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DOI: 10.1039/A605349A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 553-558

The [ICNI]+ cation: a combined experimental and theoretical study. Reaction of [ICNI]+[AsF6]- with CsN3[hair space]

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Thomas M. Klapötke

Abstract

(Iodocyano)iodine hexafluoroarsenate, [ICNI]+[AsF6]-, containing the linear 22-valence-electron [ICNI]+ cation was synthesized either by the reaction of iodine cyanide with [I3]+[AsF6]- or directly from ICN, I2 and AsF5 and characterized by chemical analysis, IR, Raman and 19F NMR data. A combined vibrational (IR, Raman) and theoretical study revealed the [ICNI]+ cation to be linear. The preference of the linear over the bent structure can easily be understood in terms of hyperconjugative interactions in the cationic species [natural bond order (NBO) analysis]. The molecular structure of the [ICNI]+ cation was computed semiempirically (Austin Model 1, AM1; reparameterization of AM1, PM3) and ab initio at the Hartree–Fock (HF/6-31G*) and correlated RMP2 (RMP, restricted Møller–Plesset) and RMP4(SDQ) levels of theory using quasi-relativistic pseudo-potentials (LANL2DZ) for the iodine atoms. The computed structural parameters at the highest level applied are: C∞v symmetry, RMP4(SDQ), d(I–C) = 2.001, d(C[triple bond, length as m-dash]N) = 1.167, d(N–I) = 2.021 Å. The N–I bond dissociation enthalpy for [ICN–I]+ was calculated ab initio at the electron-correlated RMP2 level of theory as 207.4 kJ mol-1. The metathetical reaction of [ICNI]+[AsF6]- with CsN3 in SO2ClF afforded IN3, Cs+[AsF6]- and ICN.

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