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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Chemical Reactivity Descriptors for Ambiphilic Reagents: Dual Descriptor, Local Hypersoftness, and Electrostatic Potential
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Chemical Reactivity Descriptors for Ambiphilic Reagents: Dual Descriptor, Local Hypersoftness, and Electrostatic Potential

机译：两性试剂的化学反应性描述子：双重描述子，局部超软性和静电势

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摘要

The second-order response of the electron density with respect to changes in electron number, known as the dual descriptor, has been established as a key reactivity indicator for reactions like pericyclic reactions, where reagents accept and donate electrons concurrently. Here we establish that the dual descriptor is also the key reactivity indicator for ambiphilic reagents: reagents that can act either as electrophiles or as nucleophiles, depending on the reaction partner. Specifically, we study dual atoms (which are proposed to act, simultaneously, as an electron acceptor and an electron donor), dual molecules (which react with both electrophiles and nucleophiles, generally at different sites), and dual ion-molecule complexes (which react with both cations and anions). On the basis of our analysis, the dual atom (an Al(I) that has been purported to be dual in the literature) is actually pseudodual in the sense that it does not truly accept electrons from a nucleophiles; rather, it serves as a conduit through which an electrophile can donate electrons to the attached aromatic ring. For understanding dual ion-molecule complexes, it helps to understand that the dual descriptor makes a key contribution to the long-range portion of the quadratic hyperpolarization. In all cases, a complete description of the reactivity of the ambiphilic reagent requires considering both an orbital-based descriptor of electron transfer (the dual descriptor or the local hypersoftness) and the electrostatic potential. The local hypersoftness strongly resembles the dual descriptor.
机译：电子密度相对于电子数变化的二次响应，被称为双重描述符，已被确立为反应的关键反应指标，如周环反应，其中试剂同时接受和提供电子。在这里，我们确定双重描述符也是含两性试剂的关键反应性指标：取决于反应伙伴，可作为亲电子试剂或亲核试剂的试剂。具体而言，我们研究了双原子（拟同时充当电子受体和电子供体），双分子（通常与亲电子和亲核试剂反应，通常在不同位置）和双离子分子复合物（其中与阳离子和阴离子反应）。根据我们的分析，双原子（在文献中一直被认为是双原子的Al（I））实际上是伪双原子，因为它并不真正接受亲核试剂中的电子。相反，它用作亲电子试剂可通过其将电子捐赠给所连接的芳环的导管。为了理解双离子-分子复合物，有助于理解双描述符对二次超极化的远距离部分起关键作用。在所有情况下，要全面描述两性试剂的反应性，既需要考虑基于轨道的电子转移描述符（双重描述符或局部超软性），也需要考虑静电势。局部超软性与双重描述符非常相似。

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