Chemistry of diphenyltetrafluorophosphazene: Reactions with dilithiated diols

Abstract

Reaction of gem-diphenyltetrafluorophosphazene, [1,1-(C6H5)2]P3N3F4 (1) with LiO(CH2)3OLi resulted in the formation of four products, spiro-{3,3-[O(CH2)3O]}[1,1-(C6H5)2]P3N3F2 (2), ansa-{3,5-[O(CH2)3O]}[1,1-(C6H5)2P3N3F2] (3), bridged-[1,1-(C6H5)2N3P3F3][O(CH2)3O][1,1-(C6H5)2N3P3F3] (4) and dangling-[HO(CH2)3O][1,1-(C6H5)2P3N3F3] (5) derivatives of 1, among which compound 5 was found to be the major product. Reaction of 1 with the dilithiated ferrocene derived diol, FcCH2P(S)(CH2OLi)2 resulted in the formation of two isomers of ansa substituted fluorophosphazenes namely endo-[1,1-(C6H5)2]{3,5-[FcCH2P(S)(CH2O)2]}P3N3F2 (6) and exo-[1,1-(C6H5)2]{3,5-[FcCH2P(S)(CH2O)2]}P3N3F2 (7). These were formed along with the spiro isomer [1,1-(C6H5)2]{3,3-[FcCH2P(S)(CH2O)2]}P3N3F2 (8) the dangling derivative [1,1-(C6H5)2P3N3F3][OCH2(FcCH2)P(S)CH2OH] (9) and the bridged compound [1,1-(C6H5)2P3N3F3][OCH2(FcCH2)P(S)CH2O][1,1-(C6H5)2P3N3F3] (10). All compounds were separated by column chromatography and characterized by 1H, 31P{1H}, 19F NMR, mass spectra and elemental analysis. The spirocyclic compound 8 was also characterized by X-ray crystallography. © 2006 Elsevier B.V. All rights reserved.