Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

1λ5,3λ5-Diphospholium ions

One example each is given for the reaction of bromoacetylenes and ethynyl-phenyliodonium tosylates with bis(diphenyl phosphino)methane. The yellow crystalline 1:1-addition products are diphospholium salts. They readily and selectively hydrolyze to give 2-phosphinoylethenyl phosphonium salts.     

1,2λ5,5λ5-azadiphospholium structures

The reactions of bromophenylacetylene with the diphenylphosphino amines (Ph₂P)₂NH and (Ph₂P)₃N result in the 1,1,3,3,4-pentaphenyl-1,2,5-azadiphospholium bromide ( 5 ) and its 4-diphenylphosphino derivative ( 7 ). Their X-ray structure analyses show planar rings for the cations. The small endocyclic angle at the nitrogen ring member is associated with PN bonds that are longer than in the acyclic cation (Ph₃P)₂N⁺. The data fit to a negative linear relationship of PN bond lengths and PNP bond angles. © 1997 John Wiley & Sons, Inc.     

1, 2λ5-azaphosphinines and a new 1λ5, 3λ5-. Diphosphinine

The 1,2-azaphosphinine, 9 , and the 1,3-diphosphinine, 10 , can be isolated from a mixture resulting from the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and ethyl isothiocyanate. The reaction of 1 with phenyl isothiocyanate yields the 1,2-azaphosphinine, 16 . Mechanisms for the formation of the compounds 9 , 10 , and 16 are suggested. The properties, the NMR, mass, and IR spectra, and the molecular and crystal structures of 9 and 10 are described and discussed.