REACTIONS OF FERROCENOL AND 1,1'-FERROCEN DIOL WITH CYCLOTRIPHOSPHAZENES, P3N3F6 AND P3N3CL6

The hexahalogeno-cyclotriphosphazenes, P3N3X6 (X = F (1a), Cl (1b)), r eact with ferrocenol (FcOH) in a molar ratio 1:1 to give the ferroceno xy derivatives, FcO[P3N3X5] (X = F (3a), Cl (3b)), in an analogous man ner the tetrameric ring P4N4Cl8 (2b) is converted to FcO[P4N4Cl7] (4b) .(1)) With 1,1'-ferrocenediol, (fc(OH)(2)), the cyclotriphosphazenes r eact in a molar ratio 1.1 to produce fcO(2)[P3N3X4] (X = F (5a), Cl (5 b)). According to the x-ray structure analysis, the 1,1'-ferrocenediol ato 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 spiro cyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All n ew products have been characterized on the basis of their H-1, C-13 an d 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.