Trirhenium nonachloride

Last updated
Trirhenium nonachloride
Re3Cl9.png
Names
IUPAC name
Rhenium(III) chloride
Other names
Rhenium trichloride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.033.610 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-987-1
PubChem CID
  • InChI=1S/3ClH.Re/h3*1H;/q;;;+3/p-3
  • Cl[Re](Cl)Cl
Properties
ReCl3
Molar mass 292.57 g/mol
Appearancered, crystalline, nonvolatile solid
Density 4800 kg/m3
Melting point N/A
Boiling point 500 °C (932 °F; 773 K) (decomposes)
hydrolyzes to form Re2O3.xH2O.
Structure
Rhombohedral, hR72
R-3m, No. 166
(trimeric solid and in solution)
(dimeric in acetic acid)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Corrosive (C)
Safety data sheet (SDS)External MSDS
Related compounds
Other anions
Rhenium tribromide
Rhenium triiodide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Trirhenium nonachloride is a compound with the formula ReCl3, sometimes also written Re3Cl9. It is a dark red hygroscopic solid that is insoluble in ordinary solvents. The compound is important in the history of inorganic chemistry as an early example of a cluster compound with metal-metal bonds. [1] It is used as a starting material for synthesis of other rhenium complexes.

Contents

Structure and physical properties

As shown by X-ray crystallography trirhenium nonachloride consists of Re3Cl12 subunits that share three chloride bridges with adjacent clusters. The interconnected network of clusters forms sheets. Around each Re center are seven ligands, four bridging chlorides, one terminal chloride, and two Re-Re bonds. [2]

Re3Cl12 cluster within ReCl3, shown with full coordination sphere around each chloride. ReCl3 showing full coordination sphere around Cl's.png
Re3Cl12 cluster within ReCl3, shown with full coordination sphere around each chloride.

The heat of oxidation is evaluated according to the equation:

1/3 Re3Cl9 + 4 OH + 2 OCl → ReO4 + 2 H2O + 5Cl

The enthalpy for this process is 190.7 ± 0.2 kcal/mol. [2]

Preparation and reactions

The compound was discovered in 1932, although these workers did not determine its structure, which is unusual for metal chlorides. [3] Trirhenium nonachloride is efficiently prepared by thermal decomposition of rhenium pentachloride or hexachlororhenic(IV) acid: [4]

3 ReCl5 → Re3Cl9 + 3 Cl2

If the sample is vacuum sublimed at 500 °C, the resulting material is comparatively unreactive, but the partially hydrated material can be more useful synthetically. Other synthetic methods include treating rhenium with sulfuryl chloride. This process is sometimes conducted with the addition of aluminium chloride. [2] It is also obtained by heating Re2(O2CCH3)4Cl2 under HCl:

3/2 Re2(O2CCH3)4Cl2 + 6 HCl → Re3Cl9 + 6 HO2CCH3

Reaction of the tri- and pentachlorides gives rhenium tetrachloride:

3 ReCl5 + Re3Cl9 → 6 ReCl4

Related Research Articles

<span class="mw-page-title-main">Group 7 element</span> Group of chemical elements

Group 7, numbered by IUPAC nomenclature, is a group of elements in the periodic table. It contains manganese (Mn), technetium (Tc), rhenium (Re) and bohrium (Bh). This group lies in the d-block of the periodic table, and are hence transition metals. This group is sometimes called the manganese group or manganese family after its lightest member; however, the group itself has not acquired a trivial name because it belongs to the broader grouping of the transition metals.

<span class="mw-page-title-main">Samarium(III) chloride</span> Chemical compound

Samarium(III) chloride, also known as samarium trichloride, is an inorganic compound of samarium and chloride. It is a pale yellow salt that rapidly absorbs water to form a hexahydrate, SmCl3.6H2O. The compound has few practical applications but is used in laboratories for research on new compounds of samarium.

<span class="mw-page-title-main">Europium(III) chloride</span> Chemical compound

Europium(III) chloride is an inorganic compound with the formula EuCl3. The anhydrous compound is a yellow solid. Being hygroscopic it rapidly absorbs water to form a white crystalline hexahydrate, EuCl3·6H2O, which is colourless. The compound is used in research.

<span class="mw-page-title-main">Dysprosium(III) chloride</span> Chemical compound

Dysprosium(III) chloride (DyCl3), also known as dysprosium trichloride, is a compound of dysprosium and chlorine. It is a white to yellow solid which rapidly absorbs water on exposure to moist air to form a hexahydrate, DyCl3·6H2O. Simple rapid heating of the hydrate causes partial hydrolysis to an oxychloride, DyOCl.

<span class="mw-page-title-main">Phosphorus pentachloride</span> Chemical compound

Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides/oxychlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive solid, although commercial samples can be yellowish and contaminated with hydrogen chloride.

<span class="mw-page-title-main">Niobium(V) chloride</span> Chemical compound

Niobium(V) chloride, also known as niobium pentachloride, is a yellow crystalline solid. It hydrolyzes in air, and samples are often contaminated with small amounts of NbOCl3. It is often used as a precursor to other compounds of niobium. NbCl5 may be purified by sublimation.

<span class="mw-page-title-main">Tantalum(V) chloride</span> Chemical compound

Tantalum(V) chloride, also known as tantalum pentachloride, is an inorganic compound with the formula TaCl5. It takes the form of a white powder and is commonly used as a starting material in tantalum chemistry. It readily hydrolyzes to form tantalum(V) oxychloride (TaOCl3) and eventually tantalum pentoxide (Ta2O5); this requires that it be synthesised and manipulated under anhydrous conditions, using air-free techniques.

<span class="mw-page-title-main">Terbium(III,IV) oxide</span> Chemical compound

Terbium(III,IV) oxide, occasionally called tetraterbium heptaoxide, has the formula Tb4O7, though some texts refer to it as TbO1.75. There is some debate as to whether it is a discrete compound, or simply one phase in an interstitial oxide system. Tb4O7 is one of the main commercial terbium compounds, and the only such product containing at least some Tb(IV) (terbium in the +4 oxidation state), along with the more stable Tb(III). It is produced by heating the metal oxalate, and it is used in the preparation of other terbium compounds. Terbium forms three other major oxides: Tb2O3, TbO2, and Tb6O11.

<span class="mw-page-title-main">Erbium(III) chloride</span> Chemical compound

Erbium(III) chloride is a violet solid with the formula ErCl3. It is used in the preparation of erbium metal.

<span class="mw-page-title-main">Gadolinium(III) chloride</span> Chemical compound

Gadolinium(III) chloride, also known as gadolinium trichloride, is GdCl3. It is a colorless, hygroscopic, water-soluble solid. The hexahydrate GdCl3∙6H2O is commonly encountered and is sometimes also called gadolinium trichloride. Gd3+ species are of special interest because the ion has the maximum number of unpaired spins possible, at least for known elements. With seven valence electrons and seven available f-orbitals, all seven electrons are unpaired and symmetrically arranged around the metal. The high magnetism and high symmetry combine to make Gd3+ a useful component in NMR spectroscopy and MRI.

<span class="mw-page-title-main">Antimony pentachloride</span> Chemical compound

Antimony pentachloride is a chemical compound with the formula SbCl5. It is a colourless oil, but typical samples are yellowish due to dissolved chlorine. Owing to its tendency to hydrolyse to hydrochloric acid, SbCl5 is a highly corrosive substance and must be stored in glass or PTFE containers.

<span class="mw-page-title-main">Molybdenum(V) chloride</span> Chemical compound

Molybdenum(V) chloride is the inorganic compound with the empirical formula MoCl5. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents.

Lanthanum chloride is the inorganic compound with the formula LaCl3. It is a common salt of lanthanum which is mainly used in research. It is a white solid that is highly soluble in water and alcohols.

Technetium compounds are chemical compounds containing the chemical element technetium. Technetium can form multiple oxidation states, but often forms in the +4 and +7 oxidation states. Because technetium is radioactive, technetium compounds are extremely rare on Earth.

<span class="mw-page-title-main">Nitrosyl chloride</span> Chemical compound

Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.

<span class="mw-page-title-main">Molybdenum(II) chloride</span> Chemical compound

Molybdenum dichloride describes chemical compounds with the empirical formula MoCl2. At least two forms are known, and both have attracted much attention from academic researchers because of the unexpected structures seen for these compounds and the fact that they give rise to hundreds of derivatives. The form discussed here is Mo6Cl12. The other molybdenum(II) chloride is potassium octachlorodimolybdate.

<span class="mw-page-title-main">Rhenium pentachloride</span> Chemical compound

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.

Organorhenium chemistry describes the compounds with Re−C bonds. Because rhenium is a rare element, relatively few applications exist, but the area has been a rich source of concepts and a few useful catalysts.

<span class="mw-page-title-main">Potassium octachlorodirhenate</span> Chemical compound

Potassium octachlorodirhenate(III) is an inorganic compound with the formula K2Re2Cl8. This dark blue salt is well known as an early example of a compound featuring quadruple bond between its metal centers. Although the compound has no practical value, its characterization was significant in opening a new field of research into complexes with quadruple bonds.

Rhenium compounds are compounds formed by the transition metal rhenium (Re). Rhenium can form in many oxidation states, and compounds are known for every oxidation state from -3 to +7 except -2, although the oxidation states +7, +6, +4, and +2 are the most common. Rhenium is most available commercially as salts of perrhenate, including sodium and ammonium perrhenates. These are white, water-soluble compounds. Tetrathioperrhenate anion [ReS4] is possible.

References

  1. Cotton, F. A.; Walton, R. A. "Multiple Bonds Between Metal Atoms" Oxford (Oxford): 1993. ISBN   0-19-855649-7.
  2. 1 2 3 Colton, R. Chemistry of rhenium and technetium. 965.
  3. Geilnann, W.; Wriuce, F. W.; Biltz. W.: Nachr. Ges. Wiss. Gottingen 1932, 579.
  4. Lincoln, R.; Wilkinson, G. (2007). "Trirhenium Nonachloride". Inorganic Syntheses. pp.  44. doi:10.1002/9780470132517.ch12. ISBN   978-0-470-13251-7.{{cite book}}: |journal= ignored (help)