Thiourea containing bipyridine transition metal complexes for the recognition of anions

• Main Author: Blackburn, Anna Louise
• Published: Queen's University Belfast 2013
• Subjects: 541.2242
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.602439

This research thesis considers the design and synthesis of a range of thiourea bipyridyl complexes and their use as anion binding receptors. A range of isothiocyanate precursors were synthesised from a reaction employing carbon disulphide. These precursors were then coupled with 5-aminomethyl-2,2’-bipyridine to prepare a group of novel bipyridyl Iigands each containing at least one thiourea functionality. Three of the Iigands were successfully reacted with [Re(CO)5Br] to create three dinuclear rhenium{l} complexes. All of the Iigands were successfully reacted with [Ru(bpy)2Cl2] to yield eight new fully characterised ruthenium(II) complexes; with each ligand forming a mononuclear and a dinuclear complex respectively. Two of the ligands were also successfully attached to both a rhenium{l} and a ruthenium{II} centre resulting in two new heterometallic complexes. Anion binding investigations with the tetrabutylammonium salts of acetatel bromidel chloridel fluoridel perchloratel nitratel dihydrogenphosphate and hydrogensulfate were carried out. The Iigandsl anion binding potential was explored by lH NMR spectroscopic titrations. In general the Iigands show an affinity for both acetate and dihydrogenphosphatel with fluoride resulting in deprotonation