Leach, John Brian (1968) Studies on the cyclotetrazenoborane ring and related systems. (PhD thesis), Kingston College of Technology.Full text not available from this archive.
Work done previously on cyclotetrazenoboranes and other boron-nitrogen ring systems, excluding borazines, has been comprehensively reviewed. The frequencies of the B-H stretching frequencies in Me[sub]2N[sub]4BH and Ph[sub]2N[sub]4BH have been studied in a range of solvents, and are shown to increase with increasing polarity of the solvent. No correlation is observed with the dielectric relationship ([epsilon]-1)/(2[epsilon]+1) and non-linear relative shift (B.H.W.) plots are obtained against N-H, C=O, P-H, and transition metal hydride M-H vibrations. The results. suggest that solvent interactions occur with parts of the molecules remote from the B-H bond, and are unlikely to be due mainly to dielectric effects. Two routes for the preparation of B-substituted cyclotetrazenoboranes have been developed. The action of Grignard reagents on derivatives of the type R[sub]2N[sub]4BH produces compounds R[sub]2N[sub]4BR' in high yield, through the intermediate formation of magnesium containing complexes. Thermal degradation of a diorganoboron azide in the presence of an organic azide also produces boron-substitutedcyclotetrazenoboranes. The preparation of B-halogeno substituted cyclotetrazenoboranes has been achieved by two routes. Direct reaction of a derivative of the type R[sub]2N[sub]4BH with N-bromosuccinimide'has led to isolation of the very readily hydrolysable compound R[sub]2N[sub]4BBr. Dehydrohalogenation of a primary amine -BC1[sub]3 adduct in the presence of triethylamine has also led to the isolation of a B-chloro cyclotetrazenoborane derivative. Attempts to prepare unsymmetrically N-substituted cyclotetrazenoboranes by the reaction of a primary amine-borane (RNH[sub]2BH[sub]3) with an organic azide (R'N[sub]3) have led to the isolation of mixtures of cyclotetrazenoborane derivatives RRN[sub]4BH, RR'N[sub]4BH and R'R'N[sub]4BH. Throughout the work the U.V., I.R. and N.M.R. spectra of the compounds have been studied. A detailed mass-spectrometric study of both B- and N-substituted clotetrazenoboranes has been made and a generalised fragmentation pattern has been derived. The use of computer techniques was also established to aid the handling and interpretation of the mass spectral data.
|Item Type:||Thesis (PhD)|
|Additional Information:||In collaboration with Royal Holloway College.|
|Physical Location:||This item is held in stock at Kingston University Library.|
|Depositing User:||Automatic Import Agent|
|Date Deposited:||09 Sep 2011 21:38|
|Last Modified:||30 May 2014 13:48|
Actions (Repository Editors)
|Item Control Page|