Tantalum(III) chloride

Tantalum(III) chloride
Names
	Other names tantalum trichloride
Identifiers
CAS Number	13569-67-0;
3D model (JSmol)	Interactive image;
ChemSpider	75412;
ECHA InfoCard	100.033.611
EC Number	236-988-7;
PubChem CID	83582;
CompTox Dashboard (EPA)	DTXSID3065538 ;
	InChI InChI=1S/3ClH.Ta/h3*1H;/q;;;+3/p-3 Key: UDKRLEXYBPHRQF-UHFFFAOYSA-K;
	SMILES Cl[Ta](Cl)Cl;
Properties
Chemical formula	Cl3Ta
Molar mass	287.30 g·mol−1
Appearance	black-green
Melting point	440 °C (824 °F; 713 K) decomposes[1]
Solubility in water	yes
Related compounds
Other anions	Tantalum(III) bromide; Tantalum(III) iodide
Other cations	Niobium(III) chloride
Related compounds	Ta6Cl15; Tantalum(IV) chloride; Tantalum(V) chloride
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Tantalum(III) chloride or tantalum trichloride is non-stoichiometric with a range of composition from TaCl_2.9 to TaCl_3.1[2] Anionic and neutral clusters containing Ta(III) chloride include [Ta₆Cl₁₈]⁴⁻ and [Ta₆Cl₁₄](H₂O)₄.[3]

Structure of edge-capped octahedral clusters such as Ta₆Cl₁₈²⁻.[4]

Formation

Tantalum(III) chloride is formed by reducing tantalum(V) chloride with tantalum metal. this is done by heating tantalum(III) chloride to 305°C, passing the vapour over tantalum foil at 600°, and condensing the trichloride at 365°C. If the condensing region is kept at too high a temperature, then TaCl_2.5 deposits instead.[5]

The trichloride can also be prepared by thermal decomposition of TaCl₄, with removal of volatile TaCl₅. TaCl₅ can be vapourised leaving behind TaCl₃.[6]

Reduction of a toluene solution of TaCl₅ with 1,4-disilyl-cyclohexadiene in the presence of ethylene produces a complex of TaCl₃:[7]

TaCl₅ + C₆H₆(SiMe₃)₂ → "TaCl₃" + C₆H₆ + 2 Me₃SiCl

Properties

Above 500 °C, TaCl₃ disproportionates further releasing TaCl₅.[6] TaCl₃ is insoluble in room temperature water, or dilute acid, but dissolves in boiling water. A blue-green solution is formed.[6]

Complexes

Tantalum(III) chloride can form complexes with some ligands as a monomer or dimer.

Complexes include Ta(=C-CMe₃)(PMe₃)₂Cl₃, [TaCl₃(P(CH₂C₆H₅)₃THF]₂μ-N₂ and [TaCl₃THF₂]₂μ-N₂ (dinitrogen complexes).[8]

As a dimer, complexes include Ta₂Cl₆(SC₄H₈)₃ (SC₄H₈=tetrahydrothiophene). Ta₂Cl₆(SMe₂)₃, Ta₂Cl₆(thiane)₃ and Ta₂Cl₆(thiolane)₃ have a double bond between the two tantalum atoms, and two bridging chlorides, and a bridging ligand.[9]

References

Haynes, William M. (2016). CRC Handbook of Chemistry and Physics (97 ed.). CRC Press. p. 4–97. ISBN 978-1-4987-5429-3.
Cotton, F Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry A Comprehensive Text. John Wiley. p. 927.
Duraisamy, Thirumalai; Hay, Daniel N. T.; Messerle, Louis (2014). "Octahedral Hexatantalum Halide Clusters". Inorganic Syntheses: Volume 36. Inorganic Syntheses. 36. pp. 1–8. doi:10.1002/9781118744994.ch1. ISBN 9781118744994.
Thaxton, C. B.; Jacobson, R. A. (1971). "The Crystal Structure of H₂(Ta₆Cl₁₈)(H₂O)₆". Inorganic Chemistry. 10: 1460–1463. doi:10.1021/ic50101a029.CS1 maint: uses authors parameter (link)
Gutmann, Viktor (2012). Halogen Chemistry. Elsevier. p. 158. ISBN 978-0-323-14847-4.
Remy, Heinrich (1963). Treatise on Inorganic Chemistry: Sub-groups of the periodic table and general topics. Elsevier Publishing Company. p. 115.
Arteaga-Müller, Rocío; Tsurugi, Hayato; Saito, Teruhiko; Yanagawa, Masao; Oda, Seiji; Mashima, Kazushi (2009). "New Tantalum Ligand-Free Catalyst System for Highly Selective Trimerization of Ethylene Affording 1-Hexene: New Evidence of a Metallacycle Mechanism". Journal of the American Chemical Society. 131 (15): 5370–5371. doi:10.1021/ja8100837. PMID 20560633.
Churchill, Melvyn Rowen.; Wasserman, Harvey J. (January 1982). "The Ta(.mu.-N2)Ta system. 2. Crystal structure of [TaCl3(P(bz)3)(THF)]2(.mu.-N2)..apprx.0.7CH2Cl2. A binuclear di-imido complex of octahedral tantalum (V)". Inorganic Chemistry. 21 (1): 218–222. doi:10.1021/ic00131a040.
Matsuura, Masatoshi; Fujihara, Takashi; Kakeya, Masaki; Sugaya, Tomoaki; Nagasawa, Akira (November 2013). "Dinuclear niobium(III) and tantalum(III) complexes with thioether and selenoether ligands [{MIIIX2(L)}2(μ-X)2(μ-L)] (M = Nb, Ta; X = Cl, Br; L = R2S, R2Se): Syntheses, structures, and the optimal conditions and the mechanism of the catalysis for regioselective cyclotrimerization of alkynes". Journal of Organometallic Chemistry. 745–746: 288–298. doi:10.1016/j.jorganchem.2013.07.035.

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[1] Haynes, William M. (2016). CRC Handbook of Chemistry and Physics (97 ed.). CRC Press. p. 4–97. ISBN 978-1-4987-5429-3.

[2] Cotton, F Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry A Comprehensive Text. John Wiley. p. 927.

[3] Duraisamy, Thirumalai; Hay, Daniel N. T.; Messerle, Louis (2014). "Octahedral Hexatantalum Halide Clusters". Inorganic Syntheses: Volume 36. Inorganic Syntheses. 36. pp. 1–8. doi:10.1002/9781118744994.ch1. ISBN 9781118744994.

[4] Thaxton, C. B.; Jacobson, R. A. (1971). "The Crystal Structure of H₂(Ta₆Cl₁₈)(H₂O)₆". Inorganic Chemistry. 10: 1460–1463. doi:10.1021/ic50101a029.CS1 maint: uses authors parameter (link)

[5] Gutmann, Viktor (2012). Halogen Chemistry. Elsevier. p. 158. ISBN 978-0-323-14847-4.

[rem-6] Remy, Heinrich (1963). Treatise on Inorganic Chemistry: Sub-groups of the periodic table and general topics. Elsevier Publishing Company. p. 115.

[7] Arteaga-Müller, Rocío; Tsurugi, Hayato; Saito, Teruhiko; Yanagawa, Masao; Oda, Seiji; Mashima, Kazushi (2009). "New Tantalum Ligand-Free Catalyst System for Highly Selective Trimerization of Ethylene Affording 1-Hexene: New Evidence of a Metallacycle Mechanism". Journal of the American Chemical Society. 131 (15): 5370–5371. doi:10.1021/ja8100837. PMID 20560633.

[8] Churchill, Melvyn Rowen.; Wasserman, Harvey J. (January 1982). "The Ta(.mu.-N2)Ta system. 2. Crystal structure of [TaCl3(P(bz)3)(THF)]2(.mu.-N2)..apprx.0.7CH2Cl2. A binuclear di-imido complex of octahedral tantalum (V)". Inorganic Chemistry. 21 (1): 218–222. doi:10.1021/ic00131a040.

[9] Matsuura, Masatoshi; Fujihara, Takashi; Kakeya, Masaki; Sugaya, Tomoaki; Nagasawa, Akira (November 2013). "Dinuclear niobium(III) and tantalum(III) complexes with thioether and selenoether ligands [{MIIIX2(L)}2(μ-X)2(μ-L)] (M = Nb, Ta; X = Cl, Br; L = R2S, R2Se): Syntheses, structures, and the optimal conditions and the mechanism of the catalysis for regioselective cyclotrimerization of alkynes". Journal of Organometallic Chemistry. 745–746: 288–298. doi:10.1016/j.jorganchem.2013.07.035.