Tris(2,6-dimethoxyphenyl)telluronium chloride hydrate, [R3Te]Cl·nH2O 1a [R = 2,6-(MeO)2C6H3, n = 2–2.5] was prepared by the reaction of RLi and TeCl4. It decomposed in hot 0.1 M hydrochloric acid to give R2TeCl23a, exclusively, from which R2TeX2 (X = Br 3b, I 3c or SCN 3d) were derived by halogen exchange. The X-ray crystallographic analyses of 3a–3d showed that these compounds have a twofold axis (except for 3d) with essentially pseudo-trigonal bypyramidal co-ordination with two R groups and a lone pair of electrons occupying the equatorial sites and two halogen atoms the apical sites. The thiocyanate groups in 3d bind to the tellurium atom via sulfur. No intermolecular Te
⋯
X secondary bond was observed for 3a–3d. The Te–C bond distances of 3a–3c [2.09 ± 0.01 Å] are somewhat shorter than those reported for phenyl derivatives, and those of 3d [2.042(3) and 2.073(2) Å] are the shortest ever reported. The C–Te–C bond angle is much larger [107.6(2)–104.37(9)°] than those reported. The X–Te–X bond angles are very close to 180°. The Te
⋯
O distances of 3a–3d [2.880–3.323 Å] are significantly shorter than the sum of the O and Te van der Waals radii [3.60 Å]. The 1H NMR spectra of 3a–3c were halogen-, solvent-, and temperature-dependent showing that the rotation of R–Te bonds was restricted due to the barrier between R groups and halogen atoms. The activation energies ΔG‡ decreased in the order 3a (90 kJ mol−1 in DMSO-d6) > 3b (80 kJ mol−1 in DMSO-d6) > 3d (≥65 kJ mol−1 in CDCl3) > 3c (60 kJ mol−1 in CDCl3) ≥ 3d (59 kJ mol−1 in CD3CN).
You have access to this article
Please wait while we load your content...
Something went wrong. Try again?