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Mooney, Eric Francis (1960) Chemistry related to borazole. Doctoral thesis, Northern Polytechnic.
The nature of the reaction products of primary amines with boron trihalides has been investigated. Primary aromatic amines afford π-complexes of the form. HX.N-H...B-X-X, and evidence for this structure is revealed by a study of chemical reactions, infra-red spectroscopy and nuclear magnetic resonance spectroscopy. Primary aliphatic amines with boron trichloride and with boron tribromide afford the alkylammonium tetrahalogenborates, whereas with boron trifluoride the normal 1:1 co-ordination complexes are obtained.
Decomposition of the π-complexes and the tetrachloroborates, affords the substituted B-trichloroborazoles, certain properties of which are discussed. The hydrolysis, alkylation, aminolysis, pyrolysis, and formation of co-ordination complexes are considered.
A critical survey of the methods of preparing substituted boron dichlorides is presented, and the formation of phenylboron dichloride from totraphenyl tin is described. The formation of B-alkyl and aryl borazoles is discussed, and chemical and spectroscopic evidence of steric inhibition to ring formation is presented.
The infra-red spectra of substituted borazoles is considered in detail, and assignments given for BN, B—Cl stretching and B—N out of plane deformational modes. Some consideration is given to the CH out of plane deformation modes of B-phenyl borazoles and boroxoles, and evidence is presented to show that extended conjugation occurs in these systems.
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