Giorgi, Romano Viviano; (2000) Synthesis and reactions of ruthenium complexes with tris (2-pyridyl) methanol and related ligands. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

This thesis describes the synthesis and reactions of a variety of (η⁶-arene)ruthenium(II) complexes with tris(2-pyridyl)methanol and related ligands. By way of an introduction to this chemistry, Chapter 1 reviews the most relevant of earlier studies, mainly concerning i) tris(2-pyridyl) compounds and derived metal complexes, and ii) (η⁶-arene)ruthenium(II) complexes and their reactions with nucleophiles. Chapter 2 describes how modifications of literature procedures led to the preparations of methyl-substituted analogs of tris(2-pyridyl)methanol, and their chloromethane, ethoxymethane and methane derivatives. The crystal structure of (3-Methyl-2-pyridyl)(5-methyl-2-pyridyl)(2-pyridyl)methanol is described. Chapter 3 reports the reactions of tris(2-pyridyl)methanol and methyl- substituted analogs with [η⁶-arene)RuCl₂]₂ dimers (arene = benzene, para-cymene). Mono and dicationic [(η⁶-arene)Ru(tris(pyridyl)methanol)] complexes were synthesised depending on whether or not the tripodal ligand had become deprotonated, however in all cases the ligand adopted the tridentate N,N',O-coordination mode. In addition, two heterometallic complexes of tris(2- pyridyl)methanol were prepared. The crystal structures of the compounds [η⁶- C₆H₆)Ru{(C₅H₄N)₃CO}]PF₆, [{(η⁶-C₆H₆)Ru{(C₅H₄N)₃CO}}₂Ag][PF₆]₃ and [(η⁶-C₆H₆)Ru{(6-MeC₅H₃N)(C₅H₄N)₂CO}]PF₆ are presented. Chapter 4 presents the syntheses of (η⁶-arene)Ru(II) complexes of the chloromethane, ethoxymethane and methane derivatives of tris(2-pyridyl)methanol and its closely related analogs. Mono and dicationic complexes were prepared depending on whether a bidentate or tridentate coordination mode had been adopted by the tripodal ligand. The compound [η⁶-MeC₆H₄Pr)Ru{(C₅H₄N)₃CH}][PF₆]₂ was crystallographically characterised. Chapter 5 describes the reactions of dicationic (η⁶-arene)Ru(II) complexes, containing either tris(2-pyridyl)ethoxymethane or tris(2-pyridyl)methane as ancillary ligands, with nucleophiles. In all cases monocationic (η⁵-cyclohexadienyl)Ru(II) products were exclusively formed. In some cases, depending upon the reaction conditions employed, either of two isomeric forms of a given cyclohexadienyl product could be obtained - a kinetic or a thermodynamic isomer. The crystal structures of the compounds [(η⁵-C₆H₇)Ru(PMe₂Ph){(C₅H₄N)₃COEt}]PF₆ and [(η⁵-C₆H₆CN)Ru(PMe₂Ph)-{(C₅H₄N)₃COEt}]PF₆ are described.

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