Katherine J. Fisher, H. Ray Kelly, Claire C. Cody, Cristina Decavoli, Brandon Q. Mercado, Jennifer L. Troiano, Robert H. Crabtree, Victor S. Batista* and Gary W. Brudvig*,
{"title":"高价铜(III)配合物及其镍(III)类似物的质子-电子协同转移的金属依赖非同步性。","authors":"Katherine J. Fisher, H. Ray Kelly, Claire C. Cody, Cristina Decavoli, Brandon Q. Mercado, Jennifer L. Troiano, Robert H. Crabtree, Victor S. Batista* and Gary W. Brudvig*, ","doi":"10.1021/acs.inorgchem.5c02005","DOIUrl":null,"url":null,"abstract":"<p >A high-valent formally copper(III) complex, [Cu(pyalk)<sub>2</sub>]<sup>+</sup>(<b>2</b>) (pyalk = 2-(2′-pyridyl)-2-propanolate), is isolated and characterized by a variety of physical methods, including X-ray crystallography and DFT computational modeling. Complex <b>2</b> is found to undergo fast proton-coupled electron transfer with phenol and hydrocarbon substrates, resulting in the reduction of the metal center and protonation of the pyalk ligand. Analysis of kinetic data for the reaction of <b>2</b> with both types of substrates suggests that <b>2</b> reacts through a concerted proton–electron transfer (CPET) pathway. Thermodynamic analysis indicates that the O–H bond formed during CPET by <b>2</b> has a high bond dissociation enthalpy of 103 kcal/mol, consistent with the fast reactivity of <b>2</b> as compared to its isostructural nickel(III) analogue, [Ni(pyalk)<sub>2</sub>]<sup>+</sup> (<b>4</b>). Compared to <b>4</b>, <b>2</b> reacts 5–10 times faster with phenol and hydrocarbon substrates and has an O–H BDE ∼6 kcal/mol higher than <b>4</b>. Further analysis suggests that <b>4</b> may undergo CPET through a more basic asynchronous pathway than <b>2</b>, which may cause the CPET rate with <b>4</b> to be much faster than expected from the Bell–Evans–Polanyi principle.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 28","pages":"14552–14565"},"PeriodicalIF":4.7000,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Metal-Dependent Asynchronicity of Concerted Proton–Electron Transfer to a High-Valent Copper(III) Complex and Its Nickel(III) Analogue\",\"authors\":\"Katherine J. Fisher, H. Ray Kelly, Claire C. Cody, Cristina Decavoli, Brandon Q. Mercado, Jennifer L. Troiano, Robert H. Crabtree, Victor S. Batista* and Gary W. Brudvig*, \",\"doi\":\"10.1021/acs.inorgchem.5c02005\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A high-valent formally copper(III) complex, [Cu(pyalk)<sub>2</sub>]<sup>+</sup>(<b>2</b>) (pyalk = 2-(2′-pyridyl)-2-propanolate), is isolated and characterized by a variety of physical methods, including X-ray crystallography and DFT computational modeling. Complex <b>2</b> is found to undergo fast proton-coupled electron transfer with phenol and hydrocarbon substrates, resulting in the reduction of the metal center and protonation of the pyalk ligand. Analysis of kinetic data for the reaction of <b>2</b> with both types of substrates suggests that <b>2</b> reacts through a concerted proton–electron transfer (CPET) pathway. Thermodynamic analysis indicates that the O–H bond formed during CPET by <b>2</b> has a high bond dissociation enthalpy of 103 kcal/mol, consistent with the fast reactivity of <b>2</b> as compared to its isostructural nickel(III) analogue, [Ni(pyalk)<sub>2</sub>]<sup>+</sup> (<b>4</b>). Compared to <b>4</b>, <b>2</b> reacts 5–10 times faster with phenol and hydrocarbon substrates and has an O–H BDE ∼6 kcal/mol higher than <b>4</b>. Further analysis suggests that <b>4</b> may undergo CPET through a more basic asynchronous pathway than <b>2</b>, which may cause the CPET rate with <b>4</b> to be much faster than expected from the Bell–Evans–Polanyi principle.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 28\",\"pages\":\"14552–14565\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-07-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02005\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02005","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Metal-Dependent Asynchronicity of Concerted Proton–Electron Transfer to a High-Valent Copper(III) Complex and Its Nickel(III) Analogue
A high-valent formally copper(III) complex, [Cu(pyalk)2]+(2) (pyalk = 2-(2′-pyridyl)-2-propanolate), is isolated and characterized by a variety of physical methods, including X-ray crystallography and DFT computational modeling. Complex 2 is found to undergo fast proton-coupled electron transfer with phenol and hydrocarbon substrates, resulting in the reduction of the metal center and protonation of the pyalk ligand. Analysis of kinetic data for the reaction of 2 with both types of substrates suggests that 2 reacts through a concerted proton–electron transfer (CPET) pathway. Thermodynamic analysis indicates that the O–H bond formed during CPET by 2 has a high bond dissociation enthalpy of 103 kcal/mol, consistent with the fast reactivity of 2 as compared to its isostructural nickel(III) analogue, [Ni(pyalk)2]+ (4). Compared to 4, 2 reacts 5–10 times faster with phenol and hydrocarbon substrates and has an O–H BDE ∼6 kcal/mol higher than 4. Further analysis suggests that 4 may undergo CPET through a more basic asynchronous pathway than 2, which may cause the CPET rate with 4 to be much faster than expected from the Bell–Evans–Polanyi principle.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.