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Cyclophosphazene Hydrazides as Scaffolds for Multi-Ferrocenyl Assemblies: Synthesis, Structure, and Electrochemistry

2003; American Chemical Society; Volume: 22; Issue: 5 Linguagem: Inglês

10.1021/om020760d

1520-6041

Vadapalli Chandrasekhar, Senthil A. Gurusamy Thangavelu, Selvarajan Nagendran, Krishnan Venkatasubbaiah, R. Azhakar, Ray J. Butcher,

Organometallic Complex Synthesis and Catalysis

Reactions of N-methylhydrazine with chlorocyclophosphazenes, N3P3Cl6 (1), N3P3(OPh)Cl5 (2), gem-N3P3Ph2Cl4 (3), spiro-N3P3(O2C12H8)2Cl2 (4), N3P3(OPh)5Cl (5), and diphenylphosphinic chloride, Ph2P(O)Cl (6), proceed in a regiospecific manner to afford the products N3P3[N(Me)NH2]6 (1a), N3P3(OPh)[N(Me)NH2]5 (2a), gem-N3P3Ph2[N(Me)NH2]4 (3a), spiro-N3P3(O2C12H8)2[N(Me)NH2]2 (4a), N3P3(OPh)5[N(Me)NH2] (5a), and Ph2P(O)[N(Me)NH2] (6a). The terminal NH2 groups in all of these compounds are reactive and have been used in the condensation reaction involving ferrrocene-2-carboxaldehyde to afford the corresponding hydrazones N3P3[N(Me)NCHC5H4FeC5H5]6 (1b), N3P3(OPh)[ N(Me)NCHC5H4FeC5H5]5 (2b), gem-N3P3Ph2[N(Me)NCHC5H4FeC5H5]4 (3b), spiro-N3P3(O2C12H8)2[N(Me)NCHC5H4FeC5H5]2 (4b), N3P3(OPh)5[N(Me)NCHC5H4FeC5H5] (5b), and Ph2P(O)[ N(Me)NCHC5H4FeC5H5] (6b). The structures of 1−6(a,b) have been determined by the use of multinuclear NMR, mass spectroscopy, and elemental analysis. X-ray crystal structures of 1b, 3b, 4b, 5b, and 6b have also been determined, which confirm their molecular structures. Cyclic voltammetric experiments on the ferrocenyl derivatives 1b−6b reveal an essentially reversible oxidation peak. Further, all of these are electrochemically quite robust and do not decompose on oxidation.