作为超卤素阴离子配体的亲电取代基

Electrophilic substituents as ligands in superhalogen anions.

作者信息

Anusiewicz Iwona

机构信息

Department of Chemistry, University of Gdańsk, Sobieskiego 18, 80-952 Gdańsk, Poland.

出版信息

J Phys Chem A. 2009 Jun 11;113(23):6511-6. doi: 10.1021/jp901910q.

DOI:10.1021/jp901910q

PMID:19492854

Abstract

The vertical electron detachment energies (VDE) of several NaL(2)(-) and MgL(3)(-) anions (where L = -NO(2), -CF(3), -CCl(3), -SHO(3), -COOH, -COOCH(3), -CHO, -CONH(2)) were calculated at the outer valence Green function level with the 6-311++G(3df,3pd) basis sets. It was proposed that some of electrophilic substituents may act as ligands in these species, analogously to halogen atoms in superhalogen anions. The largest values of the electron binding energies were found for the anions containing -SHO(3) ligands (VDE = 6.0-8.2 eV) and -CF(3) groups (VDE = 5.2-6.6 eV).

摘要

在使用6-311++G(3df,3pd)基组的外价层格林函数水平上，计算了几种NaL₂⁻和MgL₃⁻阴离子（其中L = -NO₂、-CF₃、-CCl₃、-SHO₃、-COOH、-COOCH₃、-CHO、-CONH₂）的垂直电子脱离能（VDE）。有人提出，一些亲电取代基可能在这些物种中充当配体，类似于超卤素阴离子中的卤素原子。发现含有-SHO₃配体（VDE = 6.0 - 8.2 eV）和-CF₃基团（VDE = 5.2 - 6.6 eV）的阴离子具有最大的电子结合能。