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Studies in ruthenium and osmium coordination chemistry

Studies in ruthenium and osmium coordination chemistry
Studies in ruthenium and osmium coordination chemistry

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.

University of Southampton
Champness, Neil Robert
Champness, Neil Robert

Champness, Neil Robert (1993) Studies in ruthenium and osmium coordination chemistry. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

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.

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Published date: 1993

Identifiers

Local EPrints ID: 462333
URI: http://eprints.soton.ac.uk/id/eprint/462333
PURE UUID: 2a7c78cf-a5dc-4547-8fe2-2caae87b661c

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Date deposited: 04 Jul 2022 19:05
Last modified: 04 Jul 2022 19:05

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Contributors

Author: Neil Robert Champness

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