Cockerton, Bruce; (1993) Ruthenium carbonyl complexes containing ligands derived from pyridine and pyridine-2-thione. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

This thesis describes the synthesis and characterisation of some ruthenium carbonyl complexes containing ligands derived from pyridine and pyridine-2-thione. These complexes have been characterised by infrared, 1H and 13C NMR and mass spectroscopy, elemental analysis and X-ray crystallography. Chapter One is an introduction to the coordination chemistry of pyridine and pyridine-2-thione and contains a brief survey of transition metal complexes containing these ligands. Chapter Two concerns the separation and structural characterisation of the two isomers of [Re2Ru2(μ4-S)(μ-C 5H4N)(μ-pyS)(CO)13]. This compound reacts with [Ru3(CO)12] to give [Re2Ru2(μ4-S)(μ-H)(μ-C 5H4N)(CO)14], the crystal structure of which was determined. The effect of altered conditions on the reaction between [Re 2(μ-pyS)2(CO)6] and [Ru3(CO) 12] was investigated. Chapters Three and Five concern the synthesis of high nuclearity clusters via thermolysis of [Ru3H(pyS)(CO) 9] and reaction of [Ru3(CO)12] with [Ru(pyS) 2(CO)2]. The 2D NMR spectrum of [Ru4(μ4-S)(μ-C 5H4N)2(CO)12] and the crystal structures of [Ru6(μ4-S)2(μ-C5H4N) 2(CO)18] and [Ru6(μ4-S)(μ-SH)(μ3-pyS)(CO) 17] are discussed. Chapter Four describes the reaction between [Ru 3(CO)12] and pyridine. At 120 °C, [Ru2(μ-C5H 4N)2(CO)6] is produced as head-to-head and head-to-tail isomers. The crystal structures of the 4-methylpyridine osmium analogues were determined. At 180 °C, [Ru2(μ-C5H4N)(μ-C 10H7N2)(CO)5] is produced, shown by X-ray diffraction to contain a bridging ortho-metallated bipy ligand formed by coupling of two 2-pyridyl ligands. A similar reaction with 4-methylpyridine gave an analogous compound as well as [Ru2Cl(μ-H)(μ-MeC 5H3N)2(Me2C10H6N 2)(CO)3]. At 180 °C, increased reaction times result in Ru-Ru bond cleavage, giving [RuCl2(CO)2(py) 2] and [RuCl2(CO)(py)3]. [Ru2(μ-C 5H4N)2(CO)6] was treated with 4-methylpyridine giving mono- or dinuclear compounds, depending on the isomer used. The crystal structure of [Ru2HCl(μ-MeC5H3N)2 (C10H8N2)(CO)3]. H 2O was determined. In summary, the pyridine-2-thionato ligand was found to coordinate in doubly- and triply-bridging modes, or to undergo S-C cleavage to give μ4-sulphido complexes containing 2-pyridyl ligands. Pyridine was found to react with [Ru3(CO)12] to give a range of products containing monodentate or ortho-metallated pyridyl ligands, as well as undergoing coupling reactions at ruthenium centres to give bipyridyl ligands.

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