Interaction of the electrophilic bis(pentafluorophenyl)iodonium cation [(C sub(6)F sub(5)) sub(2)I] super(+) with the ambident pseudohalogenide anions [SCN] super(-) and [CN] super(-)

The iodonium pseudohalide compounds, [(C sub(6)F sub(5)) sub(2)I][X] (X = SCN and CN) were synthesized by means of fluoride substitution in [(C sub(6)F sub(5)) sub(2)I][F] with the Lewis acidic reagents (CH sub(3)) sub(3)Si-NCS and (CH sub(3)) sub(3)Si-CN. The isolated iodonium pseudohalides are int...

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Bibliographic Details
Published in:Journal of fluorine chemistry 2014-07, Vol.163, p.28-33
Main Authors: Hirschberg, Markus E, Barthen, Peter, Frohn, Hermann-Josef, Blaeser, Dieter, Tobey, Briac, Jansen, Georg
Format: Article
Language:English
Subjects:
Anions
Atomic structure
Cations
Crystal structure
Dimerization
Dimers
Fluorides
Gas phases
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Summary:The iodonium pseudohalide compounds, [(C sub(6)F sub(5)) sub(2)I][X] (X = SCN and CN) were synthesized by means of fluoride substitution in [(C sub(6)F sub(5)) sub(2)I][F] with the Lewis acidic reagents (CH sub(3)) sub(3)Si-NCS and (CH sub(3)) sub(3)Si-CN. The isolated iodonium pseudohalides are intrinsically unstable solids. Decomposition resulted in equimolar amounts of C sub(6)F sub(5)I and C sub(6)F sub(5)SCN or C sub(6)F sub(5)I and C sub(6)F sub(5)CN, respectively. In case of [(C sub(6)F sub(5)) sub(2)I][SCN] single crystals could be grown from CH sub(2)Cl sub(2). The crystal structure revealed a dimer with an eight membered ring formed by two ambident anions bridging the iodine atoms of two cations by N and S coordination. The favored dimerization of [(C sub(6)F sub(5)) sub(2)I][SCN] and [(C sub(6)F sub(5)) sub(2)I][CN] in the gas phase is supported by ab initio computations.
ISSN:0022-1139
DOI:10.1016/j.jfluchem.2014.04.006