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The ligand 1-oxa-4,8-diazacyclodecane ([10]aneN2O) was synthesised, along with the [special characters omitted] complexes. Bis-ligand complexes are formed with facial coordination of the ligand to the transition metals, with two nitrogen donors from each ligand forming an equatorial plane around the metal ion. The crystal structure of [special characters omitted] was determined, as is described. The copper(II), nickel(II) and palladium(II) complexes have been characterised by FAB MS, electronic spectroscopy, elemental analysis and where possible by NMR and EPR spectroscopy. The nickel(II) and copper(II) complexes have distorted octahedral geometries, while the palladium(II) complex has square planar geometry with no observable axial interaction from the ether donors. The redox characteristics of the complexes formed have been determined, and are described within. The synthesis of the novel tricyclic ligand, 7,16-dioxa-1,4,10,13- tetraazatricyclo[11.5.3.3]octadecane [special characters omitted] is described. The [special characters omitted] conplex has been synthesised and characterised. The complex gives an unusually stable [special characters omitted] complex compared to complexes where a similar donor set is present A novel template synthesis was utilised to synthesise the bicyclic ligand 1,2-bis(1-oxa-5,8-diazacyclodecanyl)ethane ([special characters omitted] earmuff). This synthesis involved reaction of secondary amines which are coordinated to a copper(II) ion, a method which to our knowledge has not been used before in the synthesis of macrocyclic ligands. The copper(II) complex synthesised during this reaction has been characterised, and the redox reactions have been examined. The synthesis of 17-oxa-1,4,8,11-tetraazabicyclo[6.6.5]tetradecane (bicyclo[12-12] [special characters omitted]) is reported. Copper(II) and nickeI(II) complexes of this ligand have been synthesised and characterised. The chloride ion substitution reaction of [Ni(bicyclo[12-12] [special characters omitted] has been examined. The reaction was found to have an inverse dependence on the acid concentration. A tentative mechanism has been proposed to explain the origin of the acid dependence. The equilibrium constant for this reaction, determined by visible spectrophotometry, was found to be [special characters omitted]. The cobalt(III) bis-ligand complex of the previously synthesised ligand, 8-aza-1,5- dithiacyclodecane ([special characters omitted]) was synthesised. Under the conditions used, two isomers were formed - a facially coordinate bis-ligand complex where the equatorial plane is defined by two sulfur and two nitrogen donors, and a more symmetrical isomer where all four sulfur donors are coordinated equatorially. Isomerisation of the unsymmetrical isomer to the symmetrical isomer occurs in solution. The [special characters omitted] complexes of the ligand 1,2-bis(8-aza-1,5-dithiacycIodecanyI)ethane ([special characters omitted] earmuff) were synthesised and characterised. The ligand coordinates to [special characters omitted] in a pseudo five coordinate manner as determined by NMR spectroscopy. A solvent molecule or anion is likely to be coordinated to the [special characters omitted] centre in order to achieve distorted octahedral coordination. The complexes were characterised by FAB MS, electronic spectroscopy, elemental analysis and ESR spectroscopy. Although the [special characters omitted] centre was found to be in the low spin state, the electron transfer self exchange rate constant could not be determined by NMR spectroscopy. The [special characters omitted] complex of this ligand was also synthesised and found to coordinate in a five coordinate manner. Evidence of axial coordination of nitrogen in the palladium complex was observed in the electronic spectrum, therefore a distorted square pyramidal geometry has been proposed for the [[special characters omitted] earmuff)] complex. The potentially binuclear ligand, 1,9-bis(4-aza-1,8-dithiacyclononane)-4,7-diaza-2,8-dionenonane, was synthesised and characterised. Preliminary results indicate that reaction with two equivalents of nickel(II) produced a binuclear complex.
Presented in this thesis is the synthesis and characterization of two new classes of mixed donor ligands, as well as several copper(II) and nickel(II) complexes. Chapter II details the synthesis and characterization of thiosemicarbazates, which are tridentate ONS (oxygen, nitrogen, sulfur) donor compounds. In Chapter III complexes of these thiosemicarbazate ligands with nickel(II) and copper(II) are prepared and characterized. Chapter IV discusses the synthesis and characterization of several different amidothiocrown and amidoazathiocrown ethers.
Reliable, simple, substitution and one-pot radical reactions have enabled the preparation of a wide variety of novel bidentate and potentially tridentate ligands bearing combinations of P/S/Se/0 and N donor atoms. The coordination chemistry of these ligands is investigated, and subsequent complexes have been tested for their potential catalytic activity in the Heck reaction. Furthermore, derivatives of these ligands have been prepared using oxidation reactions. The coordination chemistry of these subsequent ligands is also investigated.
Conducting polymers that contain metals are remarkable materials, because they have the properties of both organic backbones and metals. Depending on the position of the metal relative to the conjugated backbone, i.e. attached to or directly in the backbone, these two can couple resulting in advancement of the functionality and therefore potential applications of these types of materials. Complexes of tridentate ligands with donor atoms such as phosphorus, nitrogen, and sulfur also have a wide variety of applications. In addition, complexes of tridentate ligands have advantages of stability and control of electron density by variation of donor atoms. Therefore, conjugated polymers with tridentate ligand units will have promise for various applications and advantages in their designs. Many types of PNP ligands have been studied in the literature because the hemilabile property of the nitrogen atom promotes some catalytic reactions and gives different coordination geometries. Complexes of a PNP ligand with molybdenum and carbonyl ancillary ligands were synthesized and characterized. Isomerization and conversion reactions between them were investigated as well as the coordination modes. Conducting polymers can be used as redox-active ligands and they can be used to control electron density on the metal attached to them. Synthesis and characterization of a novel polymerizable ligand 3,5-bis-EDOT-N,N-bis[2-diphenylphosphinoethyl]aniline was achieved. Related molybdenum complexes with ancillary ligands as carbonyls were also synthesized and characterized. Monomer complexes and the free ligand were electropolymerized and studied. Tris(bipyridine)ruthenium(II) chloride and analogous complexes have been studied extensively in the literature due to their luminescent and photochemical properties, and excited state lifetimes. Conducting polymers with similar ruthenium groups have been investigated for various applications. Synthesis of ruthenium complexes with 2,6-Bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine and four different bidentate ligands were reproduced; electropolymerizations of the complexes were achieved; electrochemical, UV-Vis and luminescence studies were performed and discussed. Various complexes of copper, silver, platinum, and palladium with nitrogen and phosphorus donors have been reported for their luminescence behavior as well as their interesting structures. Model complexes of these metals with a PNP ligand have been synthesized and characterized. Absorption and luminescence behaviors as well as the coordination modes were investigated.
The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.