Rhenium pentachloride

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Rhenium pentachloride
Identifiers
CAS number 13596-35-5 YesY
PubChem 83602
EC number 237-042-6
Jmol-3D images {{#if:Cl[Re](Cl)(Cl)(Cl)Cl|Image 1
Properties
Molecular formula ReCl5
Molar mass 363.471 g/mol
Appearance red-brown
Density 4.9 g/cm3, solid
Melting point 220 °C
Boiling point N/A
Solubility in water Will react to decompose and release HCl (g)
Structure
Crystal structure Monoclinic, mP48; a = 0.924 nm, b = 1.154 nm, c = 1.203 nm, α = 90°, β = 109.1°, γ = 90° [1]
Space group P21/c, No. 14
Molecular shape Octahedral
Hazards
MSDS MSDS
R/S statement R: 36, 37, 38
Main hazards releases HCl upon hydrolysis
NFPA 704
 
1
0
Related compounds
Other anions Rhenium hexafluoride
Related compounds Trirhenium nonachloride, rhenium tetrachloride, rhenium hexachloride
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Infobox references

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

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,[2] 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.

Being formed by burning Re metal in chlorine, ReCl5 is the most oxidized binary chloride of Re. With a d2 configuration, ReCl5 could conceivably be further chlorinated. Rhenium hexachloride (ReCl6) is uncertain, but rhenium hexafluoride and rhenium heptafluoride are known.[4]

Uses and reactions

It degrades in air to a brown liquid.[5]

Although rhenium pentachloride has no commercial applications, it is of historic significance as one of the early catalysts for olefin metathesis.[6] Reduction gives Trirhenium nonachloride.

Oxygenation affords the Re(VII) oxychloride:[7]

ReCl5 + 3 Cl2O → ReO3Cl + 5 Cl2

References

  1. 1.0 1.1 Mucker, K. F.; Smith, G. S.; Johnson, Q. (1968). "The crystal structure of ReCl5". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 24 (6): 874. doi:10.1107/S0567740868003316. 
  2. Geilmann, Wilhelm; Wrigge, Friedrich W.; Biltz, Wilhelm. (1933). "Rheniumpentachlorid". Z. anorg. allgem. Chem. (in German) 214 (3): 244. doi:10.1002/zaac.19332140304. 
  3. 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.
  4. 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
  5. Edwards, D. A.; Ward, R. T. (1970). "Some reactions of rhenium(V) chloride". Journal of the Chemical Society a Inorganic Physical Theoretical: 1617. doi:10.1039/J19700001617. 
  6. 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.
  7. Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. ISBN 978-0130399137. 

External links

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