Reactivity of [Te6Fe8(CO)24]2− and Its Conversion to [Te4Fe5(CO)14]2−

Whereas reaction of [PhCH₂NMe₃]₂|Te₆Fe₈(CO)₂₄] (1) in refluxing CH₂CI₂ forms Fe₂(CO)₆(μ0-) TeCH₂Te), treatment of 1 with Ph₂SnCl ₂ or Mel gave the oxidation product Te₂Fe₃(CO)₉. Oxidation of 1 with [Cu(CH₃CN)₄]BF₄ afforded Te₂Fe₃(CO)₉ in good yield. Cluster 1 was converted to [PhCH₂NMe₃][Te₄Fe₅(CO)₁₄] (2) in MeOH/CH₂Cl₂ solution. Cluster 2 was structurally characterized by single-crystal X-ray diffraction and spectral methods. Complex 2 is composed of two Te₂Fe₂(CO)₆ fragments linked by one Fe(CO)₂ group. 2 crystallizes in the orthorhombic space group Pbcn with a = 13.351 (4) Å, b = 13.417 (4) Å, c = 26.077 (3) Å, V = 4671 (2) Å ₃, Z = 4.