Zirconocene dichloride may be prepared from zirconium(IV) chloride-tetrahydrofuran complex and sodium cyclopentadienide: The closely related compound Cp2ZrBr2 was first described by Birmingham and Wilkinson.

The Negishi reagent is prepared by treating zirconocene dichloride with n-BuLi, leading to replacement of the two chloride ligands with butyl groups.

[4] Zirconocene dichloride catalyzes the carboalumination of alkynes by trimethylaluminium to give a (alkenyl)dimethylalane, a versatile intermediate for further cross coupling reactions for the synthesis of stereodefined trisubstituted olefins.

[5] The use of trimethylaluminium for this reaction results in exclusive formation of the syn-addition product and, for terminal alkynes, the anti-Markovnikov addition with high selectivity (generally > 10:1).

Although this is a major limitation, the synthetic utility of this process remains significant, due to the frequent appearance of methyl-substituted alkenes in natural products.