Organozirconium chemistry is the science of exploring the properties, structure, and reactivity of organozirconium compounds, which are organometallic compounds containing chemical bonds between carbon and zirconium.[2] Organozirconium compounds have been widely studied, in part because they are useful catalysts in Ziegler-Natta polymerization.
Comparison with organotitanium chemistry
Many organozirconium compounds have analogues on organotitanium chemistry. Zirconium(IV) is more resistant to reduction than titanium(IV) compounds, which often convert to Ti(III) derivatives. By the same token, Zr(II) is a particularly powerful reducing agent, forming robust dinitrogen complexes. Being a larger atom, zirconium forms complexes with higher coordination numbers, e.g. polymeric [CpZrCl3]n vs monomeric CpTiCl3 (Cp = C5H5).
Extensive chemistry has also been demonstrated from decamethylzirconocene dichloride, Cp*2ZrCl2. Well-studied derivatives include Cp*2ZrH2, [Cp*2Zr]2(N2)3, Cp*2Zr(CO)2, and Cp*2Zr(CH3)2.
Zirconocene dichloride can be used to cyclise enynes and dienes to give cyclic or bicyclic aliphatic systems.[14][15]
[16]
Alkyl and CO complexes
The simplest organozirconium compounds are the homoleptic alkyls. Salts of [Zr(CH3)6]2- are known. Tetrabenzylzirconium is a precursor to many catalysts for olefin polymerization. It can be converted to mixed alkyl, alkoxy, and halide derivatives, Zr(CH2C6H5)3X (X = CH3, OC2H5, Cl).
Whitby, R. J.; Dixon, S.; Maloney, P. R.; Delerive, P.; Goodwin, B. J.; Parks, D. J.; Willson, T. M. (2006). "Identification of Small Molecule Agonists of the Orphan Nuclear Receptors Liver Receptor Homolog-1 and Steroidogenic Factor-1". Journal of Medicinal Chemistry. 49 (23): 6652–6655. doi:10.1021/jm060990k. PMID 17154495.
Kasatkin, A.; Whitby, R. J. (1999). "Insertion of 1-Chloro-1-lithioalkenes into Organozirconocenes. A Versatile Synthesis of Stereodefined Unsaturated Systems". Journal of the American Chemical Society. 121 (30): 7039–7049. doi:10.1021/ja9910208.
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