Reactions of ferrocenol and 1,1'-ferrocendiol with cyclotriphosphazenes, P3N3F6 and P3N3Cl6

The hexahalogeno-cyclotriphosphazenes, P3N3X6 (X = F (1a), Cl (1b)), react with ferrocenol (FcOH) in a molar ratio 1:1 to give the ferrocenoxy derivatives, FcO[P3N3X5] (X = F (3a), Cl (3b)), in an analogous manner the tetrameric ring P4N4Cl8 (2b) is converted to FcO[P4N4Cl7] (4b).(1)) With 1,1'-ferrocenediol, (fc(OH)(2)), the cyclotriphosphazenes react in a molar ratio 1.1 to produce fcO(2)[P3N3X4] (X = F (5a), Cl (5b)). According to the x-ray structure analysis, the 1,1'-ferrocenediolato group in 5a, b is bound to two different phosphorus atoms. On the contrary, the 1,1'-ferrocenedithiolato- and 1,1'-ferrocenediselenolato units in fcS(2)[P3N3X5] (X = F (6a), Cl (6b)) and fcSe(2)[P3N3X5] (X = F (7a), Cl (7b)) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their H-1, C-13 and P-31 NMR as well as EI mass spectra. The molecular structures of 5 a, b and 6a have been determined by x-ray structure analyses.