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dc.contributor.advisorRillema, D. Paul
dc.contributor.authorKirgan, Robert A.
dc.date.accessioned2011-11-23T16:21:54Z
dc.date.available2011-11-23T16:21:54Z
dc.date.copyright2007
dc.date.issued2007-08
dc.identifier.otherd07035
dc.identifier.urihttp://hdl.handle.net/10057/3981
dc.descriptionDissertation(Ph.D.)--Wichita State University, College of Liberal Arts and Sciences, Dept. of Chemistry
dc.description.abstractThe chloro and pyridinate derivatives of rhenium(I) tricarbonyl complexes containing the diimine ligands 2,2’-bipyrazine (bpz) and 5,5’-dimethyl-2,2’-bipyrazine (Me2bpz) are discussed. When compared to similar rhenium(I) tricarbonyl complexes of 2,2’-bipyridine (bpy) and 2,2’-bipyrimidine (bpm), the Me2bpz complexes are comparable to bpm derivatives and their properties are intermediate between those of bpy and bpz complexes. Also discussed is the synthesis and properties of two new analogues of ruthenium(II) tris-bipyridine, a monomer and dimer. The complexes contain the ligand 6,6’-(1,2-ethanediyl)bis-2,2’-bipyridine (O-bpy) which contains two bipyridine units bridged in the 6,6’ positions by an ethylene group. Crystal structures of the two complexes formulated as [Ru(bpy)(O-bpy)](PF6)2 and [(Ru(bpy)2)2(O-bpy)](PF6)4 reveal structures of lower symmetry than D3 which affects the electronic properties of the complexes as revealed by Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TDDFT) calculations. Iron(II) tris-bipyrazine undergoes dissociation in solution with loss of the three bipyrazine ligands. The rate of the reaction in acetonitrile depends on the concentration of anions present in the solution. The rate is fastest in the presence of Cl- and slowest in the presence of Br-. In a second discussion DFT calculations are used to explore four iron(II) diimine complexes. DFT calculations show the higher energy HOMO (highest occupied molecular orbital) orbitals of the four complexes are metal centered and the lower energy LUMO (lowest unoccupied molecular orbitals) are ligand centered.en_US
dc.format.extentxx, 351 p.en
dc.language.isoen_USen_US
dc.publisherWichita State Universityen_US
dc.rights© Copyright 2007 by Robert Anthony Kirgan. All rights reserveden
dc.subjectDiimine ligands
dc.subjectRhenium(I) complexes
dc.subjectDensity Functional Theory
dc.subject.lcshElectronic dissertationsen
dc.titleDiimine complexes of ruthenium(ii), rhenium(i) and iron(ii): from synthesis to DFT studiesen_US
dc.typeDissertationen_US


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