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Title: Organo-nitrogen compounds of cobalt
Author: Fisher, Keith John
ISNI:       0000 0004 2740 9009
Awarding Body: Queen Mary University of London
Current Institution: Queen Mary, University of London
Date of Award: 1968
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The reactions of cobalt halides with lithium dialkylamides have been investigated. The reaction with lithium diethylamide proved to be very unusual. This reaction was fully studied and the main products were shown to be lithium chloride, cobalt metal and bis(4-ethylimino-2-butene-2-ethylamino)Cob~lt(II). The latter product which was a volatile brown liquid was identified by its physical and . . chemical properties and the physical properties of derivatives prepared from the ligand after removal of the cobalt. Bis-(4-ethylimino-2-butene-2-ethylamino)cobalt(II) is a nitrogen analogue of the metal acetylacetonates and shows many similar properties. The ligand 4-ethylimino-2-ethylamino-2-butene • was shown, by the magnetic moment and electronic spectra of the tetrahedral cobalt compound, to produce a very high ligand field. A reaction mechanism has been proposed to explain the products 'of the reaction of cobalt chloride with lithium diethylamide. The reactions of other lithium dialkylamides with cobalt halides haye shown that dialkylamino compounds of cobalt(II) exist but are generally unstable thermally and very oxygen sensitive. The only stable (thermally) dialkylamino cobalt(II) compound prepared was bis-hexamethyldisilylamino cobalt(II). In solution this compound was shown· to be a linear two coordinate compound of cobalt(II). This unusual stereochemistry for cobalt(II) presents many theoretical problems before the magnetic and spectral properties ,are fully understood. It was found that the other dialkylamino cobalt(II) compounds produced were u!lstable.thermally decomposing above room temperature. The most stable compounds were formed when the dialkyl- group produced large steric hindrance. Two new alkolides were prepared from the dialkyamino cobalt(II) compounds. The magnetic and spectral properties of these compounds indicate that they are polymeric. possibly three coordinate compounds of cobalt.
Supervisor: Not available Sponsor: Draper's Company Research Studentship
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: cobalt halides ; lithium dialkylamides ; reaction mechanisms ; .