Rhenium pentachloride is an inorganic compound with the formula . This red-brown solid is paramagnetic.
Structure and preparation Rhenium pentachloride has a bioctahedral structure and can be described as Cl4Re(μ-Cl)2ReCl4. The (μ-Cl)2 part of this formula indicates that two chloride ligands are bridging ligands, i.e. they connect to two Re atoms. The Re-Re distance is 3.74 Å. The motif is similar to that seen for tantalum pentachloride.
This compound was first prepared in 1933, a few years after the discovery of rhenium. The preparation involves chlorination of rhenium at temperatures up to 900 °C.Roger Lincoln, Geoffrey Wilkinson "Rhenium Pentachloride and Volatile Metal Chlorides by Direct Chlorination Using a Vertical-Tube Reactor" Inorganic Syntheses, 1980, Volume 20, Pages 41–43. . The material can be purified by sublimation.
ReCl5 is one of the most oxidized binary chlorides of Re. It does not undergo further chlorination. ReCl6 has been prepared from rhenium hexafluoride. Rhenium heptafluoride is known but not the heptachloride.
Uses and reactions It degrades in air to a brown liquid.
Although rhenium pentachloride has no commercial applications, it is of historic significance as one of the early catalysts for olefin metathesis.Ring-opening polymerization of endo and exo-dicyclopentadiene and their 7,8-dihydro derivatives, Hamilton, J.G.; Ivin, K.J.; Rooney, J.J. Journal of Molecular Catalysis 1986, 36, 115. Reduction gives trirhenium nonachloride.
Oxygenation affords the Re(VII) oxychloride: ReCl5 + 3 Cl2O → ReO3Cl + 5 Cl2
Comproportionation of the penta- and trichloride gives rhenium tetrachloride.
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