Macromolecular complexes of gold(I) and silver(I)

This thesis describes the synthesis and characterisation of gold(I) and silver(I) coordination polymers and macromolecules. The complexes [{lcub}Ph ₂P(CH₂)nPPh₂-AuNC₅H₄-C ₅H₄N-Au-{rcub}_x]2x+ (CF₃CO ₂−)_2x (n = 1–6) were prepared by the reaction of 4,4′-dipyridyl with the precursor complexes [(CH₂)_n(Ph₂PAuO₂CCF ₃)₂] (n = 1–6). The complexes are suggested to exist in solution as an equilibrium mixture of linear oligomers and cyclic complexes. When n = 1, 3 or 5 the complexes were shown to exist as rings. Crystal structures of some complexes of the form [CF₃CO₂-Au-Ph₂P-R-PPh ₂Au-O₂CCF₃] are reported, and intermolecular aurophilic interactions link the complexes to form polymeric structures.; The complexes [{lcub}(P4VP)_10eq-Au-Ph₂P(CH₂) _nPPh₂-Au-)_x]2x+ (CF₃CO ₂−)_2x, (n = 1–6) were prepared from the reaction of [(CH₂)_n(Ph₂PAuO ₂CCF₃)₂] (n = 1–6) with poly(4-vinylpyridine). The features of the polymer backbones were studied by powder X-ray diffraction, and crystal structures were obtained for model compounds.; The gold(I) complexes of empirical formula Au{lcub}Ph₂P(CH ₂)_nPPh₂{rcub}+ crystallise as rings [Au₂(Ph₂P(CH₂)_nPPh₂) ₂]2+ when n = 3 or 5 but as a polymer [{lcub}Au(Ph₂P(CH ₂)_nPPh₂)₂{rcub}_x]x+ when n = 4. In favourable cases, the ring complexes can be connected through three-centred aurophilic interactions by addition of [Au(CN)₂] −, and crystals contain pentagold units when n = 3 or polymeric pleated chains when n = 5.; The first three-coordinate gold(I) polymers containing only phosphorus-donor ligands are reported. The gold(I)-diphosphine complexes adopt polymeric 1-D “chain-link fence” or 2-D “chickenwire” structures and have been synthesised by simple self-assembly.; Interesting molecular architectures are obtained by self-assembly from silver(I) trifluoroacetate with a combination of the diphosphine ligands and trans-1,2-bis(4-pyridyl)ethylene (bipyen). The complexes crystallise in the form of macrocyclic rings [Ag₄(O₂CCF₃) ₄{lcub}μ-Ph₂P(CH₂)_nPPh₂) ₂(μ-bipyen)₂] when n = 1 or 5, but as a one-dimensional polymer [(Ag₂(O₂CCF₃)₂{lcub}μ-Ph ₂P(CH₂)_nPPh₂{rcub}(μ-bipyen){rcub}_x] when n = 6. The complex [{lcub}Ag{lcub}μ-Ph₂P(CH₂)₃PPh ₂{rcub}(μ-bipyen){rcub}_x] (O₂CCF₃)_x has a three-dimensional network structure.; Binuclear cyclic silver(I) complexes of the form [{lcub}Ag-Ph₂P-(CH ₂)_n-PPh₂₋)₂] (CF ₃CO₂)₂ (n = 1–6) were prepared. Also, the synthesis and crystal structure of polymeric silver(I)-diphosphine complexes is reported. These complexes have varying coordination number and stereochemistry (AgP, AgP₂, AgP₃) around the silver(I) centre, and they adopt a linear polymeric structure, or a two-dimensional puckered sheet structure. The use of the “node + spacer” co...