Transition metal oxy chloride complexes

Structure of [Ta2OCl10]2−. Ru, Os form similar complexes.

In inorganic chemistry, transition metal oxy chloride complexes are coordination complexes that consists of a transition metal coordinated to chloride and oxide ligands. These complexes are molecular (discrete) in contrast to the ternary phase metal oxychloride. The class of complexes is extensive.

Bonding

Chloride and oxide are X-type ligands in coordination chemistry. Chloride is both σ-donor and a weak π-donor. Oxide is strong σ-donor and a strong π-donor. Both occur as terminal ligand and a bridging ligand.

Molecular M-O-Cl complexes

A selection of transition metal oxochloride complexes.

Metalexamplescomment
Ti[TiOCl4]2−, Cl3TiOTiCl3exclusively Ti(IV)
VVOCl3, [VOCl4]2−exclusively V(V), NbOCl3 is polymeric
Ta[Ta2OCl10]2−
CrCrO2Cl2, [CrO3Cl]−exclusively Cr(VI)
MoMoOCl4,exclusively Mo(VI)
WWOCl4, [W2O4Cl6]2−exclusively W(VI)
ReReO3Cl, Re2O4Cl6see
Fe[Fe2OCl6]2-corner-shared bitetrahedral
Ru[Ru2OCl10]4−corner-shared biooctahedral
Os[Os2OCl10]4−[OsO2Cl4]2−osmium oxides are numerous, exception to the pattern that terminal oxo ligands are associated with d0 metal centers.

The compounds [Ta2OCl10]2− and [M2OCl10]4− (M = W, Ru, Os) have two MCl5 groups joined by a bridging oxygen atom. Each metal has an octahedral environment. The linear M−O−M structure can be rationalized in terms of molecular orbital theory, indicating the presence of dπ — pπ bonding between the metal and oxygen atoms.

structure of an oxychloride of iron(III)

References

  1. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
  2. ↑ Greenwood & Earnshaw, Chapters 22–25, section halides and oxohalides
  3. ↑ Willing, Wolfgang; Schmock, Fritjof; Müller, Ulrich; Dehnicke, Kurt (1986). "(PPH4)2[WO2Cl3]2 · 2 CH2Cl2: Synthese, Schwingungsspektrum und Kristallstruktur". Zeitschrift für Anorganische und Allgemeine Chemie. 532: 137–144. doi:10.1002/zaac.19865320119.
  4. ↑ Supeł, Joanna; Seppelt, Konrad (2006). "Rhenium Trichloride Dioxide, ReO2Cl3". Angewandte Chemie International Edition. 45 (28): 4675–4677. doi:10.1002/anie.200504468. PMID 16789054.
  5. ↑ Haselhorst, Gabriele; Wieghardt, Karl; Keller, Stefan; Schrader, Bernhard (1993). "The (μ-Oxo)bis[trichloroferrate(III)] Dianion Revisited". Inorganic Chemistry. 32 (5): 520–525. doi:10.1021/ic00057a006.
  6. ↑ Do, Y.; Simhon, E. D.; Holm, R. H. (1983). "Improved Syntheses of Tetrachlorodi-μ-sulfidodiferrate Dianion ([Fe2S2Cl4]2-) and Hexachloro-μ-oxodiferrate2- ([Fe2OCl6]2-) and Oxo/Sulfido Ligand Substitution by Use of Silylsulfide Reagents". Inorg. Chem. 22: 3809-12. doi:10.1021/ic00167a027.μ
  7. ↑ Li+ saltMudiyanselage, Ranuri S Dissanayaka; Marshall, Madalynn; Kong, Tai; Xie, Weiwei (2020). "Li4Ru2OCl10·10H2O: Crystal structure, magnetic properties and bonding interactions in ruthenium-oxo complexes". Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials. 76 (5): 884–891. doi:10.1107/S2052520620010914. OSTI 1851622. PMID 33017321.
  8. ↑ NH4+)4 saltRudnitskaya, O. V.; Kultyshkina, E. K.; Popova, M. S.; Stash, A. I. (2013). "Structure of ammonium decachloro-μ-oxodiosmate(IV) (NH4)4[Os2OCl10] and its behavior in solutions". Russian Journal of Inorganic Chemistry. 58 (10): 1227–1230. doi:10.1134/S0036023613100185.
  9. ↑ Kruse, F. H. (1961). "Potassium osmyl chloride – refinement of the crystal structure". Acta Crystallographica. 14 (10): 1035–1041. doi:10.1107/S0365110X61003004.
  10. ↑ Housectroft & Sharpe, Figure 22.5.
  11. ↑ Housectroft & Sharpe, Figure 22.15.