A Route to Monosubstituted Ferrocene Compounds

Benkeser, Robert A.; Goggin, Donald; Schroll, G.

doi:10.1021/ja01644a047

Cited by 120 publications

(51 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…D values are themselves inversely proportional to the viscosity of the solvent medium, given by the Stokes-Einstein equation [30]; as [36] and of the acidity of FcCOOH (pK a = 6.7 in water/ethanol [37]), it is reasonable that FcCOOH be completely dissociated to the ferrocenyl carboxylate anion.…”

Section: Introductionmentioning

confidence: 99%

Diffusion regimes at nanoelectrode ensembles in different ionic liquids

Ugo

Moretto

Leo

et al. 2010

Electrochimica Acta

View full text Add to dashboard Cite

a b s t r a c tThe electrochemical and diffusion behaviour of different redox probes in different ionic liquids is studied at gold nanoelectrode ensembles (NEEs) in comparison with millimetre sized gold (Au-macro) and glassy carbon (GC) disk electrodes. The redox probes are neutral ferrocene (Fc), the ferrocenylmethyltrimetylammonium cation (FA + ) and the ferrocenylmonocarboxylate anion (FcCOO The CVs of the redox probes at the NEEs are peak shaped at low scan rate (v), while they are sigmoidally shaped at high v, but with some shift between forward and backward patterns. This is indicative of the occurrence of a total overlap (TO) diffusion condition when v is low which becomes a mixed diffusion layers (MDL) regime, with only a partial overlapping of individual diffusion layers, at high v values. In the most viscous IL, namely [P 14,666 ] [N(Tf) 2 ], at v higher than 0.8 V s −1 , a plateau current independent on the scan rate is achieved, indicating the tendency to reach the pure radial regime in this IL. The v values at which the transition between TO and MDL is observed scales directly with D and inversely with the IL viscosity. This behaviour is interpreted on the basis of the dependence of individual diffusion layers at each nanoelectrode on redox probe/IL interaction which fits with existing theoretical models very recently developed for nanoelectrode arrays.

show abstract

Section: Introductionmentioning

confidence: 99%

Diffusion regimes at nanoelectrode ensembles in different ionic liquids

Ugo

Moretto

Leo

et al. 2010

Electrochimica Acta

View full text Add to dashboard Cite

show abstract

“…Während zu Beginn der Ferrocenchemie extensive Reaktivitätsstudien durchgeführt wurden, [1] wird es gegenwärtig breit in der Polymerchemie genutzt, [2] für die asymmetrische Katalyse [3] oder für medizinische Anwendungen.…”

unclassified

Funktionalisierung eines cyclo‐P₅‐Liganden durch Hauptgruppenelement‐Nukleophile

et al. 2014

View full text Add to dashboard Cite

. Die berechneten Energieprofile der Reaktionen liefern eine Erklärung für die Bildung der unterschiedlichen Produkte.Ferrocen, der erste metallorganische Sandwichkomplex, der vor über 60 Jahren entdeckt wurde, ist eine erprobte vielseitige und wichtige Verbindung in der Chemie. Während zu Beginn der Ferrocenchemie extensive Reaktivitätsstudien durchgeführt wurden, [1] wird es gegenwärtig breit in der Polymerchemie genutzt, [2] für die asymmetrische Katalyse [3] oder für medizinische Anwendungen.[4] Eine der bemerkenswertesten Reaktionen von Ferrocen ist die mit starken metallorganischen Basen, wie Organolithiumverbindungen, [5,6] die zur Deprotonierung der C 5 H 5 -Einheit und damit zu Mono-und Dilithioferrocenen führt. Dies zeigt, dass das Reaktionsverhalten von Ferrocen gegenüber Nukleophilen durch den C 5 H 5 -Liganden dominiert wird. Das ähnlichste Polyphosphorderivat ist Pentaphosphaferrocen [Cp*Fe(h 5 -P 5 )] (Cp* = h 5 -C 5 Me 5 ) (1). [7] Wir und die Gruppe um Scherer sind an der Reaktivität von 1 interessiert, und es konnte gezeigt werden, dass die cylco-P 5 -Einheit an Übergangsmetall-carbonyle koordinieren kann, wobei Tripeldecker-Komplexe und andere metallorganische Verbindungen mit verzerrten P 5 -Einheiten gebildet werden, [8] und an Kupfer(I)-Halogenide, was zur Entstehung von 1D-und 2D-Polymeren [9] oder sogar sphärischen Fulleren-artigen Superbällen führt.[10] Die [12] Jedoch fehlt in der Chemie von 1 dessen Reaktivität gegenüber Hauptgruppennukleophilen, um seine Reaktivität im Vergleich mit seinem Kohlenstoffanalogon Ferrocen besser zu verstehen. Dichtefunktionaltheoretische Rechnungen an 1 zeigen, dass die LUMO-und LUMO + 1-Orbitale hauptsächlich an den P-Atomen des cyclo-P 5 -Liganden lokalisiert sind, was auch für die positive Ladung gilt.[13] Daher konnte man vermuten, dass der nukleophile Angriff am cyclo-P 5 -Liganden erfolgt. Hier berichten wir erstmals über die Reaktivität von Pentaphosphaferrocen gegenüber Hauptgruppen-Nukleophilen, die zu einer beispiellosen Funktionalisierung des cyclo-P 5 -Liganden führt. Durch diese Ergebnisse wird dieses Molekül zu einem wertvollen Ausgangsstoff in der metallorganisch basierten Hauptgruppenchemie.Das Vermischen einer grünen Lçsung von 1 und

show abstract

“…At first, we studied the effect of TA and MES adsorbed on the surface of the nanoelectrodes by analyzing the cyclic voltammetric behavior of two ferrocene derivatives used as redox probes, that are the cationic probe FA + and the weak acid FcCOOH, which dissociates to the anion FcCOO − in slightly alkaline solutions (pK a of FcCOOH is 6.7 in water/methanol [29]). Relevant CV patterns are reported in Figs.…”

Section: Redox Probes At Sam Modified Neesmentioning

confidence: 99%

Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

Silvestrini

Schiavuta²,

Scopece³

et al. 2011

Electrochimica Acta

View full text Add to dashboard Cite

a b s t r a c tThe possibility to functionalize selectively with thiols or disulfides the surface of the gold nanoelectrodes of polycarbonate templated nanoelectrode ensembles (NEEs) is studied. It is shown that the Au nanoelectrodes can be coated by a self assembled monolayer (SAM) of thioctic acid (TA) or 2-mercaptoethanesulfonic (MES) acid. The study of the electrochemical behavior of SAM-modified NEEs by cyclic voltammetry (CV) at different solution pH, using ferrocenecarboxylate as an anionic redox probe (FcCOO − ) and (ferrocenylmethyl)trimethylammonium (FA + ) as a cationic redox probe, demonstrate that the SAM-modified nanoelectrodes are permselective, in that only cationic or neutral probes can access the SAM-coated nanoelectrode surface. CV, AFM and FTIR-ATR data indicate that proteins such as casein or bovine serum albumin, which are polyanionic at pH 7, adsorb on the surface of NEEs untreated with thiols, tending to block the electron transfer of the ferrocenyl redox probes. On the contrary, the pretreatment of the NEE with an anionic SAM protects the nanoelectrodes from protein fouling, allowing the detection of well shaped voltammetric patterns for the redox probe. Experimental results indicate that, in the case of MES treated NEEs, the protein is bound only onto the polycarbonate surface which surrounds the nanoelectrodes, while the tips of the gold nanoelectrodes remain protein free.

show abstract

A Route to Monosubstituted Ferrocene Compounds

Cited by 120 publications

References 1 publication

Diffusion regimes at nanoelectrode ensembles in different ionic liquids

Diffusion regimes at nanoelectrode ensembles in different ionic liquids

Funktionalisierung eines cyclo‐P₅‐Liganden durch Hauptgruppenelement‐Nukleophile

Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

Contact Info

Product

Resources

About

A Route to Monosubstituted Ferrocene Compounds

Cited by 120 publications

References 1 publication

Diffusion regimes at nanoelectrode ensembles in different ionic liquids

Diffusion regimes at nanoelectrode ensembles in different ionic liquids

Funktionalisierung eines cyclo‐P5‐Liganden durch Hauptgruppenelement‐Nukleophile

Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

Contact Info

Product

Resources

About

Funktionalisierung eines cyclo‐P₅‐Liganden durch Hauptgruppenelement‐Nukleophile