The synthesis of 3,6,9-trithia-15-azabicyclo[9.3.1]pentadeca-1(15)-11,13-triene, âS3Nâ, 15 and its complexation with Au(I), Ru(II) and Ag(I) is described. The single crystal X-ray structure of the Ru(II) complex Ru(S3N)(PPh3)Cl2, 41 has been determined and the solid-state structure has been compared to solution-state structures using DOSY-NMR techniques. The catalytic activity of these complexes in multicomponent, Aldehyde-Alkyne-Amine coupling reactions (âA3-reactionsâ), leading to propargyl amines, is also described. Whereas the Au(I) and Au(I) complexes derived from 3,6,9-trithia-15-azabicyclo[9.3.1]pentadeca-1(15),11,13-triene, 15 are catalytically active in these reactions the analogous Ru(II) and Rh(III) complexes appear to be devoid of catalytic activity. The iridium-catalysed borylation of 3,6,9-trithia-15-azabicyclo[9.3.1]pentadeca-1(15),11,13-triene, 15 and related compounds has also been investigated. These borylation reactions are very sensitive to substituent effects where, for example, borylation of lutidine-N-oxide, 50 affords the expected borylated product 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 1-oxide 51 together with 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine, 49 , the result of N-deoxygenation.
Date of Award | 1 Aug 2018 |
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Original language | English |
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Awarding Institution | - The University of Manchester
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Supervisor | Peter Quayle (Supervisor) & Stephen Yeates (Supervisor) |
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On the synthesis of new ligands for complexation to group 8 to 11 metal ions
Davies, D. (Author). 1 Aug 2018
Student thesis: Master of Philosophy