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dc.contributor.authorAlley, Steven R.
dc.contributor.authorHenderson, William
dc.date.accessioned2009-11-17T03:10:25Z
dc.date.available2009-11-17T03:10:25Z
dc.date.issued2001
dc.identifier.citationAlley, S. R., & Henderson, W. (2001).Synthesis and characterisation of ferrocenyl-phosphonic and –arsonic. Journal of Organometallic Chemistry, 637-639, 216-229.en
dc.identifier.urihttps://hdl.handle.net/10289/3375
dc.description.abstractThe ferrocene-derived acids FcCH₂CH₂E(O)(OH)₂ [4, E=P; 10, E=As; Fc=Fe(η₅-C₅H₅)(η⁵-C₅H₄)] have been synthesized by the reaction of FcCH₂CH₂Br with either P(OEt)₃ followed by hydrolysis, or with sodium arsenite followed by acidification. Reaction of FcCH₂OH with (EtO)₂P(O)Na gave FcP(O)(OEt)(OH), which was converted to FcCH₂P(O)(OH)₂ (3) by silyl ester hydrolysis using Me₃SiBr–Et₃N followed by aqueous work-up. Similarly, the known phosphonic acid FcP(O)(OH)₂and the new derivatives 1,1′-Fc′[P(O)(OH)₂]₂ [Fc′=Fe(η⁵-C₅H₄)₂] and 1,1′-Fc′[CH₂P(O)(OH)₂]₂(7) have been synthesized via their corresponding esters. X-ray crystal structure determinations have been carried out on 3 and 7, and the hydrogen-bonding networks discussed. Electrospray mass spectrometry has been employed in the characterization of the various acids. Phosphonic acids give the expected [M–H]− ions and their fragmentation at elevated cone voltages has been found to be dependent on the acid. FcP(O)(OH)₂ fragments to [C₅H₄PO₂H]−, but in contrast Fc(CH₂)nP(O)(OH)₂ (n=1, 2) give Fe{η⁵-C₅H₄(CH₂)nP(O)O₂]− ions, which are proposed to have an intramolecular interaction between the Fe atom and the phosphonate group. In contrast, arsonic acid (10), together with PhAs(O)(OH)₂for comparison, undergo facile alkylation (in methanol or ethanol solvent), and at elevated cone voltages (e.g. >60 V) undergo carbon–arsenic bond cleavage giving [CpFeAs(O)(OR)O]− (R=H, Me, Et) and ultimately [AsO₂]− ions.en
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherELSEVIER SCIENCE SAen_NZ
dc.rightsThis is an author’s accepted version of an article published in the Journal of Organometallic Chemistry.en
dc.subjectferroceneen
dc.subjectphosphonic aciden
dc.subjectarsonic aciden
dc.subjectcrystal structuresen
dc.subjectelectrospray mass spectrometryen
dc.titleSynthesis and characterisation of ferrocenyl-phosphonic and -arsonicen
dc.typeJournal Articleen
dc.identifier.doi10.1016/S0022-328X(01)00908-1en
dc.relation.isPartOfJournal of Organometallic Chemistryen_NZ
pubs.begin-page216en_NZ
pubs.elements-id27193
pubs.end-page229en_NZ
pubs.volume637-639en_NZ
uow.identifier.article-noCen_NZ


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