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Title: Studies on macrocyclic complexes
Author: Radek, Christian
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1995
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The work described in this thesis deals with the co-ordination chemistry of the macrocyclic ligands [9]aneS3 (1,4,7-trithiacyclononane), [12]aneS4 (1,4,7,10-tetrathiacyclododecane), [14]aneS4 (1,5,8,12-tetrathiacyclotetradecane), [16]aneS4 (1,5,9,13-tetrathiahexadecane), [15]aneS5 (1,4,7,10,13-pentathiacyclopentadecane), [18]aneS6 (1,4,7,10,13,16-hexathiacyclooctadecane), [24]aneS8 (1,4,7,10,13,16,19,22-octathiacyclotetraeicosane), [15]aneS2O3 (1,4,7-trioxa-10,13-dithiacyclopentadecane), [18]aneS2O4 (1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane), benzo[18]aneS2O4 (4,7,10,13-tetraoxa-1,16-dithial[16]-o-cyclophane), [21]aneS2O5 (1,4,7,10,13-pentaoxa-16,19-dithiacycloheneicosane), [18]aneS3O3 (1,4,7-trioxa-10,13,16-trithiacyclooctadecane) and [20]ane3O3 (1,4,7-trioxa-10,14,18-trithiacycloeicosane). The synthesis of [18]aneS2O4, [18]aneS3O3 benzo[18]aneS2O4 and [20]aneS3O3, the single crystal X-ray structures of [15]aneS2O3, [18]aneS2O4 and ([21]aneS2O5)1.1/2H2O, and molecular mechanics calculations on [18]aneS2O4 are described. ([21]aneS2O5). 11/2H2O is the first example of a neutral molecule binding to a mixed O/S-donor ionophore with H-bonding to the hard polyether binding site. Studies of Ru(II) and Pd(II) complexes with these ligands were initiate in order to establish the fundamental co-ordination chemistry between mixed O/S-donor ionophores and to establish the potential of these complexes to be used in the development of a metal mixed O/S-donor macrocyclic host guest chemistry. [RuC12PPh3([15]aneS2O3)] and [RuCI(PPh3)([15]aneS2O3)2]PF6 were prepared by the reaction of [15]aneS2O3 with [RuCI2(PPh3)3]. The role of [RuCI2PPh3([15]aneS2O3)] as a potential intermediate in the formation of the two isomers of [RuCI(PPh3)([15]aneS2O3)2]PF6 is discussed. The reaction of [18]ane2O4 with [RuC12(PPh3)3] afforded [RuCI(PPh3)([18]aneS2O4)2]PF6. [Ru([18]aneS2O4)3](PF6)2 was prepared by the reaction of [18]aneS2O4 and 'RuCI3.xH2O' in the presence of K2(C2O4) as a reducing agent. Reactions of [18]aneS2O4 with [Ru2CI46-C6H6)2] and [RuCI(PPh3)25-C5H5)] afforded the organometallic species [RuCI(η6-C6H6)([18]aneS2O4)]PF6, [RuCI(η6-C6H6)([18]aneS2O4)]BPh4 and [Ru(η5-C5H5)(PPh3)([18]aneS2O4)]PF6. The single crystal X-ray structures of all compounds prepared are described. In all cases the macrocyclic ligands co-ordinate to the RU(II) ion in an exo bidentate manner.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available