Rhenium pentachloride

Rhenium pentachloride is an inorganic compound of chlorine and rhenium. The compound has the formula Re2Cl10 but it is usually referred to as rhenium pentachloride. It is a red-brown solid.

Rhenium pentachloride
Names
IUPAC name
Rhenium pentachloride
Other names
Rhenium(V) chloride, Rhenium chloride, pentachlororhenium
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.660
EC Number
  • 237-042-6
  • InChI=1S/5ClH.Re/h5*1H;/q;;;;;+5/p-5
    Key: XZQYTGKSBZGQMO-UHFFFAOYSA-I
  • InChI=1/5ClH.Re/h5*1H;/q;;;;;+5/p-5/rCl5Re/c1-6(2,3,4)5
    Key: XZQYTGKSBZGQMO-PXGBCINVAP
  • Cl[Re](Cl)(Cl)(Cl)Cl
Properties
ReCl5
Molar mass 363.471 g/mol
Appearance red-brown
Density 4.9 g/cm3, solid
Melting point 220 °C (428 °F; 493 K)
Boiling point N/A
Will react to decompose and release HCl (g)
+1225.0·10−6 cm3/mol
Structure
Monoclinic, mP48; a = 0.924 nm, b = 1.154 nm, c = 1.203 nm, α = 90°, β = 109.1°, γ = 90° [1]
P21/c, No. 14
Octahedral
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 releases HCl upon hydrolysis
GHS labelling:[2]
GHS07: Exclamation mark
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
1
0
W
Safety data sheet (SDS) MSDS
Related compounds
Other anions
 Rhenium hexafluoride
Related compounds
 Trirhenium nonachloride, rhenium tetrachloride, rhenium hexachloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Structure and preparation

Rhenium pentachloride has a bioctahedral structure and can be formulated as Cl4Re(μ-Cl)2ReCl4. 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,[3] a few years after the discovery of rhenium. The preparation involves chlorination of rhenium at temperatures up to 900 °C.[4] 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.[5] Rhenium heptafluoride is known but not the heptachloride.[6]

Uses and reactions

It degrades in air to a brown liquid.[7]

Although rhenium pentachloride has no commercial applications, it is of historic significance as one of the early catalysts for olefin metathesis.[8] Reduction gives trirhenium nonachloride.

Oxygenation affords the Re(VII) oxychloride:[9]

ReCl5 + 3 Cl2O → ReO3Cl + 5 Cl2

Comproportionation of the penta- and trichloride gives rhenium tetrachloride.

References
  1. Mucker, K. F.; Smith, G. S.; Johnson, Q. (1968). "The crystal structure of ReCl5" (PDF). Acta Crystallographica Section B. 24 (6): 874. doi:10.1107/S0567740868003316.
  2. GHS: PubChem 83602
  3. Geilmann, Wilhelm; Wrigge, Friedrich W.; Biltz, Wilhelm. (1933). "Rheniumpentachlorid". Z. Anorg. Allg. Chem. (in German). 214 (3): 244. doi:10.1002/zaac.19332140304.
  4. 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. doi:10.1002/9780470132517.ch11.
  5. Tamadon, Farhad; Seppelt, Konrad (2013). "The Elusive Halides VCl5, MoCl6, and ReCl6". Angew. Chem. Int. Ed. 52 (2): 767–769. doi:10.1002/anie.201207552. PMID 23172658.
  6. Stuart A. Macgregor and Klaus H. Moock "Stabilization of High Oxidation States in Transition Metals. 2.1 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−)" pp 3284–3292. doi:10.1021/ic9605736
  7. Edwards, D. A.; Ward, R. T. (1970). "Some reactions of rhenium(V) chloride". Journal of the Chemical Society A: 1617. doi:10.1039/J19700001617.
  8. 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.
  9. Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. ISBN 978-0-13-039913-7.
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