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Title: Studies on some unsaturated organonitrogen metal systems
Author: El Erian, M. A. I.
ISNI:       0000 0001 3442 7182
Awarding Body: Durham University
Current Institution: Durham University
Date of Award: 1983
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This thesis describes studies on the coordination chemistry and reactions with metal halides of some unsaturated organonitrogen compounds. The systems studied included various ketimines, R(^1)R(^2) C = NH, and derivatives thereof, R(^1)R(^2) C = NH, MX(_n) or R(^1)R(^2) C = NMX(_n-1) containing antimony or tin atoms attached to the imino-nitrogen atoms. Aspects of the coordination chemistry of acrylonitrile CH(_2) : CHC : N and its methyl derivatives, CH(_2) : CMe C : N and MeCH : CH C : N have also been studied as well as their reactions with ether/SnCℓ(_2)/HCℓ systems. The main feature studied in the imine work was the tendency of compounds (4-XC(_6)H(_4))(_2)C = NSbCℓ(_n) (X = H or Me, n = 2 or 4) to undergo cyclometallation reaction forming a new type of antimony ring compound; 2 - SbCℓ(_n) – 4 – XC(_6)H(_3)C(4 – XC(_6)H(_4)) – NH. Related cyclometallation reactions are surveyed in chapter 1. During attempts to prepare other diarylketimino antimony tetrachlorides such as o-tolyl, ph C = NSbCℓ(_4); m-tolyl, ph C = NSbCℓ(_4) and (4 – FC(_6)H(_4))(_2) C = NSbCℓ(_4), no analogous cyclometallated products were obtained. Instead two different products were isolated: Aryℓ(_2)CNH(^+)(_2)SbCℓ(^-)(_4) and Aryℓ(_2)CNH(^+)(_2)SbCℓ(^-)(_6). Attempts to prepare t-butyl derivatives of general formula Ar, Bu(^t) C = NSbCℓ(_4) (Ar = o-tolyl, p-tolyl; m-tolyl) afforded arylnitrile, HCℓ and SbCℓ(_3), probably by elimination of Me(_2)C = CH(_2). Chloroform solutions of diphenylketimine and antimony penta- or tri- chloride deposited ph(_2)CNH(^+)(_2) SbCℓ(^-)(_6) or (ph(_2)CNH(^+)(_2))(_2) SbCℓ(_5)(^2-) respectively. In the nitrile work, using ether/SnCℓ(_2)/HCℓ systems which contain R(_2)OH(^+). SnCℓ(_3)(^-) and (R(_2)O(^+)H)(_2) ∙ SnCℓ(_4)(^2-), addition to the C = C bond of the acrylonitrile yielded Cℓ(_3)Sn.CK(_2).CH(_2).CN. Methacrylonitrile and crotononitrile gave more complicated reactions with ether/SnCℓ(_2)/HCℓ systems, apparently undergoing dimerization to form amidinium cations containing C = N - CR = NH(_2)(^+) units. Finally, several complexes were isolated from reactions between acrylonitrile or its methyl derivatives and the metal chlorides TiCℓ(_4), SnCℓ(_4), SbCℓ(_5), BCℓ(_3) CoCℓ(_2), ZnCℓ(_2), TiBr(_4), TaCℓ(_5), NiCℓ(_2)/2SbCℓ(_5) and NiCℓ(_2)/2ZnCℓ(_2). Spectroscopic and conductivity studies of these complexes were carried out, and used to deduce their probable structures.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Organic chemistry