<i>N</i>-(Ferrocenylmethyl)-<i>N</i>-methylaminocyclotriphosphazenes

The reactions of N-(ferrocenylmethyl)-N-methylamine, C(5)H(5)FeC(5)H(4)CH(2)(Me)NH, with hexachlorocyclotriphosphazene, N(3)P(3)Cl(6), led to the formation of the N-(ferrocenylmethyl)-N-methylaminocyclotriphosphazene derivatives, N(3)(-)P(3)Cl(6-n)[N(Me)CH(2)C(5)H(4)FeC(5)H(5)](n) (n = 1-3). Only small amounts of higher degrees of substitution could be detected. In the case of the disubstituted products, the ratio of isomers was dependent on the polarity of the solvent. In nonpolar solvents the ratio was trans > geminal > cis while in acetonitrile only equal amounts of trans and cis isomers were observed. The reaction of N-(ferrocenylmethyl)-N-methylamine with (methacryloylbutenedioxy)pentachlorocyclotriphosphazene, N(3)P(3)Cl(5)O(CH(2))(4)OC(O)C(Me)=CH(2), gives the surprising geminal isomer 2,2-N(3)P(3)Cl(4)[O(CH(2))(4)OC(O)C(Me)=CH(2)]N(Me)CH(2)C(5)H(4)FeC(5)H(5) and the tris derivative 2,2',4-N(3)P(3)Cl(3)[O(CH(2))(4)OC(O)C(Me)=CH(2)][N(Me)CH(2)C(5)H(4)FeC(5)H(5)](2). All of the phosphazene derivatives were characterized by elemental analyses, mass spectrometry, IR and NMR ((1)H, (13)C, (31)P) spectroscopy, and electrochemical techniques (cyclic, normal pulse, and differential pulse voltametry). The compounds all undergo a single, reversible oxidation reduction process.