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Nature of the Xe VI −N Bonds in F 6 XeNCCH 3 and F 6 Xe(NCCH 3 ) 2 and the Stereochemical Activity of Their Xenon Valence Electron Lone Pairs
Author(s) -
Haner Jamie,
Matsumoto Kazuhiko,
Mercier Hélène P. A.,
Schrobilgen Gary J.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504904
Subject(s) - natural bond orbital , lone pair , crystallography , chemistry , covalent bond , octahedron , valence (chemistry) , molecule , crystal structure , organic chemistry
The recently reported syntheses and X‐ray crystal structures of the highly endothermic compounds F 6 XeNCCH 3 and F 6 Xe(NCCH 3 ) 2 ⋅ CH 3 CN provide the first, albeit weakly covalent, Xe VI −N bonds. The XeF 6 unit of F 6 XeNCCH 3 possesses distorted octahedral ( C 3 v ) symmetry similar to gas‐phase XeF 6 , whereas the XeF 6 unit of F 6 Xe(NCCH 3 ) 2 ⋅ CH 3 CN possesses C 2 v symmetry. Herein, the natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe valence electron lone pairs (VELPs) of both compounds are stereochemically active. The Xe VELPS are diffuse and ineffectively screen their Xe cores so that the Xe VELP positions correspond to the most electrophilic regions of the MEPS, which enables the opposing N VELP of CH 3 CN to coordinate to this region. These bonds are predominantly electrostatic in nature and are interpreted as σ‐hole interactions.