128925-12-2

Upstream product

• 59568-28-4 1,1',2,2',3,3',4,4'-octamethylferrocene 
• 68-12-2 N,N-dimethyl-formamide 
• 127-09-3 sodium acetate 

Downstream Products

• 1425938-44-8 C₃₉H₂₈Cl₁₄Fe 

Relevant academic research and scientific papers

Synthesis, characterization and electrochemical behaviour of dimethyleneamine-bridged methylated and non-methylated biferrocenyl derivatives

Two dimethyleneamine-bridged octamethylated and non-methylated biferrocenyl complexes, compounds 1 and 2, have been synthesized and characterized by 1H, 29Si{1H} and 13C{1H} NMR spectroscopy, and mass spectrometry. The redox activity of the ferrocenyl centers in 1 and 2 has been characterized by cyclic voltammetry in dichloromethane containing [n-Bu4N][PF6], [n-Bu4N][B(C6F5)4] or [n-Bu4N]Cl as electrolyte support. Their electrochemistry is not only strongly dependent on the solvent/electrolyte medium but also on the substituents of the ferrocenyl moieties. Studies of the electrochemical oxidation of 1 provide evidence of the grafting of a ferrocene species onto platinum electrode surfaces.

Tuning of Oxidation Potential of Ferrocene for Ratiometric Redox Labeling and Coding of Nucleotides and DNA

Three sets of 7-deazaadenine and cytosine nucleosides and nucleoside triphosphates bearing either unsubstituted ferrocene, octamethylferrocene and ferrocenecarboxamide linked through an alkyne tether to position 7 or 5, respectively, were designed and synthesized. The modified dNFcXTPs were good substrates for KOD XL DNA polymerase in primer extension and were used for enzymatic synthesis of redox-labelled DNA probes. Square-wave voltammetry showed that the octamethylferrocene oxidation potential was shifted to lower values, whilst the ferrocenecarboxamide was shifted to higher potentials, as compared to ferrocene. Tailed PEX products containing different ratios of Fc-labelled A (dAFc) and FcPa-labelled C (dCFcPa) were synthesized and hybridized with capture oligonucleotides immobilized on gold electrodes to study the electrochemistry of the redox-labelled DNA. Clearly distinguishable, fully orthogonal and ratiometric peaks were observed for the dAFc and dCFcPa bases in DNA, demonstrating their potential for use in redox coding of nucleobases and for the direct electrochemical measurement of the relative ratio of nucleobases in an unknown sequence of DNA.

Stepwise synthesis of octamethylferrocene-1,1′-dicarbaldehyde. Preparation of new electron donors for charge-transfer complexes

A stepwise synthesis of octamethylferrocene-1,1′-dicarbaldehyde (3), starting from 1,2,3,4-tetramethyl-5-(methoxycarbonyl)cyclopentadiene (7) is described, involving ferrocene formation, ester reduction to the corresponding bis(hydroxymethyl) derivative 9, and MnO2 oxidation. The aldehyde 3 readily reacts with different phosphonates derived from sulfurcontaining heterocycles in a Wittig-Horner reaction to form new electron donors that may be used in the preparation of various charge transfer complexes. The X-ray crystal structures of 1-[(1,3-benzodithiol-2-ylidene)methyl]-2,2′,3,3′,4,4′,5, 5′-octamethylferrocene (11a), 1-[(1,3-dithiolo[4,5-b][1,3]dithiol-2-ylidene)methyl]-2,2′,3,3′,4, 4′,5,5′-octamethylferrocene (11b), 1,1′-bis[(1,3-benzodithiol-2-ylidene)methyl]-2,2′,3,3′,4, 4′,5,5′-octamethylferrocene (12a), and 1,1′-bis[(5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiol-2-ylidene)methyl]-2, 2′,3,3′,4,4′,5,5′-octamethylferrocene (12c) have been determined. In these compounds the planes of the sulfur heterocycles are oriented at angles of 60-75°, with respect to the plane of the respective Cp ring.

Hydrogen production catalyzed by bidirectional, biomimetic models of the [FeFe]-hydrogenase active site

Active site mimics of [FeFe]-hydrogenase are shown to be bidirectional catalysts, producing H2 upon treatment with protons and reducing equivalents. This reactivity complements the previously reported oxidation of H2 by these same catalysts in the presence of oxidants. The complex Fe2(adtBn)(CO)3(dppv)(PFcEt2) ([1]0; adtBn = (SCH2)2NBn, dppv = cis-1,2-bis(diphenylphosphino)ethylene, PFcEt2 = Et2PCH2C5Me4FeCp) reacts with excess [H(OEt2)2]BArF4 (BArF4- = B(C6H3-3,5-(CF3)2)4-) to give ～0.5 equiv of H2 and [Fe2(adtBnH)(CO)3(dppv)(PFcEt2)]2+ ([1H]2+). The species [1H]2+ consists of a ferrocenium ligand, an N-protonated amine, and an FeIFeI core. In the presence of additional reducing equivalents in the form of decamethylferrocene (Fc), hydrogen evolution is catalytic, albeit slow. The related catalyst Fe2(adtBn)(CO)3(dppv)(PMe3) (3) behaves similarly in the presence of Fc, except that in the absence of excess reducing agent it converts to the catalytically inactive μ-hydride derivative [μ-H3]+. Replacement of the adt in [1]0 with propanedithiolate (pdt) results in a catalytically inactive complex. In the course of synthesizing [FeFe]-hydrogenase mimics, new routes to ferrocenylphosphine ligands and nonamethylferrocene were developed.

Synthesis of octamethylferrocene derivatives via reaction of (octamethylferrocenyl)methyl carbocation with nucleophiles and application to functionalization of surfaces

Formylation of octamethylferrocene, Fe(C5Me4H)2, using N,N'-dimethylformamide/OPCI3 in CHCI3 solvent at 60-70 °C gives octamethylformylferrocene in high yield (～95%). The aldehyde can be converted to a CN group to give octamethylcyanoferrocene or can be used to prepare ethyl 0-(octamethylferrocenyl)acrylate. Most important, reductionn of octamethylformylferrocene using LiAIH4 in Et2O yields the alcohol in ～95% yield. Acid-catalyzed (HBF4) dehydration of the alcohol. III, leads to formation of (octamethylferrocenyl)methyl carbocation in almost quantitative yield. The carbocation I can be isolated as an orange-red BF4- salt in ～ 90% yield from octamethylferrocene. I shows sharp 13C and 1H NMR spectral features consistent with formulation as a diamagnetic Fe(II) species with the positive charge localized on the C having two H's. I slowly dimerizes, even in the solid state, to a C-C coupled product with two Fe(III) centers. The paramagnetic, blue-green dimer can be reduced with cobaltocene or aqueous Na2S2O4 to l,2-bis(octamethylferrocenyl)ethane. Reaction of (octamethylferrocenyl)methyl carbocation with nucleophiles is a convenient synthetic route to octamethylferrocene derivatives, which have proved difficult to obtain by electrophilic substitution of octamethylferrocene. Reaction of the new carbocation I has been used to synthesize octamethylferrocenyl derivatives in good to excellent yields (～60-95%) via reaction with amines, thiols, or CN- Reaction of (octamethylferrocenyl)methyl carbocation with surface-confined nucleophiles such as NH2 or SH [surfaces derivatized with (MeO)3Si(CH2)3NH2 or (MeO)3Si(CH2)3SH] is a convenient way to attach octamethylferrocene derivatives to surfaces including SiO2, Pt, and indium tin oxide (ITO).