Niobium(III) chloride

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Niobium(III) chloride
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.033.608 Edit this at Wikidata
EC Number
  • 236-985-0
  • InChI=1S/3ClH.Nb/h3*1H;/q;;;+3/p-3
    Key: VPDYSPXEGTXWEU-UHFFFAOYSA-K
  • 1,2-dimethoxyethane complex: InChI=1S/C4H10O2.3ClH.Nb/c1-5-3-4-6-2;;;;/h3-4H2,1-2H3;3*1H;/q;;;;+3/p-3
    Key: SBSZUBUHOUKQMN-UHFFFAOYSA-K
  • [Cl-].[Cl-].[Cl-].[Nb+3]
  • 1,2-dimethoxyethane complex: COCCOC.Cl[Nb](Cl)Cl
Properties
Cl3Nb
Molar mass 199.26 g·mol−1
Appearance black solid
Density 3.75
Structure[1]
hexagonal
P3m1
a = 6.744, c = 12.268
2
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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.

Synthesis

Structure of NbCl3(dimethoxyethane)(3-hexyne).[2]

Nb3Cl8 is produced by reduction of

hydrogen
, or just by heating.

3-hexyne produces the coordination complex
NbCl3(dimethoxyethane)(3-hexyne):

NbCl5 + C6H6(SiMe3)2 + C2Et2 + dme → NbCl3(dme)(C2Et2) + C6H6 + 2 Me3SiCl

An impure dimethoxyethane (dme) adduct of niobium trichloride was produced by reduction of a dme solution of niobium pentachloride with tributyltin hydride:[3]

NbCl5 + 2 Bu3SnH + MeOCH2CH2OMe → NbCl3(MeOCH2CH2OMe) + 2 Bu3SnCl

Structure

Nb3Cl8 has a

nonstoichiometric compounds. NbCl4 has this pattern of vacancies stretched until the niobium atoms are in pairs rather than triangles. So NbCl3 can be considered as a solid solution of Nb3Cl8 and Nb2Cl8.[4]

The colour of niobium trichloride varies depending on the niobium:chloride ratio. NbCl2.67 is green, while NbCl3.13 is brown.[1]

Reactions

Structure of Nb2Cl6(SMe2)3.[5]

When heated to over 600 °C niobium trichloride disproportionates to niobium metal and niobium pentachloride.

Adducts

NbCl3(dimethoxyethane) has received significant attention as a reagent for reductive coupling of carbonyls and imines.

1,4-dioxane and diethyl ether
.

Niobium(III) chloride forms a series of compounds with the formula Nb2Cl6Lx with Nb=Nb

tertiary phosphines and arsines, the complexes are edge-share bioctahedra, e.g., Nb2Cl6(PPhMe2)4.[7]
Thioethers form adducts with one bridging thioether (R2S). These face-sharing bioctahedra have the formula Nb2X6(R2S)3 (X = Cl, Br).

References

  1. ^
    ISBN 978-0-323-14847-4
    .
  2. S2CID 73505603
    .
  3. ISBN 9780470132609
    .
  4. ^ Cotton, F. Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry: A Comprehensive Text. John Wiley. p. 927.
  5. doi:10.1107/S1600536806005149
    .
  6. ISBN 0471936235
    .
  7. ISSN 0975-0975
    .
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