H. Fleischer et D. Schollmeyer, Molecular structure of Te(OMe)(4)center dot ClTe(OMe)(3), a model for ligand exchange between Te(IV) centers, INORG CHEM, 40(2), 2001, pp. 324-328
ClTe((OPr)-Pr-i)(3) could be prepared from stoichiometric amounts of TeCl4
and Te((OPr)-Pr-i)(4), a reaction that requires the exchange of ligands bet
ween different Te centers. Ligand redistribution between telluranes was stu
died, and rapid exchange of -Cl and -OR (R = Me,Pr-i) ligands in solutions
df several binary mixtures of Te(OMe)(4), Te((OPr)-Pr-i)(4), ClTe(OMe)(3),
and ClTe((OPr)-Pr-i)(3) was established by multinuclear NMR spectroscopy. T
he solid-state structure of Te(OMe)(4). ClTe(OMe)(3), the first structurall
y characterized adduct between different telluranes, was investigated by si
ngle-crystal X-ray diffraction. It exhibits a very short Te-O . . . Te brid
ge between the two Te centers and additional Te . . .O and Te . . . Cl cont
acts between different adduct molecules. Selected structural parameters of
Te(OMe)(4). ClTe(OMe)(3) are Te1-Cl1 274.6(3), Te1-O13 191.0(5), Te1-O12 19
4.9(6), Te1-O11 200.9(7), Te1 . . . O24 26.8(5), Te1 . . . 11a 314.2(8), Te
2-O21 191.6(5), Te2-O22 198.7(5), Te2-O23 190.1(5), Te2-O24 225.35), Te2 .
. . O13 307.8(6), and Te2 . . . O22b 269.2(6) pm and Te2-O24 . . . Te1 126.
1(2)degrees. Ab initio (MP2/LANL2DZP) geometry optimization of the model co
mpound Te(OH)(4). . . ClTe(OH)(3) revealed that the central Te-O . . . Te b
ridge is less symmetric and hence weaker in the isolated adduct molecule th
an in the solid state. The stability of Te(OMe)(4). . . ClTe(OMe)(3) toward
decomposition in Te(OMe)(4) and ClTe(OMe)(3) is attributed to the strength
s of the short Te-O . . . Te bridge between Te(OMe)(4) and ClTe(OMe)(3). On
the basis of the molecular structures of Te(OH)(4). ClTe(OH)(3) and Te(OMe
)(4). ClTe(OMe)(3), a mechanism for the exchange of -OR groups between Te(I
V) centers is proposed.