Alkin-Komplexe des Rheniums in hohen Oxidationsstufen / Alkyne Complexes of Rhenium in High Oxidation States

The class of π-alkyne complexes of metals in medium and high oxidation states has been extended by the type CH3ReO2(RC≡CR′) (3a—i). Exchange of alkyne for oxo ligands under reducing conditions has been employed as a new general synthesis. Compounds 3 are thus obtained by reaction of methyltrioxorhenium(VII) (1) with the alkynes 2a—i in the presence of a ca. 1.1-fold molar amount of polymer-bound triphenylphosphane as reducing agent (desoxygenation). The structural characterization was carried out for the example of the tolan complex 3 e by virtue of a single-crystal X-ray diffraction study at —80 °C, according to which the description of compounds 3 as “rhenacyclopropenes” seems justified. Evidence from NMR investigations of 3 a and 3 c shows that no fast rotation of the respective alkyne ligand around the axis to the metal atom occurs on the NMR time scale up to at least 105 °C. A minimal rotation barrier of approximately 20 kcal/mol is thus to be estimated. Reaction of type 3 compounds (R = R′ = CH3, b; R = R′ = C2H5, c) with polymer-bound triphenylphosphane under more drastic conditions (boiling toluene) for two days effects further reduction, with the dinuclear, diamagnetic rhenium(IV) complexes 4b and 4c, resp., being formed. Sterically demanding alkynes (e.g., R = R′ = Si(CH3)3, C6H5) seem to prevent this type of reaction. According to an X-ray diffraction study, 4b has an equilateral Re2O-triangular core geometry, with the ligands O, CH3, and butyne(2) arranged in such a way that C2-symmetry results. The alkyne complexes reported here are the first ones of tetra- and pentavalent rhenium.