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DOI	10.1073/pnas.1806399115
	Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity
	Bím D.; Maldonado-Domínguez M.; Rulísek L.; Srnec M.
发表日期	2018
ISSN	0027-8424
起始页码	E10287
结束页码	E10294
卷号	115 期号:44
英文摘要	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. © 2018 National Academy of Sciences. All rights reserved.
英文关键词	Acidity constant; Asynchronicity factor; Hydrogen atom transfer; Reduction potential; Reorganization energy
语种	英语
scopus关键词	enzyme; hydrogen; iron oxide; metalloenzyme; oxidizing agent; unclassified drug; Article; Bell-Evans-Polanyi effect; carbon hydrogen bond; catalysis; catalyst; chemical bond; chemical parameters; chemical reaction; computer analysis; controlled study; correlation analysis; dehydrogenation; deprotonation; hydrogen atom abstraction reactivity; hydrogenation; Marcus theory; oxidation; oxidation reduction reaction; oxygen hydrogen bond; physical chemistry; priority journal; protonation; reaction free energy; reduction (chemistry); thermodynamics
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/160451
作者单位	Bím, D., J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Prague 8, 18223, Czech Republic, Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague 6, 16000, Czech Republic; Maldonado-Domínguez, M., J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Prague 8, 18223, Czech Republic; Rulísek, L., Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague 6, 16000, Czech Republic; Srnec, M., J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Prague 8, 18223, Czech Republic
推荐引用方式 GB/T 7714	Bím D.,Maldonado-Domínguez M.,Rulísek L.,et al. Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity[J],2018,115(44).
APA	Bím D.,Maldonado-Domínguez M.,Rulísek L.,&Srnec M..(2018).Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity.Proceedings of the National Academy of Sciences of the United States of America,115(44).
MLA	Bím D.,et al."Beyond the classical thermodynamic contributions to hydrogen atom abstraction reactivity".Proceedings of the National Academy of Sciences of the United States of America 115.44(2018).