- Ferro-self-assembly: Magnetic and electrochemical adaptation of a multiresponsive zwitterionic metalloamphiphile showing a shape-hysteresis effect
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Metallosurfactants are molecular compounds which combine the unique features of amphiphiles, like their capability of self-organization, with the peculiar properties of metal complexes like magnetism and a rich redox chemistry. Considering the high relevance of surfactants in industry and science, amphiphiles that change their properties on applying an external trigger are highly desirable. A special feature of the surfactant reported here, 1-(Z)-heptenyl-1′-dimethylammonium-methyl-(3-sulfopropyl)ferrocene (6), is that the redox-active ferrocene constituent is in a gemini-position. Oxidation to 6+ induces a drastic change of the surfactant's properties accompanied by the emergence of paramagnetism. The effects of an external magnetic field on vesicles formed by 6+ and the associated dynamics were monitored in situ using a custom-made optical birefringence and dual dynamic light scattering setup. This allowed us to observe the optical anisotropy as well as the anisotropy of the diffusion coefficient and revealed the field-induced formation of oriented string-of-pearls-like aggregates and their delayed disappearance after the field is switched off.
- Bitter, Stefan,Schl?tter, Moritz,Schilling, Markus,Krumova, Marina,Polarz, Sebastian,Winter, Rainer F.
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- Synthesis, structure, and properties of 1,1′-diamino- and 1,1′-diazidoferrocene
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We report an improved synthesis of 1,1′-diaminoferrocene, employing the reduction of 1,1′-diazidoferrocene with H2-Pd/C, along with extensive characterization data for both compounds. Diaminoferrocene undergoes a reversible 1e- oxidation in CH3CN at a potential of -602 mV vs Fc0/+, one of the most negative redox potentials for a ferrocene derivative. The chemical reversibility of this process was confirmed by isolation of the stable, 17-electron [Fc(NH2)2]+ cation as PF6-, OTf-, and TCNE- salts. In the solid state, diaminoferrocene exists in two conformations: one with the NH2 groups eclipsed, and the other with the NH2 groups offset by one-fifth turn around the Cp-Fe-Cp axis. Diazidoferrocene, on the other hand, exhibits only the fully eclipsed conformation in the solid state. The Fe-Cp(centroid) vectors in the diazidoferrocene molecules are roughly aligned with the crystallographic c-axis, and the molecules form layers perpendicular to this axis. The compound is thermally unstable at elevated temperatures, and rapid heating above its melting point results in explosion.
- Shafir, Alexandr,Power, Maurice P.,Whitener, Glenn D.,Arnold, John
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- Synthesis and (spectro)electrochemistry of 1′,1′′′-disubstituted biferrocenes
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A series of 1′,1′′′-disubstituted biferrocenes was synthesized to study the influence of electron-withdrawing and electron-donating groups on the electronic interaction within the biferrocenyl unit. Therefore, biferrocenes of type R-bfc-R (bfc = 1:1″-bife
- Gottwald, Dominique,Korb, Marcus,Lang, Heinrich,Mahrholdt, Julia,Schreiter, Katja,Spange, Stefan,Speck, Matth?us,Yuan, Qing
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- Photoresist based on metallocene compound and preparation method and application thereof
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The invention belongs to the technical field of photoresist, and particularly relates to a photoresist based on a metallocene compound as well as a preparation method and application of the photoresist. The metallocene compound disclosed by the invention adopts metal as a central core structure, so that the metallocene compound has a relatively high melting point and glass-transition temperature, can meet the requirements of a photoetching technology, and is stable in structure, and a film structure is not changed during high-temperature baking. In addition, the photoresist composition provided by the invention can be used in modern photoetching processes such as 248nm photoetching, 193nm photoetching, extreme ultraviolet (EUV) photoetching, nanoimprint lithography (NIL), electron beam lithography (EBL) and the like, and is particularly suitable for being used in an extreme ultraviolet (EUV) photoetching process.
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Paragraph 0067; 0074; 0078-0079
(2021/05/26)
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- Scalable Synthesis of Functionalized Ferrocenyl Azides and Amines Enabled by Flow Chemistry
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A scalable access to functionalized ferrocenyl azides has been realized in flow. By halogen-lithium exchange of ferrocenyl halides and trapping with tosyl azide, a variety of functionalized ferrocenyl azides were obtained in high yields. To allow a scalable preparation of these potentially explosive compounds, a flow protocol was developed accelerating the reaction time to minutes and circumventing accumulation of potentially hazardous intermediates. The corresponding ferrocenyl amines were then prepared by a reliable reduction process.
- Boeser, Lisa,Christmann, Mathias,Hartmayer, Bence,Heretsch, Philipp,Kleoff, Merlin,Sarkar, Biprajit,Schwan, Johannes
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supporting information
(2020/02/04)
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- Synergistic effects in ambiphilic phosphino-borane catalysts for the hydroboration of CO2
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The benefit of combining both a Lewis acid and a Lewis base in a catalytic system has been established for the hydroboration of CO2, using ferrocene-based phosphine, borane and phosphino-borane derivatives.
- Tlili, Anis,Voituriez, Arnaud,Marinetti, Angela,Thuéry, Pierre,Cantat, Thibault
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supporting information
p. 7553 - 7555
(2016/07/06)
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- Synthesis of 1-[bis(trifluoromethyl)phosphine]-1'- oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates
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A class of novel, easily accessible and air-stable 1-[bis(trifluoromethyl) phosphine]-1'-oxazolinylferrocene ligands has been synthesized from ferrocene. It became apparent that these ligands can be used in the regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates in a highly efficient manner. Excellent regio- and enantioselectivity could be obtained for a wide range of substrates.
- Lai, Zeng-Wei,Yang, Rong-Fei,Ye, Ke-Yin,Sun, Hongbin,You, Shu-Li
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p. 1261 - 1266
(2014/06/24)
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- Platinum complexes of a borane-Appended Analogue of 1,1'-Bis(diphenylphosphino)ferrocene: Flexible borane coordination modes and in situ vinylborane formation
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A bis(phosphine)borane ambiphilic ligand, [Fe(h5-C5H4PPh2)(h5-C5H4PtBu{C6H4 (BPh2)-ortho})] (FcPPB), in which the borane occupies a terminal posi
- Cowie, Bradley E.,Emslie, David J.H.
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p. 16899 - 16912
(2015/02/19)
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- Oxidative purification of halogenated ferrocenes
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We report the large scale syntheses and 'oxidative purification' of fcI2, fcBr2 and FcBr (fc = ferrocene-1,1′-diyl, Fc = ferrocenyl). These valuable starting materials are typically laborious to separate via conventional techniques, but can be readily isolated by taking advantage of their increased E1/2 relative to FcH/FcX contaminants. Our work extends this methodology towards a generic tool for the separation of redox active mixtures.
- Inkpen, Michael S.,Du, Shuoren,Driver, Mark,Albrecht, Tim,Long, Nicholas J.
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p. 2813 - 2816
(2013/03/14)
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- Acceptor-substituted ferrocenium salts as strong, single-electron oxidants: Synthesis, electrochemistry, theoretical investigations, and initial synthetic application
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A series of mono- and 1,1'-diheteroatom-substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono- and 1,1'-dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3-dichloro-5,6- dicyanobenzoquinone, AgPF6, or 2,2,6,6-tetramethyl-1-oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas-phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030-V and the maximum deviation to 0.1-V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties. Copyright
- Khobragade, Dushant A.,Mahamulkar, Shraddha G.,Pospí?il, Lubomír,Císa?ová, Ivana,Rulí?ek, Lubomír,Jahn, Ullrich
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supporting information
p. 12267 - 12277
(2012/11/14)
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- The conversion of 1,1′-dibromoferrocene to 1,2-dibromoferrocene: The ferrocene-chemist's dream reaction
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The conversion of 1,1′-dibromoferrocene to a range of 2-substituted bromoferrocenes is described. The products are useful in the preparation of a wide number of 1,2-disubstituted ferrocenes. This includes the preparation of 1,2-dibromoferrocene and 2-(diisopropylphosphino)bromoferrocene in what is a clean and simple synthesis. The synthesis may be carried out on a large scale and for the first time produces multigram quantities of these important precursor compounds. In addition the synthetic procedure may be modified to produce a new family of ferrocene-based tris-phosphine ligands such as bis(2-diphenylphosphinoferrocenyl)phenylphosphine.
- Butler, Ian R.
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- A novel method to synthesize asymmetrical disubstituted ferrocenes
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A convenient new method was developed for the preparation of 1′-substituted-1-bromoferrocenes which are important precursors for the preparation of 1′,1?-disubstituted-biferrocenes. This method can also be applied to prepare asymmetrical disubstituted ferrocenes, which are potentially useful materials possessing non-linear optical and liquid crystalline properties.
- Dong, Teng-Yuan,Lai, Long-Li
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p. 131 - 134
(2007/10/03)
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- Formation and reactivity of halogen derivatives of (η5-cyclopentadienyl)thallium
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Reactions of chloro-, bromo-, or iodocyclopentadiene, generated in ethyl ether solution from cyclopentadienylthallium and N-halosuccinimides or iodine, with thallous ethoxide has afforded the respective (halocyclopentadienyl)thallium compounds in 72-96% yield. (Chlorocyclopentadienyl)thallium can also be formed in good yield from chlorocyclopentadiene, thallium(I) chloride, and potassium hydroxide in aqueous solution. These new reagents have served as convenient intermediates in the formation of the following compounds: (η5-C5H4X)2Fe (X = Cl, Br); (η5-C5H5)(η5-C 5H4Cl)TiCl2; (η5-C5H4Cl)2TiCl2; (η5-C5H4X)Mn(CO)3 (X = Cl, Br); (η5-C5H4X)Co(CO)2 (X = Cl, Br, I); (η5-C5H4Cl)Rh(CO)2; (η5-C5H4Cl)2Ni; and (η5-C5H4Cl)Cu[P(C2H 5)3]. A reaction between (η5-C5H4Br)Co(CO)2 and n-butyllithium in ethyl ether solution at -78 °C has generated (η5-C5H4Li)Co(CO)2, which reacts with carbon dioxide and with acetone to produce (η5-C5H4CO2H)Co(CO)2 and [η5-C5H4C(CH3) 2OH]Co(CO)2, respectively.
- Conway, Brian G.,Rausch, Marvin D.
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p. 688 - 693
(2008/10/08)
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