Martínez-Araya Jorge I
Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello (UNAB), Santiago, Chile.
Front Chem. 2022 Mar 24;10:869110. doi: 10.3389/fchem.2022.869110. eCollection 2022.
The Janus-faced ligand behavior of diiodine (I) was evidenced after applying the dual descriptor (DD or second-order Fukui function), thus providing additional support to the work performed by Rogachev and Hoffmann in 2013. Along with its capacity to reveal sites susceptible to undergo attacks simultaneously of nucleophilic and electrophilic types, another advantage of DD lies in being an orbital-free descriptor. That means it is based only upon total electron densities when written in its most accurate operational formula. This quality is not exclusive of DD because when Fukui functions are written in terms of electron densities instead of densities of frontier molecular orbitals, they become orbital-free descriptors too. Furthermore, the present work is an application of the generalized operational formula of the dual descriptor published in 2016 that takes into account any possible degeneracy in frontier molecular orbitals. As a proof about capabilities of DD, the possible sites for a favorable interaction between I with two organometallic compounds [Rh(OCCF)] and [(CHN)Pt (CH)] were correctly revealed by overlapping the biggest lobe for receiving nucleophilic attacks of one molecule with the biggest lobe for receiving electrophilic attacks of the other molecule, so allowing to predict the same coordination modes as experimentally known: linear "end-on" for the [(CHN)Pt (CH)]…I, and bent "end-on" for the [Rh(OCCF)]…I interactions.
在应用双描述符（DD或二阶福井函数）后，二碘（I）的两面配体行为得到了证实，从而为罗加乔夫和霍夫曼在2013年所做的工作提供了额外支持。除了能够揭示易受亲核和亲电类型同时攻击的位点外，DD的另一个优点在于它是一个无轨道描述符。这意味着当以其最精确的运算公式书写时，它仅基于总电子密度。这种性质并非DD所独有，因为当福井函数以电子密度而非前沿分子轨道密度来书写时，它们也会变成无轨道描述符。此外，本工作是对2016年发表的双描述符广义运算公式的应用，该公式考虑了前沿分子轨道中任何可能的简并性。作为DD能力的一个证明，通过将一个分子接受亲核攻击的最大叶瓣与另一个分子接受亲电攻击的最大叶瓣重叠，正确地揭示了I与两种有机金属化合物[Rh(OCCF)]和[(CHN)Pt(CH)]之间有利相互作用的可能位点，从而能够预测与实验已知相同的配位模式：[(CHN)Pt(CH)]…I为线性“端对端”，[Rh(OCCF)]…I相互作用为弯曲“端对端”。
