Coordination chemistry of crown thiothers

Liang, Weimin (1994) Coordination chemistry of crown thiothers. Masters thesis, Memorial University of Newfoundland.

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Abstract

This thesis describes the properties of thio-oxa crown ligands and their coordination chemistry. Chapter I briefly reviews the synthesis, conformation and coordination chemistry of crown thioethers. In Chapter II, synthesis and characterization of l-oxa-4,7-dithiacyclononane ([9]aneOS₂) and 1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane ([18]aneO₂S₄) are reported. Molecular mechanics calculations are reported on [9]aneOS₂ and the molecular structure of [18]aneO₂S₄ has been determined by X-ray methods. In Chapter III, synthesis and properties of [Pd([9]aneOS₂)Cl₂] and [Pt([9]aneOS₂)Cl₂] have been described. Variable-temperature ¹H and ¹³C NMR studies reveal the unusual stereochemical non-rigidity in [Pd([9]aneOS₂)Cl₂], and the mechanism has been proposed. In Chapter IV and V, the structures of [Cu([9]ane0S₂)₂][ClO₄]CH₃CN and [Cu([9]aneOS₂)Br]₂ are presented together with their electrochemical properties. The results indicate that ligand [9]aneOS₂ considerably stabilizes Cu(I) over Cu(II). The synthesis and structure of [Ag([18]aneO₂S₄)]ClO₄ are reported in Chapter VI.

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