076 hasConcept C178790620 @default.
• W2893669076 hasConcept C185592680 @default.
• W2893669076 hasConcept C204787440 @default.
• W2893669076 hasConcept C2776640939 @default.
• W2893669076 hasConcept C2776910235 @default.
• W2893669076 hasConcept C2780263894 @default.
• W2893669076 hasConcept C63338738 @default.
• W2893669076 hasConcept C71924100 @default.
• W2893669076 hasConcept C97355855 @default.
• W2893669076 hasConceptScore W2893669076C118629725 @default.
• W2893669076 hasConceptScore W2893669076C121332964 @default.
• W2893669076 hasConceptScore W2893669076C142724271 @default.
• W2893669076 hasConceptScore W2893669076C145148216 @default.
• W2893669076 hasConceptScore W2893669076C147597530 @default.
• W2893669076 hasConceptScore W2893669076C161790260 @default.
• W2893669076 hasConceptScore W2893669076C178790620 @default.
• W2893669076 hasConceptScore W2893669076C185592680 @default.
• W2893669076 hasConceptScore W2893669076C204787440 @default.
• W2893669076 hasConceptScore W2893669076C2776640939 @default.
• W2893669076 hasConceptScore W2893669076C2776910235 @default.
• W2893669076 hasConceptScore W2893669076C2780263894 @default.
• W2893669076 hasConceptScore W2893669076C63338738 @default.
• W2893669076 hasConceptScore W2893669076C71924100 @default.
• W2893669076 hasConceptScore W2893669076C97355855 @default.
• W2893669076 hasFunder F4320321006 @default.
• W2893669076 hasIssue "44" @default.
• W2893669076 hasLocation W28936690761 @default.
• W2893669076 hasLocation W28936690762 @default.
• W2893669076 hasLocation W28936690763 @default.
• W2893669076 hasLocation W28936690764 @default.
• W2893669076 hasOpenAccess W2893669076 @default.
• W2893669076 hasPrimaryLocation W28936690761 @default.
• W2893669076 hasRelatedWork W1991299723 @default.

• next