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。

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
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*, 
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引用次数: 0

摘要

高价形式铜(III)配合物[Cu(pyalk)2]+(2) (pyalk = 2-(2'-pyridyl)-2-propanolate)被分离并通过各种物理方法进行表征,包括x射线晶体学和DFT计算模型。发现配合物2与苯酚和碳氢化合物底物发生快速质子耦合电子转移,导致金属中心的还原和pyalk配体的质子化。对2与两种底物反应的动力学数据分析表明,2通过协调的质子-电子转移(CPET)途径反应。热力学分析表明,2在CPET过程中形成的O-H键具有103 kcal/mol的高键解离焓,与同结构的镍(III)类似物[Ni(pyalk)2]+(4)相比,2具有较快的反应活性。与4相比,2与苯酚和碳氢化合物底物的反应速度快5-10倍,O-H BDE比4高~ 6 kcal/mol。进一步分析表明,4可能比2通过更基本的异步途径进行CPET,这可能导致4的CPET速率比Bell-Evans-Polanyi原理预期的要快得多。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Metal-Dependent Asynchronicity of Concerted Proton–Electron Transfer to a High-Valent Copper(III) Complex and Its Nickel(III) Analogue

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.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
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.
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