dc.contributor.author | Alley, Steven R. | |
dc.contributor.author | Henderson, William | |
dc.date.accessioned | 2009-11-17T03:10:25Z | |
dc.date.available | 2009-11-17T03:10:25Z | |
dc.date.issued | 2001 | |
dc.identifier.citation | Alley, S. R., & Henderson, W. (2001).Synthesis and characterisation of ferrocenyl-phosphonic and –arsonic. Journal of Organometallic Chemistry, 637-639, 216-229. | en |
dc.identifier.uri | https://hdl.handle.net/10289/3375 | |
dc.description.abstract | The 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.mimetype | application/pdf | |
dc.language.iso | en | |
dc.publisher | ELSEVIER SCIENCE SA | en_NZ |
dc.rights | This is an author’s accepted version of an article published in the Journal of Organometallic Chemistry. | en |
dc.subject | ferrocene | en |
dc.subject | phosphonic acid | en |
dc.subject | arsonic acid | en |
dc.subject | crystal structures | en |
dc.subject | electrospray mass spectrometry | en |
dc.title | Synthesis and characterisation of ferrocenyl-phosphonic and -arsonic | en |
dc.type | Journal Article | en |
dc.identifier.doi | 10.1016/S0022-328X(01)00908-1 | en |
dc.relation.isPartOf | Journal of Organometallic Chemistry | en_NZ |
pubs.begin-page | 216 | en_NZ |
pubs.elements-id | 27193 | |
pubs.end-page | 229 | en_NZ |
pubs.volume | 637-639 | en_NZ |
uow.identifier.article-no | C | en_NZ |