Hexa(tert-butoxy)ditungsten(III)

Summary

Hexa(tert-butoxy)ditungsten(III) is a coordination complex of tungsten(III). It is one of the homoleptic alkoxides of tungsten. A red, air-sensitive solid, the complex has attracted academic attention as the precursor to many organotungsten derivatives. It an example of a charge-neutral complex featuring a W≡W bond, arising from the coupling of a pair of d3 metal centers. It has attracted particular attention for its reactions with alkynes, leading to alkyne metathesis.[1]

Hexa(tert-butoxy)ditungsten(III)
W2(OC(CH3)3)6.svg
Identifiers
  • 57125-20-9
3D model (JSmol)
  • Interactive image
ChemSpider
  • 26567629
  • 13634733
  • InChI=1S/6C4H9O.2W/c6*1-4(2,3)5;;/h6*1-3H3;;/q6*-1;2*+3
    Key: YKZVERBZIZOWIZ-UHFFFAOYSA-N
  • CC(C)(C)O[W](#[W](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C
Properties
C24H54O6W2
Molar mass 806.37 g·mol−1
Appearance red solid
Density 1.651 g/cm3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

It can be prepared by the salt metathesis reaction from the thf complex of ditungsten heptachloride:[2]

NaW2Cl7(THF)5 + 6 NaOBu-t → W2(OBu-t)6 + 7 NaCl + 5 THF

It was originally prepared by alcoholysis of the amide W2(NMe2)6.[3]

The complex and its dimolybdenum analogue adopt a staggered, ethane-like conformation. The M-M distance is 233 pm.[4] The complex is a weak Lewis acid, forming adducts with two pyridine ligands, for example.[5]

See alsoEdit

ReferencesEdit

  1. ^ Listemann, Mark L.; Schrock, Richard R. (1985). "Multiple metal carbon Bonds. 35. A General Route to tri-tert-Butoxytungsten Alkylidyne complexes. Scission of Acetylenes by Ditungsten Hexa-tert-butoxide". Organometallics. 4: 74–83. doi:10.1021/om00120a014.
  2. ^ Broderick, Erin M.; Browne, Samuel C.; Johnson, Marc J. A. (2014). Dimolybdenum and Ditungsten Hexa(Alkoxides). Inorganic Syntheses. Vol. 36. pp. 95–102. doi:10.1002/9781118744994.ch18. ISBN 9781118744994.
  3. ^ Chisholm, M. H.; Extine, M. (1975). "New Metalloorganic Compounds of Tungsten(III)". Journal of the American Chemical Society. 97 (19): 5625–5627. doi:10.1021/ja00852a074.
  4. ^ Chisholm, Malcolm H.; Gallucci, Judith C.; Hollandsworth, Carl B. (2006). "Crystal and molecular structure of W2(OBut)6 and electronic structure calculations on various conformers of W2(OMe)6". Polyhedron. 25 (4): 827–833. doi:10.1016/j.poly.2005.07.010.
  5. ^ Budzichowski, Theodore A.; Chisholm, M.H.; Folting, Kristen; Huffman, John C.; Streib, William E.; Tiedtke, Darin B. (1998). "Pyridine, isocyanide, carbodiimide and allene adducts of hexakis (Trifluoromethyl t-botoxy) ditungsten. A comparison of ligand binding to W2(Ot-Bu)6 and W2(OCMe2CF3)6". Polyhedron. 17 (5–6): 857–867. doi:10.1016/S0277-5387(97)00290-8.