Tools
Tools
Twaits, R. (1962) Some complexes involving organo-phosphorus oxygen ligands. Doctoral thesis, Northern Polytechnic.
Forty two metal and non-metal halide complexes of triphenyl phosphine oxide were prepared and their infrared spectra recorded. This large number of complexes was prepared to show the wide applicability of this ligand, and to determine whether the shift in the phosphoryl frequency in the infrared spectra, resulting from complex formation, showed any relation to the Lewis acid strength of the acceptor. Only for the first series transition metal halides did the variation in shift follow with any accuracy the variation in Lewis acid strength. The reactions of substituted chlorosilanes and of B-chloroborazoles with compounds containing a phosphoryl bond were studied, with special reference to the nature of the products. In these systems the formation of, M-O-M1, mixed anhydrides was shown, the reaction probably starting with an initial coordination of silicon or boron to the phosphoryl oxygen atom. Diethyl alkanephosphonates react with alkyl or aryl chlorosilanes to give ethyl chloride and mixed polyanhydrides. The nature of the product can be variation of the substituents on varied considerably by the phosphorus or silicon atoms Dialkyl hydrogen phosphites or diethyl alkanephosphonates react with B-trichloroborazole or with N-alkyl or N-aryl substituted B-trichloroborazoles to give alkyl chloride and a polymeric solid containing - links. With B-trichloroborazole or N-triphenyl-B-trichloroborazole an intermolecular reaction is shorwn to occur giving a cross-linked polymer. The pyrolysis of B-trichloroborazole gave hydrogen chloride and a polymer composed of a network of borazole rings. Alkyl phosphorochloridates with B-trichloroborazole gave ethyl chloride, hydrogen chloride and hard brittle polymers containing links and possibly —P—N links. The physical properties of the polymers obtained varied greatly but all were hydrolysed relatively easily
 |
View Item |