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Zirconocene dichloride

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Zirconocene dichloride

Zirconocene dichloride
Identifiers
CAS number 1291-32-3 YesY
PubChem 10891641
ChemSpider 29081433 N
Jmol-3D images Image 1
Properties
Molecular formula C10H10Cl2Zr
Molar mass 292.32 g mol−1
Appearance white solid
Solubility in water Soluble (Hydrolysis)
Hazards
MSDS CAMEO Chemicals MSDS
 N (verify) (what is: YesY/N?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Zirconocene dichloride is an organozirconium compound composed of a zirconium central atom, with two cyclopentadienyl and two chloro ligands. It is a colourless diamagnetic solid that is somewhat stable in air.

Preparation and structure

Zirconocene dichloride may be prepared from zirconium(IV) chloride-THF complex and sodium cyclopentadienide:

ZrCl4(THF)2 + 2 NaCp → Cp2ZrCl2 + 2 NaCl + 2 THF

The closely related compound Cp2ZrBr2 was first described by Birmingham and Wilkinson.[1]

The compound is a bent metallocene: the Cp rings are not parallel, the average Cp(centroid)-M-Cp angle being 128°. The Cl-Zr-Cl angle of 97.1° is wider than in niobocene dichloride (85.6°) and molybdocene dichloride (82°). This trend helped to establish the orientation of the HOMO in this class of complex.[2]

Reactions

Schwartz's reagent

Zirconocene dichloride reacts with lithium aluminium hydride to give Cp2ZrHCl Schwartz's reagent:

(C5H5)2ZrCl2 + 1/4 LiAlH4 → (C5H5)2ZrHCl + 1/4 "LiAlCl4"

Since lithium aluminium hydride is a strong reductant, some over-reduction occurs to give the dihydrido complex, Cp2ZrH2; treatment of the product mixture with methylene chloride converts it to Schwartz's reagent.[3]

Negishi reagent

Zirconocene dichloride can also be used to prepare the Negishi reagent, Cp2Zr(η2-butene) which is used as a source for Cp2Zr in oxidative cyclisation reactions. This reagent is prepared by treating zirconacene dichloride with n-BuLi leading to replacement of the two chloride ligands with butyl. The dibutyl compound subsequently undergoes alpha-elimination give one η2-butene ligand, eliminating the other butyl ligand as butane.[4]

References

Further reading

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