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dc.contributor.authorClarke, Hannah M.
dc.contributor.authorHenderson, William
dc.contributor.authorNicholson, Brian K.
dc.identifier.citationClarke, H.M., Henderson, W. & Nicholson, B.K. (2011). Extending the coordination chemistry of cobalt with the metalloligand [Pt₂(μ-S) ₂ (PPh₃)₄]: Synthesis of the first cobalt(III) derivatives. Inorganica Chimica Acta, available online 23 July 2011.en_NZ
dc.description.abstractThe coordination chemistry of the metalloligand [Pt₂(μ-S) ₂ (PPh₃)₄] towards cobalt(II) and cobalt(III) centres has been explored using an electrospray ionisation mass spectrometry (ESI MS)-directed methodology. Reaction of [Pt₂(μ-S) ₂ (PPh₃)₄] with CoCl₂•6H₂O in methanol gave a green-yellow suspension of the known adduct [Pt₂(μ-S) ₂ (PPh₃)₄CoCl₂], and the CoBr₂ adduct could be similarly prepared. When in situ-generated [Pt₂(μ-S) ₂ (PPh₃)₄CoCl₂] is reacted with 8-hydroxyquinoline (HQ) and base, the initial product is the cobalt(II) adduct [Pt₂(μ-S)₂(PPh₃)₄CoQ]⁺, which is then converted in air to the cobalt(III) adduct [Pt₂(μ-S)₂(PPh₃)₄CoQ₂]⁺, isolated as its hexafluorophosphate salt. The corresponding picolinate (Pic) derivative [Pt₂(μ-S) ₂ (PPh₃)₄Co(Pic)₂]⁺ was similarly prepared, however reaction of [Pt₂(μ-S) ₂ (PPh₃)₄], CoCl₂•6H₂O and 8-(tosylamino)quinoline (HTQ) produced only the cobalt(II) adduct [Pt₂(μ-S)₂(PPh₃)₄CoTQ]⁺. Reactions of [Pt₂(μ-S)₂ (PPh₃)₄], CoCl₂•6H₂O and dithiocarbamates gave cobalt(III) complexes [Pt₂(μ-S)₂(PPh₃)₄Co(S₂CNR₂)₂]⁺ [R = Et or R₂ = (CH₂)₄], and proceeded much more rapidly, consistent with the known ability of the dithiocarbamate ligand to stabilize cobalt in higher oxidation states. A study of the fragmentation of cobalt(III) adducts by positive-ion ESI mass spectrometry indicated that [Pt₂(μ-S)₂(PPh₃)₄CoQ₂]⁺ fragments to form the radical cation [Pt₂(μ-S)₂(PPh₃)₄]⁺, which could also be generated by ESI MS analysis of [Pt₂(μ-S)₂(PPh₃)₄] in methanol–NaOH solution. In contrast, the corresponding indium(III) derivative [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺, and the cobalt(III) dithiocarbamate [Pt₂(μ-S)₂(PPh₃)₄Co(S₂CN(CH₂)₄)₂]⁺ are much more reluctant to fragment under analogous conditions, and the differences are discussed in terms of cobalt(III) redox chemistry.en_NZ
dc.subjectPlatinum complexesen_NZ
dc.subjectCobalt complexesen_NZ
dc.subjectElectrospray ionisation mass spectrometryen_NZ
dc.subjectX-ray crystal structureen_NZ
dc.titleExtending the coordination chemistry of cobalt with the metalloligand [Pt₂(μ-S) ₂ (PPh₃)₄]: Synthesis of the first cobalt(III) derivativesen_NZ
dc.typeJournal Articleen_NZ
dc.relation.isPartOfInorganica Chimica Actaen_NZ

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