Rhenium pentachloride

Rhenium pentachloride
Names
	IUPAC name Rhenium pentachloride
	Other names Rhenium(V) chloride, Rhenium chloride, pentachlororhenium
Identifiers
CAS Number	13596-35-5 ;
3D model (JSmol)	monomer: Interactive image; dimer: Interactive image;
ChemSpider	75428;
ECHA InfoCard	100.033.660
EC Number	237-042-6;
PubChem CID	83602;
CompTox Dashboard (EPA)	DTXSID1065552 ;
	InChI InChI=1S/5ClH.Re/h51H;/q;;;;;+5/p-5 Key: XZQYTGKSBZGQMO-UHFFFAOYSA-I; InChI=1/5ClH.Re/h51H;/q;;;;;+5/p-5/rCl5Re/c1-6(2,3,4)5 Key: XZQYTGKSBZGQMO-PXGBCINVAP;
	SMILES monomer: Cl[Re](Cl)(Cl)(Cl)Cl; dimer: Cl[Re-]1(Cl)(Cl)(Cl)[Cl+][Re-]([Cl+]1)(Cl)(Cl)(Cl)Cl;
Properties
Chemical formula	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
Solubility in water	Will react to decompose and release HCl (g)
Magnetic susceptibility (χ)	+1225.0·10−6 cm3/mol
Structure
Crystal structure	Monoclinic, mP48; a = 0.924 nm, b = 1.154 nm, c = 1.203 nm, α = 90°, β = 109.1°, γ = 90°
Space group	P21/c, No. 14
Molecular shape	Octahedral
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	releases HCl upon hydrolysis
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	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)	1 0 W
Safety data sheet (SDS)	MSDS
Related compounds
Other anions	Rhenium pentafluoride
Other cations	Osmium pentachloride
Related Rhenium chlorides	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). verify (what is ?) Infobox references

Rhenium pentachloride is an inorganic compound with the formula Re₂Cl₁₀. This red-brown solid^[3] is paramagnetic.^[4]

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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.^[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]

Uses and reactions

It degrades in air to a brown liquid.^[8]

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.

Oxygenation affords the Re(VII) oxychloride:^[10]

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. Bibcode:1968AcCrB..24..874M. doi:10.1107/S0567740868003316.
[2]
GHS: PubChem 83602
[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]
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.
[5]
Geilmann, Wilhelm; Wrigge, Friedrich W.; Biltz, Wilhelm. (1933). "Rheniumpentachlorid". Z. Anorg. Allg. Chem. (in German). 214 (3): 244. doi:10.1002/zaac.19332140304.
[6]
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.
[7]
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.
[8]
Edwards, D. A.; Ward, R. T. (1970). "Some reactions of rhenium(V) chloride". Journal of the Chemical Society A: 1617. doi:10.1039/J19700001617.
[9]
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.
[10]
Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. ISBN 978-0-13-039913-7.

[s1-1] [1]
Mucker, K. F.; Smith, G. S.; Johnson, Q. (1968). "The crystal structure of ReCl₅" (PDF). Acta Crystallographica Section B. 24 (6): 874. Bibcode:1968AcCrB..24..874M. doi:10.1107/S0567740868003316.

[2] [2]
GHS: PubChem 83602

[Linc-3] [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] [4]
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.

[5] [5]
Geilmann, Wilhelm; Wrigge, Friedrich W.; Biltz, Wilhelm. (1933). "Rheniumpentachlorid". Z. Anorg. Allg. Chem. (in German). 214 (3): 244. doi:10.1002/zaac.19332140304.

[6] [6]
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.

[7] [7]
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.

[8] [8]
Edwards, D. A.; Ward, R. T. (1970). "Some reactions of rhenium(V) chloride". Journal of the Chemical Society A: 1617. doi:10.1039/J19700001617.

[9] [9]
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.

[10] [10]
Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. ISBN 978-0-13-039913-7.

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