New
products of coordination of anions X– (X
= F, I, PhS) to the Te atom of 3,4-dicyano-1,2,5-telluradiazole (1) were synthesized in high yields and characterized by X-ray
diffraction (XRD) as the salts [(Me2N)3S]+[1-F]− (9), [K(18-crown-6)]+[1-I]− (10), and
[K(18-crown-6)]+[1-SPh]−
·THF (11), respectively. In the crystal
lattice of 10, I atoms are bridging between two Te atoms.
The bonding situation in anions of the salts 9–11 and some other adducts of 1,2,5-chalcogenadiazoles (chalcogen
= S, Se, Te) and anions X– (X = F, Cl, Br, I, PhS)
was studied using DFT, QTAIM, and NBO calculations, for 9–11 in combination with UV–vis, IR/Raman,
and MS-ESI techniques. In all cases, the nature of the coordinate
bond is negative hyperconjugation involving the transfer of electron
density from X– to the heterocycles. The energy
of the bonding interaction varies in a range from ∼30 kcal
mol–1 comparable with energies of weak chemical
bonds (e.g., internal N–N bond in organic azides) to ∼86
kcal mol
–1 comparable with an energy
of the C–C covalent bonds. The thermodynamics of the anions’
coordination to 1 and their Se and S congeners was also
studied by quantum chemical calculations. The general character of
this reaction and favorable thermodynamics in the case of heavier
chalcogens (Se, Te) were established. Comparison with available data
on acyclic analogues, i.e. the chalcogen diimines RNXNR,
reveals that they also coordinate various anions but in addition reactions
across XN (X = S, Se, Te) double bonds. Attempts to prepare
the anion [1-TePh]− led to disintegration
of 1. The only unambiguously identified product was a
rather rare tellurocyanate that was characterized by XRD and elemental
analysis as the salt [K(18-crown-6)]+[TeCN]− (13).