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Title: Studies on thioether macrocyclic complexes
Author: Sullivan, Martin J.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1993
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An introduction to macrocyclic chemistry, with particular emphasis on [9]aneS3 (1,4,7 - trithiacyclononane) and thioether macrocyclic transition metal complexes of groups VIII and IX is presented. The reaction of [RuC12(PPh3)([9]aneS3)] with TIPF6 in CH2C12 at 298K results in the formation of a mixture of complexes, [Ru(PPh3)([9]aneS3)(μ-C1)]2(PF6)2 and [Ru(PPh3)([9]aneS3)(μ-C1)2T1]2(PF6)2, which have been both characterised by X-ray crystallography. The synthesis of pure [Ru(PPh3)([9]aneS3)(μ-C1)]2(PF6)2 and [Ru(PPh3)([9]aneS3)(μ-C1)2T1]2(PF6)2 is described. Both complexes react with acetonitrile to form [Ru(NCCH3)C1(PPh3)([9]aneS3)](PF6). The reaction of [RuC12(PPh3)([9]aneS3)] with TIPF6 in CH3NO2 leads to the isolation of the complexes [Ru(NCCH2CH3)C1(PPh3)([9]aneS3)](PF6) and [RuC1(NC3H3O)(PPh3)([9]aneS3)](PF6). The X-Ray structure of the latter complex is described. The complexes form by reacting with two impurities (ethyl cyanide and isoxazole) present in CH3NO2. The addition of TIPF6 TO [RuC12(PPh3)([9]aneS3)] in CH3NO2 and THT forms the complex [Ru(C1(PPh3)(THT)([9]aneS3)](PF6). The single crystal X-ray structure of this complex reveals the presence of a 1:1 mixture of the THT complex, [Ru(C1(PPh3)(THT)([9]aneS3)](PF6) and a THT-S-oxide complex, [Ru(C1(PPh3)(THT-S-oxide)([9]aneS3)](PF6). The THT-S-oxide complex forms during crystallisation.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available