Synthesis of fluoroalkoxide trirhenium(III) clusters

The cluster Re3(μ-Cl)3Cl6(THF)3 reacted at room temperature in THF with 5 equivalents of NaOCMe(CF3)2 to give [Na(THF)2][Re3(μ-Cl)3Cl2{OCMe(CF3)2}5]. The salt [Na(THF)2][Re3(μ-Cl)3Cl2{OCMe(CF3)2}5] reacted with a large excess of pyridine to produce Re3(μ-Cl)3Cl2[OCMe(CF3)2]4(py)2, which was isolated as a crystalline mixture of two isomers. The mono-pyridine adduct Re3(μ-Cl)3Cl2[OCMe(CF3)2]4(py) was observed as a side product in reactions between the salt and pyridine. The mono-pyridine adduct Re3(μ-Cl)3Cl2[OCMe(CF3)2]4(py) and one of the two isomers of the di-pyridine adduct Re3(μ-Cl)3Cl2[OCMe(CF3)2]4(py)2 were characterized by X-ray crystallography. The other isomer of Re3(μ-Cl)3Cl2[OCMe(CF3)2]4(py)2 and [Na(THF)2][Re3(μ-Cl)3Cl2{OCMe(CF3)2}5] were identified by X-ray crystallography but the structures were not fully refined.