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Title: Studies in ruthenium and osmium coordination chemistry
Author: Champness, Neil Robert
ISNI:       0000 0001 3526 4741
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 1993
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Complexes of ruthenium and osmium with bidentate phosphine and arsine ligands have been prepared and their properties investigated. Ruthenium(III) complexes of the form trans-[Ru(L-L)₂X₂]⁺ ((L-L) = diphosphine or diarsine; X = Cl, Br) and the analogous osmium(III) and (IV) compounds, trans-[Os(L-L)₂X₂]⁺/2+ were synthesised and studied using u.v.-visible and infra-red spectroscopies. The redox properties of the complexes were studied using cyclic voltammetry and their properties compared. The stereochemistry was confirmed by x-ray crystal structures of trans-[Ru(o-C₆F₄(AsMe₂)₂Br₂]BF₄ and trans-[Os(o-C₆H₄(AsMe₂)₂)₂Cl₂]ClO₄. The variation of Os-As and Os-X (X = Cl, Br) bond lengths with osmium oxidation state was investigated by the use of Os Lm-edge EXAFS 9Extended X-ray Absorption Fine Structure). Ruthenium compounds with bidentate Group 16 ligands, trans-[Ru(L-L)₂X₂]n+ (N = 0, (L-L) = diselenoether or ditelluroether; n = 1, (L-L) = dithioether, diselenoether; X = Cl, Br) have also been prepared and studied spectroscopically and electrochemically. 77Se and 125Te n.m.r. spectra were recorded for the ruthenium(II) compounds. The trans stereochemistry was confirmed by the x-ray crystal structure of trans-[Ru(PhSeCH₂CH₂SePh)₂Cl₂]. Ruthenium-stibine compounds of the form trans-[Ru(SbPh₃)₄X20+ (X = Cl, Br) have been studied and their properties investigated. The six-coordination was confirmed by an x-ray crystal structure of trans-[Ru(SbPh₃)₄Cl₂] and this contrasts with the well-known five-coordinate phosphine compound [Ru(PPh₃)₃Cl₂]. A functionalised o-phenylene diphosphine has been prepared and bound to a polystyrene polymer-support. Nickel, platinum, rhodium and ruthenium complexes of this supported diphosphine and model precursors have been synthesised and their properties investigated by the use of diffuse reflectance u.v.-visible and metal-edge EXAFS spectroscopies.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Inorganic chemistry