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.[1] The motif is similar to that seen for tantalum pentachloride.
This compound was first prepared in 1933,[5] a few years after the discovery of rhenium. The preparation involves chlorination of rhenium at temperatures up to 900 °C.[3] 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.[6]Rhenium heptafluoride is known but not the heptachloride.[7]
Although rhenium pentachloride has no commercial applications, it is of historic significance as one of the early catalysts for olefin metathesis.[9] Reduction gives trirhenium nonachloride.
^ abRoger 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. doi:10.1002/9780470132517.ch11.
^Shaik, Sason; Hoffmann, Roald; Fisel, C. Richard; Summerville, Richard H. (1980). "Bridged and Unbridged M2L10 Complexes". Journal of the American Chemical Society. 102 (14): 4555–4572. doi:10.1021/ja00534a001.
^MacGregor, Stuart A.; Moock, Klaus H. (1998). "Stabilization of High Oxidation States in Transition Metals. 2. WCl6 Oxidizes [WF6]−, but Would PtCl6 Oxidize [PtF6]−? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF6] z versus [MCl6] z (M = Ta to Pt; z = 0, 1−, 2−)". Inorganic Chemistry. 37 (13): 3284–3292. doi:10.1021/ic9605736.
^Edwards, D. A.; Ward, R. T. (1970). "Some reactions of rhenium(V) chloride". Journal of the Chemical Society A: 1617. doi:10.1039/J19700001617.
^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 Catalysis1986, 36, 115.
^Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. ISBN978-0-13-039913-7.