On the synthesis of new ligands for complexation to group 8 to 11 metal ions

  • David Davies

Student thesis: Master of Philosophy


The synthesis of 3,6,9-trithia-15-azabicyclo[9.3.1]pentadeca-1(15)-11,13-triene, “S3N”, 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 (“A3-reactions”), 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 Award1 Aug 2018
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorPeter Quayle (Supervisor) & Stephen Yeates (Supervisor)

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