Reactions of Ferrocenyl Amines and Alcohols with Hexachlorocyclotriphosphazene

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, N₃P₃Cl_6-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.

Keywords::

• cyclophosphazenes
• polyphosphazenes
• ferrocene derivatives
• redox active phosphazenes
• electrochemistry