Pyridine N-oxides as Versatile Ligands for Silver(I)
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
Chapter 1 gives a brief introduction to metallosupramolecular chemistry, silver(I) chemistry and the synthesis and coordination chemistry of pyridine mono-, di- and tri-N-oxides. Chapter 2 describes the syntheses of 17 [16 known and 1 new] pyridine N-oxides using either mCPBA or 50% H₂O₂ as the oxidising agent. It also describes 33 new X-ray crystal structures, of which 23 are silver(I) complexes and the remaining are molecular species, protonated ligands and unreported ligand crystal structures. The N-O group is shown to coordinate with up to three silver atoms with dimensionalities ranging from 0 to 2.
Chapter 3 describes the syntheses of 21 [16 known and 5 new] bipyridine N,N′-dioxides. This chapter also contains 27 new crystal structures, with 23 being silver(I) complexes, 1 molecular species and three unreported ligand crystal structures. The N,N′-dioxide ligands adopted upto µ₆-O,O,O,O′,O′,O′ denticity with polymer dimensionality varying from 0 to 2.
Chapter 4 involves the syntheses of 4 N,N′,N′′-trioxides and 7 new silver(I) complexes with 2,6′:2′,6′′-terpyridine N,N′,N′′-trioxide and 2 ligand crystal structures. This ligand adopted up to µ₆-O,O,O′,O′,O′′,O′′ with network dimensionality ranging from 0 to 3.
Chapter 5 summarises the results with final conclusions and future prospects.
Chapter 6 details the synthetic procedures for the ligands and their silver(I) complexes. All the N-oxide ligands were characterised by melting point, ¹H NMR, ¹³C NMR, IR, ESI-MS and elemental analysis, while the silver(I) complexes were characterised by melting point, elemental analysis, IR and ESI-MS.