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Title: Hydrido complexes of platinum metals
Author: Thomas, Kenneth
Awarding Body: University of London
Current Institution: Imperial College London
Date of Award: 1969
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The preparation of a series of salts of the hydridopentamminerhodium(III) cation is described and spectroscopic data for these compounds are presented. The aqueous equilibrium between the hydridopentammine and the hydridoaquotetramminerhodium(III) complexes is discussed in terms of the trans effect of the hydrido ligand. Olefins and fluoro-olefins are shown to 'insert' into the (Rh-H) bonds of both complexes to form σ-bonded alkyl and fluoroalkyl complexes all of which have been isolated as crystalline salts. These complexes show pentammine-aquotetrammine equilibria in the same way as do the parent hydrides. The replacement of ammonia in the hydridopentammine complex by a number of aliphatic amines leads to the formation of new hydrides, some of which have been isolated as crystalline salts. In these, the complexes are shown to have the trans configuration by their infrared spectra. The trans hydridoamminebisethylenediaminerhodium(III) complex has been studied in some detail and evidence for the existence of a cis-trans isomeric equilibrium, in aqueous solution, is presented. The efficiency of the zincamine couple as a source of hydride ion is compared with that of sodium borohydride. Two paramagnetic compounds have been isolated from the reaction of hydridoaquotetramminerhodium(III) sulphate with molecular oxygen. The complex cations are proposed as being binuclear in having two rhodium atoms linked by oxygen ligands.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available