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The Binary Iodine‐Chlorine Octahalide Series [I n Cl 8− n ] 2− ( n =3, 3.6, 4)
Author(s) -
Abdelbassit Mohammed S.,
Curnow Owen J.,
Dixon Miriam K.,
Waterland Mark R.
Publication year - 2019
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.201902135
Subject(s) - trihalide , halogen , chemistry , chlorine , melting point , iodine , stoichiometry , crystallization , salt (chemistry) , raman spectroscopy , chloride , crystallography , inorganic chemistry , halide , organic chemistry , alkyl , physics , optics
The octanuclear iodine‐chlorine interhalides [I 4 Cl 4 ] 2− and [I 3 Cl 5 ] 2− were prepared in two steps. Firstly, addition of ICl to the triaminocyclopropenium chloride salt [C 3 (NEt 2 ) 3 ]Cl forms the trihalide ICl 2 − salt, secondly, addition of half an equivalent of I 2 or ICl, respectively, gave the desired products upon crystallization at low temperature. The non‐stoichiometric octahalide [I 3.6 Cl 4.4 ] 2− was obtained after heating a CH 2 Cl 2 solution of the ICl 2 − salt to reflux for 2 hours followed crystallization. [I 4 Cl 4 ] 2− is best described as two ICl 2 − anions bridged by I 2 , whereas [I 3 Cl 5 ] 2− is best described as an [I 2 Cl 3 ] − pentahalide with a weak halogen bond to an ICl 2 − trihalide. The octahalides were characterized by X‐ray crystallography, computational studies, Raman and Far‐IR spectroscopies, as well as by TGA and melting point.