Niobium(V) chloride

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Niobium(V) chloride
Niobium pentachloride solid.jpg
Niobium-pentachloride-dimer-2D.png
Names
IUPAC names
Niobium(V) chloride
Niobium pentachloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.042 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 233-059-8
PubChem CID
RTECS number
  • QU0350000
UNII
  • InChI=1S/5ClH.Nb/h5*1H;/q;;;;;+5/p-5
    Key: YHBDIEWMOMLKOO-UHFFFAOYSA-I
  • Cl[Nb](Cl)(Cl)(Cl)Cl
  • dimer:Cl[Nb-]1(Cl)(Cl)(Cl)[Cl+][Nb-]([Cl+]1)(Cl)(Cl)(Cl)Cl
Properties
NbCl5
Molar mass 270.17 g/mol
Appearanceyellow monoclinic crystals
deliquescent
Density 2.75 g/cm3
Melting point 204.7 °C (400.5 °F; 477.8 K)
Boiling point 248.2 °C (478.8 °F; 521.3 K)
decomposes
Solubility HCl, chloroform, CCl4
Thermochemistry
214.05 J K−1 mol−1
-797.47 kJ/mol
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H302, H312, H314, H332
P260, P261, P264, P270, P271, P280, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P312, P321, P322, P330, P363, P405, P501
Flash point Non-flammable
Related compounds
Other anions
Niobium(V) fluoride
Niobium(V) bromide
Niobium(V) iodide
Other cations
Vanadium(IV) chloride
Tantalum(V) chloride
Related niobium chlorides
 Niobium(III) chloride
Niobium(IV) chloride
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

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. [1]

Contents

Structure and properties

Ball-and-stick model of niobium pentachloride Niobium-pentachloride-from-xtal-3D-balls.png
Ball-and-stick model of niobium pentachloride

Niobium(V) chloride forms chloro-bridged dimers in the solid state (see figure). Each niobium centre is six-coordinate, but the octahedral coordination is significantly distorted. The equatorial niobium–chlorine bond lengths are 225 pm (terminal) and 256 pm (bridging), whilst the axial niobium-chlorine bonds are 229.2 pm and are deflected inwards to form an angle of 83.7° with the equatorial plane of the molecule. The Nb–Cl–Nb angle at the bridge is 101.3°. The Nb–Nb distance is 398.8 pm, too long for any metal-metal interaction. [2] NbBr5, TaCl5 and TaBr5 are isostructural with NbCl5, but NbI5 and TaI5 have different structures.

Preparation

Niobium pentachloride liquid and vapor. Niobium pentachloride2.jpg
Niobium pentachloride liquid and vapor.

Industrially, niobium pentachloride is obtained by direct chlorination of niobium metal at 300 to 350 °C: [3]

2 Nb + 5 Cl2 → 2 NbCl5

In the laboratory, niobium pentachloride is often prepared from Nb2O5, the main challenge being incomplete reaction to give NbOCl3. The conversion can be effected with thionyl chloride: [4] It also can be prepared by chlorination of niobium pentoxide in the presence of carbon at 300 °C.

Uses

Niobium(V) chloride is the main precursor to the alkoxides of niobium, which find uses in sol-gel processing. It is also the precursor to many other Nb-containing reagents, including most organoniobium compounds.

In organic synthesis, NbCl5 is a very specialized Lewis acid in activating alkenes for the carbonyl-ene reaction and the Diels-Alder reaction. Niobium chloride can also generate N-acyliminium compounds from certain pyrrolidines which are substrates for nucleophiles such as allyltrimethylsilane, indole, or the silyl enol ether of benzophenone. [5]

Related Research Articles

Hypochlorite Ion

In chemistry, hypochlorite is an anion with the chemical formula ClO−. It combines with a number of cations to form hypochlorite salts. Common examples include sodium hypochlorite and calcium hypochlorite. The Cl-O distance in ClO− is 210 pm.

Iron(II) chloride Chemical compound

Iron(II) chloride, also known as ferrous chloride, is the chemical compound of formula FeCl2. It is a paramagnetic solid with a high melting point. The compound is white, but typical samples are often off-white. FeCl2 crystallizes from water as the greenish tetrahydrate, which is the form that is most commonly encountered in commerce and the laboratory. There is also a dihydrate. The compound is highly soluble in water, giving pale green solutions.

Phosphorus pentachloride Chemical compound

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

Phosphorus trichloride Chemical compound

Phosphorus trichloride is a inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

Tantalum(V) chloride 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.

Hafnium tetrachloride Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Zirconium(IV) chloride Chemical compound

Zirconium(IV) chloride, also known as zirconium tetrachloride, is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

Vanadium tetrachloride is the inorganic compound with the formula VCl4. This bright red liquid serves as a useful reagent for the preparation of other vanadium compounds.

Molybdenum(V) chloride Chemical compound

Molybdenum(V) chloride is the inorganic compound with the formula [MoCl5]2. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents. Usually called molybdenum pentachloride, it is in fact a dimer with the formula Mo2Cl10.

Tantalum(V) bromide Chemical compound

Tantalum(V) bromide is the inorganic compound with the formula Taa2Br10. Its name comes from the compound's empirical formula, TaBr5. It is a diamagnetic, orange solid that hydrolyses readily. The compound adopts an edge-shared bioctahedral structure, which means that two TaBr5 units are joined by a pair of bromide bridges. There is no bond between the Ta centres. Niobium(V) chloride, niobium(V) bromide, niobium(V) iodide, tantalum(V) chloride, and tantalum(V) iodide all share this structural motif.

Niobocene dichloride is the organometallic compound with the formula (C5H5)2NbCl2, abbreviated Cp2NbCl2. This paramagnetic brown solid is a starting reagent for the synthesis of other organoniobium compounds. The compound adopts a pseudotetrahedral structure with two cyclopentadienyl and two chloride substituents attached to the metal. A variety of similar compounds are known, including Cp2TiCl2.

Trirhenium nonachloride Chemical compound

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. It is used as a starting material for synthesis of other rhenium complexes.

Rhenium pentachloride 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.

Niobium pentoxide Chemical compound

Niobium pentoxide is the inorganic compound with the formula Nb2O5. A colorless, insoluble, and fairly unreactive solid, it is the most widespread precursor for other compounds and materials containing niobium. It is predominantly used in alloying, with other specialized applications in capacitors, optical glasses, and the production of lithium niobate.

Niobium(IV) chloride Chemical compound

Niobium(IV) chloride, also known as niobium tetrachloride, is the chemical compound of formula NbCl4. This compound exists as dark violet crystals, is highly sensitive to air and moisture, and disproportiates into niobium(III) chloride and niobium(V) chloride when heated.

Niobium oxychloride Chemical compound

Niobium oxychloride is the inorganic compound with the formula NbOCl3. It is a white, crystalline, diamagnetic solid. It is often found as an impurity in samples of niobium pentachloride, a common reagent in niobium chemistry.

Organotantalum chemistry Chemistry of compounds containing a carbon-to-tantalum bond

Organotantalum chemistry is the chemistry of chemical compounds containing a carbon-to-tantalum chemical bond. A wide variety of compound have been reported, initially with cyclopentadienyl and CO ligands. Oxidation states vary from Ta(V) to Ta(-I).

Niobium(III) chloride also known as niobium trichloride is a compound of niobium and chlorine. The binary phase NbCl3 is not well characterized but many adducts are known.

Transition metal chloride complex Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

Lanthanide trichlorides are a family of inorganic compound with the formula LnCl3, where Ln stands for a lanthanide metal. The trichlorides are standard reagents in applied and academic chemistry of the lanthanides. They exist as anhydrous solids and as hydrates.

References

  1. ↑ Cotton, F. Albert; Wilkinson, Geoffrey (1980), Advanced Inorganic Chemistry (4th ed.), New York: Wiley, ISBN   0-471-02775-8
  2. ↑ Cotton, F.A., P. A. Kibala, M. Matusz and R. B. W. Sandor (1991). "Structure of the Second Polymorph of Niobium Pentachloride". Acta Crystallogr. C . 47 (11): 2435–2437. doi:10.1107/S0108270191000239.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  3. ↑ Joachim Eckert, Hermann C. Starck (2005). "Niobium and Niobium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_251. ISBN   3527306730.{{cite encyclopedia}}: CS1 maint: uses authors parameter (link)
  4. ↑ Brown, D. (1957). "Niobium(V) Chloride and Hexachloroniobates(V)". Inorganic Syntheses. Inorganic Syntheses. Vol. 9. pp. 88–92. doi:10.1002/9780470132401.ch24. ISBN   9780470132401.
  5. ↑ Andrade, C. K. Z.; Rocha, R. O.; Russowsky, D. & Godoy, M. N. (2005). "Studies on the Niobium Pentachloride-Mediated Nucleophilic Additions to an Enantiopure Cyclic N-acyliminium Ion Derived from (S)-malic acid". J. Braz. Chem. Soc. 16 (3b): 535–539. doi: 10.1590/S0103-50532005000400007 .
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