Abstract
Anodic oxidation of tantalum in isopropyl alcohol or prolonged reflux of an alcohol solution of Ta(OPri)5 afford crystalline oxoisopropoxide Ta2O(OPri)8 · PriOH (1). In its molecule, two octahedra about Ta atoms are linkedvia the shared edge [(OPri)O]. Compound1 is the first example of oxoalkoxide containing such a small number of metal atoms. Unlike the known polynuclear molecules M n O m (OR) p , oxoalkoxide1 is stable in solutions; on transition to the gas phase, this compound is desolvated to form a very stable molecule Ta2O(OPri)8 (apparently, consisting of two octahedra with a shared edge). According to the data of mass spectrometry, analogous molecules exist in the gas phase over Ta(OAlk)5 (Alk = Me, Et, Pri, or Bu11). When compound1 is heated invacuo (10−2–10−3 Torr), Ta(OPri)5 is sublimated. Crystals of Ta7O9(OPri)17 (2) were formed upon prolonged storage of solutions of1 in PriOH. Heptanuclear molecule2 consists of two [Ta4] tetrahedra with a shared vertex. These tetrahedra are additionally linked togethervia one μ3-oxo and two μ2-OPri groups. Complex2 is a representative of heptameric oxoalkoxides of a new structural type.
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