Other Polymetallocenes with Short Spacers Obtained by Polycondensation Routes

Other Polymetallocenes with Short Spacers Obtained by Polycondensation Routes 

A similar route was reported in the mid-1960s for the synthesis of polyferrocenes with phosphorus spacers (3.11, 3.12) [42, 43]. Reaction of ferrocene with PPhCl2, P(0)PhCl2 or P(S)PhCl2 in the presence of a Lewis acid catalyst such as ZnCl2 in the melt or in solution at 80-170 °C yielded low molecular weight materials 

The air- and thermally stable (to 350°C) polyferrocenylphenylphosphine 3.11 was shown to react with low concentrations of Co2(CO)g, leading to products containing chelated cobalt centers [46]. According to IR and P NMR data, three Co-P bonds were present per metal atom, and the cobalt environments possessed a pseudo-trigonal bipyramidal geometry. The catalytic potential of the materials in the hydroformylation of 1-hexene was studied and was shown to be similar to that of the complex HCo(CO)3PPh3. 

15 V) that provided further evidence for substantial electronic communication between the metallocene units [54], 

Disulfide-bridged oligoferrocenes 3.18 (M 3500) were prepared in an attempt to copolymerize ferrocenedithiol with norbomadiene in the presence of AIBN in toluene [55, 56]. Rather than the expected radical-induced polyaddition [57] to give 3.17 (Eq. 3.8), condensation of the ferrocene monomer was observed with norbor-nene and nortricydane units as end-groups (Eq. 3.9). The isolated oligomers (3.18) were characterized by NMR spectroscopy and field-desorption mass spectrometry, and possessed a chain length of 2-12 repeat units as determined by GPC. 

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