Abstract
The reactions of ferrocenyl methanol, ferrocenyl 2-propanol and N-methyl-2-ferrocenylmethylamine with chlorocyclophosphazenes have been examined. The pentachlorocyclotriphosphazene derivative of ferrocenylmethanol undergoes rapid decomposition via a phosphazene-phosphazane rearrangement, however when the alcohol function is β to the cyclopentadienyl ring modest yields of N3P3Cl5OCHMeCH2C2H4FeCp may be obtained. By way of contrast N-methyl-2-ferrocenylmethylamine gives a broad range of stable derivatives, N3P3Cl6-n[NMeCH2C5H4FeCp]n(n=l-3). The substitution process follows a predominantly trans non-geminal pathway. The corresponding reaction with the butylmethacrylate derivative, N3P3Cl5O(CH2)4OC(O)CMe=CH2 leads to the unexpected geminal product, 2,2′-N3P3Cl4[O(CH2)4OC(O)CMe=CH2]NMeCH2C5H4FeCp. Polymers containing the 2-ferrocenylmethylamine function have been obtained by reactions of poly(dichlorophosphazene) with the ferrocenylamine and by radical addition polymerization of the aforementioned mixed ferrocenylamino butylmethacrylphosphazene. The new materials have been characterized by standard methologies including 31P NMR spectroscopy, cyclic voltametry and gel permeation chromatography.
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