Fragmentation pathways of [Re₂(μ-OR)₃(CO)₆]– (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry

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dc.contributor.authorJiang, Chenghua
dc.contributor.authorHor, T.S. Andy
dc.contributor.authorYan, Yaw Kai
dc.contributor.authorHenderson, William
dc.contributor.authorMcCaffrey, Louise J.
dc.date.accessioned2009-11-18T03:24:41Z
dc.date.available2009-11-18T03:24:41Z
dc.date.issued2000
dc.description.abstractThe rhenium hydroxy and methoxy carbonyl complexes [Re₂(μOR)₃(CO)₆]⁻ (R = H or Me) have been studied by negative-ion electrospray mass spectrometry (ESMS). The complexes undergo facile exchange reactions with protic compounds, including alcohols and phenols. With dimethyl malonate, ester hydrolysis occurs giving carboxylate-containing complexes, and with H₂O₂ or ButOOH, oxidation to ReO₄⁻occurs. The feasibility and extent of these reactions can conveniently, rapidly, and unambiguously be determined by electrospray mass spectrometry, and is dependent on the acidity and steric bulk of the protic compound. The results also suggest that the complexes can be used as versatile starting materials for the synthesis of a wide range of analogous [Re₂(μ-OR)₃(CO)₆]⁻ complexes by simple reaction with an excess of the appropriate alcohol. By varying the applied cone voltage the fragmentation pathways have been investigated; the hydroxy complex undergoes dehydration followed by CO loss, whereas for the methoxy complex -hydride elimination (and CO loss) is observed, with confirmation provided by deuterium labelling studies. Under ESMS conditions, the neutral complexes [Re₂(μ-OR)₂(μ-dppf )(CO)₆] [R = H or Me; dppf = 1,1 -bis(diphenylphosphino)ferrocene] undergo substantial solvolysis and hydrolysis to give mainly mononuclear species; simple parent ions (e.g. [M + H]⁺) are not formed in appreciable abundance, probably due to the lack of an efficient ionisation pathway.en
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dc.identifier.citationJiang, C., Hor, T. S. A., Yan, Y. K., Henderson, W., & McCaffrey, L. J. (2000). Fragmentation pathways of [Re₂(μ-OR)₃(CO)₆]– (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry. Journal of Chemical Society Dalton Transactions, 3197-3203.en
dc.identifier.doi10.1039/b003893hen
dc.identifier.urihttps://hdl.handle.net/10289/3380
dc.language.isoen
dc.publisherROYAL SOC CHEMISTRYen_NZ
dc.relation.isPartOfJournal of the Chemical Society Dalton Transactionsen_NZ
dc.rightsThis is an author’s accepted version of an article published in the Journal of Chemical Society Dalton Transactions. Used with permission.en
dc.subjectchemistryen
dc.subjectfragmentationen
dc.subjectspectrometryen
dc.titleFragmentation pathways of [Re₂(μ-OR)₃(CO)₆]– (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometryen
dc.typeJournal Articleen
pubs.begin-page3197en_NZ
pubs.elements-id41634
pubs.end-page3203en_NZ
pubs.issue18en_NZ
pubs.volume18en_NZ
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