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Mononuclear Zr complexes CpZrCl2{eta5-C 5H4(CH2)nCH=CH2} (n = 1, 2, 3) undergo intermolecular metathesis of the vinyl group catalyzed by a Ru complex to produce dinuclear complexes with bridging ligands, (CpZrCl 2)2 {mu-eta5-eta5-C 5H4(CH2)nC5H 4}. Hydrogenation of the products catalyzed by Pd/C affords complexes with a flexible polymethylene chain that bridges two Cp2ZrCl 2 groups. A dinuclear complex with a bridging bisfluorenyl ligand, (CpZrCl2)2(mu-eta5,eta5-C 13H8CH2CH=CHCH2C13H 8), is also obtained from the metathesis of a mononuclear Zr complex with the allylfluorenyl ligand. X-ray crystallography of (CpZrCl 2)2(mu-eta5,eta5-C 13H8CH2CH=CHCH2C13H 8) revealed the molecular structure with a trans-C=C double bond and the two Zr centers situated at different sides of the bridging bisfluorenyl ligand. Cross metathesis reaction of CpZrCl2{eta5-C 5H4(CH2)2CH=CH2} and ferrocenylmethyl acrylate produces the Zr/Fe dinuclear complex CpZrCl 2{mu-eta5,eta5-C5H 4(CH2)2-CH=CHCOOCH2C 5H4}FeCp. The dinuclear complexes catalyze polymerization of ethylene and propylene in the presence of MAO (methylaluminoxane). The activity of the Zr/Zr dinuclear complexes for ethylene polymerization is higher than that of the mononuclear precursors. The length and flexibility of the bridging group of the biscyclopentadienyl ligand also influence the catalytic activity.
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Reference：
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion