Mesityltellurenyl Cations Stabilized by Triphenylpnictogens [MesTe(EPh3)]+ (E = P, As, Sb)

The homoleptic 1:1 Lewis pair (LP) complex [MesTe­(TeMes2)]­O3SCF3 (1) featuring the cation [MesTe­(TeMes2)]+ (1a) was obtained by the reaction of Mes2Te with HO3SCF3. The reaction of 1 with Ph3E (E = P, As, Sb, Bi) proceeded with substitution of Mes2Te and provided the heteroleptic 1:1 LP complexes [MesTe­(EPh3)]­O3SCF3 (2, E = P; 3, E = As) and [MesTe­(SbPh3)]­[Ph2Sb­(O3SCF3)2] (4) featuring the cations [MesTe­(EPh3)]+ (2a, E = P; 3a, E = As; 4a, E = Sb) and the anion [Ph2Sb­(O3SCF3)2]− (4b). In the reaction with Ph3Bi, the crude product contained the cation [MesTe­(BiPh3)]+ (5a) and the anion [Ph2Bi­(O3SCF3)2]− (5b); however, the heteroleptic 1:1 LP complex [MesTe­(BiPh3)]­[Ph2Bi­(O3SCF3)2] (5) could not be isolated because of its limited stability. Instead, fractional crystallization furnished a large amount of Ph2BiO3SCF3 (6), which was also obtained by the reaction of Ph3Bi with HO3SCF3. The formation of the anions 4b and 5b involves a phenyl group migration from Ph3E (E = Sb, Bi) to the MesTe+ cation and afforded MesTePh as the byproduct, which was identified in the mother liquor. The heteroleptic 1:1 LP complexes 2–4 were also obtained by the one-pot reaction of Mes2Te, Ph3E (E = P, As, Sb) and HO3SCF3. Compounds 1–4 and 6 were investigated by single-crystal X-ray diffraction. The molecular structures of 1a–4a were used for density functional theory calculations at the B3PW91/TZ level of theory and studied using natural bond order (NBO) analyses as well as real-space bonding descriptors derived from an atoms-in-molecules (AIM) analysis of the theoretically obtained electron density. Additionally, the electron localizability indicator (ELI-D) and the delocalization index are derived from the corresponding pair density.