Informing our understanding of the copper–cuprizone reaction with computational chemistry,Dalton Transactions

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Informing our understanding of the copper–cuprizone reaction with computational chemistry
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-06-23 , DOI: 10.1039/d2dt01476a
M Jake Pushie ₁ , Graham N George _{2,

3}

Affiliation

The reaction of copper with bis(cyclohexanone)oxaldihydrazone (cuprizone) is a challenging coordination chemistry problem that has confounded attempts at elucidation for the past 70 years. The product of the reaction, a blue copper complex, wherein the cuprizone ligand is hydrolyzed, has been the primary focus during its history. We have recently characterized an additional green multi-copper product which contains unhydrolyzed cuprizone, which only added to the mystery. Using density functional structure models and thermodynamic calculations we address several of the long-standing questions surrounding the copper–cuprizone reaction, as well as identify the likely reaction pathway that gives rise to the blue and green products. Cu(II)-induced asymmetric hydrolysis of the cuprizone ligand is essential for formation of the blue product, followed by a series of Cu(II)-induced deprotonation and coordination events, with complex formation terminating with hydrolyzed cuprizone tautomerization and intramolecular electron transfer, generating a pseudo-macrocyclic Cu(III) species. Alternatively, in the presence of excess Cu(II), or in non-aqueous solvents, a green multi-Cu(II) complex forms comprised of alternating Cu(II)–cuprizone units. Structure calculations are supported by experimental data and represent the most rigorous approach to-date toward understanding the complex solution chemistry of copper with cuprizone.

中文翻译：

用计算化学告诉我们对铜-铜酮反应的理解

铜与双（环己酮）草二腙（cuprizone）的反应是一个具有挑战性的配位化学问题，在过去 70 年中一直困扰着人们的阐明尝试。该反应的产物，一种蓝铜络合物，其中铜酮配体被水解，在其历史上一直是主要焦点。我们最近发现了一种额外的绿色多铜产品，其中含有未水解的铜酮，这只会增加谜团。使用密度泛函结构模型和热力学计算，我们解决了围绕铜-铜酮反应的几个长期存在的问题，并确定了产生蓝色和绿色产物的可能反应途径。铜( Ⅱ) 诱导的铜酮配体不对称水解对于蓝色产物的形成至关重要，随后是一系列 Cu( II ) 诱导的去质子化和配位事件，复合物的形成以水解铜酮互变异构和分子内电子转移终止，产生伪-大环Cu( III )物种。或者，在过量的 Cu( II ) 存在下，或在非水溶剂中，由交替的 Cu( II )-铜酮单元组成的绿色多 Cu( II ) 配合物形成。结构计算得到实验数据的支持，代表了迄今为止了解铜与铜宗的复杂溶液化学的最严格的方法。

更新日期：2022-06-23

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