Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.307370
Title: Ruthenium complexes as potential aqueous romp catalysts
Author: Bouic, Phillip J.
ISNI:       0000 0001 3472 0688
Awarding Body: Aston University
Current Institution: Aston University
Date of Award: 1996
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Abstract:
The research described herein relates to studies into the Aqueous Ring-Opening Metathesis Polymerisation (ROMP) of bicyclic monomers using ruthenium complex catalysts. Two monomers were synthesised for the purpose of these studies, namely exo, exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (7-oxanorbornenedicarboxylic acid) and exo, exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (norbornene dicarboxylic acid). A number of ruthenium complexes were synthesised, amongst them a novel complex containing the water soluble phosphine ligand trist(hydroxymethyl)phosphine P(CH2OH)3. Its synthesis and characterisation are described and its physical properties compared and contrasted to analogous compounds of platinum and palladium. Its peculiar properties are ascribed to a trans-placement of the phosphine ligands. Dilatometry was investigated as a technique for the acquisition of kinetic data from aqueous metathesis reactions. For the attempted polymerisation of 7-oxanorbonenedicarboxylic acid the results are explained in terms of a reverse Diels-Alder reaction of the monomer. The reaction between Ru(CO)Cl2(H2O) and 7-oxanorbonenedicarboxylic acid was monitored using UV/Vis spectrometry and kinetic data retrieved. The data are explained in terms of a two stage reaction consisting of consecutive first order processes. The reaction between 7-oxanorbornenedicarboxylic acid and Ru(CO)Cl2(H2O) or Ru(P(CH2OH)3)3Cl2 was found to produce fumaric acid as one of the major products. This reaction is previously unreported in the literature and a mechanism is proposed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Phd
EThOS ID: uk.bl.ethos.307370  DOI: Not available
Keywords: Chemical Engineering ; Applied Chemistry ; Chemical Engineering Chemistry, Organic
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