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 [CpZrCl3n 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]
The simplest organozirconium compounds are the
homoleptic alkyls. Salts of [Zr(CH3)62- 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).
In addition to mixed Cp2Zr(CO)2, zirconium forms the binary carbonyl [Zr(CO)62-.[18]
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.
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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.
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References
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