A matrix isolation study of main group and transition metal atom cryochemistry
The majority of the work described in this thesis is concerned with the isolation of transition metal and main group atoms in dilute reactive ligand matrices. The previously uncharacterised matrix isolated species were characterised using IR, UV-Vis-NIR and XAFS spectroscopic techniques. Various metal atom sources were investigated for the production and subsequent isolation of atomic species in both inert and reactive ligand matrices. Some 4d and 5d transition metals atoms were produced from a hollow cathode sputtering source (laser ablation was also employed as an atom source in some of the work) and isolated in argon matrices. The isolation of both platinum and palladium atoms in chlorine containing argon matrices has been shown to result in the formation of linear PtCl₂ and PdCl₂ molecules. The isolation of gold atoms has led to the formation of a monomeric chloride, suspected to be either AuCl3 or AuCI₂.The structure of the silver chloride remains undetennined. The pseudo-gas phase structure of these monomeric species is presented for the first time. In addition to this work tellurium atoms have been generated from the photodecomposition of matrix isolated H₂Te. The use of CO containing matrices has led to the isolation and characterisation of carbonyl telluride, OCTe, the structure and composition of which (either in the solid or gas phase) is presented for the first time. In complementary work, an investigation into carbonyl complexes formed on isolation of some 3d transition metal bromides in dilute carbon monoxide / argon matrices is also presented, together with their photochemistry in neat CO matrices.