Chalcogen-carbon-nitrogen rings, chains and coordination compounds
Abstract
This thesis describes the general area of chalcogen-carbon-nitrogen compounds. The first part of Chapter 1 provides an introduction to chalcogen donor ligands. The second part of Chapter 1 considers the literature reports on polythiocyanogen and related compounds. Chapter 2 details the synthesis and characterisation of a series of homoleptic, heteroleptic and dimeric cyanodithioimidocarbonate complexes prepared by the reaction of dipotassium cyanodithioimidocarbonate with the appropriate transition metal starting materials. Chapter 3 describes the synthesis and characterisation of the cyanodiselenoimidocarbonate complexes. In Chapter 4 we report a convenient one pot synthesis for the preparation of triselenocarbonate complexes. We have prepared mononuclear, binuclear and tetranuclear complexes of this ligand including the first crystallographically characterised example of a triselenocarbonate complex. In Chapter 5 we have prepared a series of 1,2,4- thiadiazole compounds for spectroscopic comparison with (SCN)ₓ. We also report the synthesis of model compounds for (SCN)ₓ composed of two 1,2,4- dithiazole rings linked by a sulfur bridge. Chapter 6 describes the synthesis and full characterisation of polythiocyanogen (SCN)ₓ the related small molecules Sₓ(CN)₂ (x = 1, 2, 3) and the selenium analogues. Using the data obtained and comparison with the 1,2,4-thiadiazole model compounds reported in Chapter 5 as well as literature compounds we have determined the structure of polythiocyanogen.
Type
Thesis, PhD Doctor of Philosopy
Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.