1271-47-2Relevant academic research and scientific papers
Ferrocenylethenylsilatranes and a cymantrenylsilatrane
Pedersen, Bjorn,Wagner, Gabriele,Herrmann, Rudolf,Scherer, Wolfgang,Meerholz, Klaus,Schmaelzlin, Elmar,Braeuchle, Christoph
, p. 129 - 137 (1999)
The syntheses, properties and crystal structures of two isomeric ferrocenylethenylsilatranes and 1-(3-methylcymantrenyl)silatrane are reported. The organometallic moieties and the silatrane show little structural influence on each other. The Si-N distance
Synthesis, Structure, Electrochemical, and Spectroscopic Properties of Hetero-Bimetallic Ru(II)/Fe(II)-Alkynyl Organometallic Complexes
Sil, Amit,Ghosh, Utsav,Mishra, Vipin Kumar,Mishra, Sabyashachi,Patra, Sanjib K.
, p. 1155 - 1166 (2019)
A series of heterobimetallic wire-like organometallic complexes [(tpy-C6H4-R)(PPh3)2Ru-C-C-Fc]+ (tpy-C6H4-R = 4′-(aryl)-2,2′:6′,2′′-terpyridyl, Fc = [(η5-Cp)2Fe], R = -H, -Me, -F, -NMe2 in complexes 5-8, respectively) featuring ferrocenyl and 4′-(aryl)-2,2′:6′,2′′-terpyridyl ruthenium(II) complexes as redox active metal termini, have been synthesized. Various spectroscopic tools, such as multinuclear NMR, IR spectra, HRMS, CHN analyses, and single crystal X-ray crystallography have been utilized to characterize the heterobimetallic complexes. The electrochemical and UV-vis-NIR spectroscopic studies have been investigated to evaluate the electronic delocalization across the molecular backbones of the Ru(II)-Fe(II) heterobinuclear organometallic dyads. Electrochemical studies reveal two well-separated reversible redox waves as a result of successive oxidation of the ferrocenyl and Ru(II) redox centers. The spin density distribution analyses reveal that the initial oxidation process is associated with the Fe(II)/Fe(III) couple followed by one electron oxidation of the ruthenium(II) center. The high Kc value (0.11-1.73 × 1012) and intense NIR absorption, with molar absorption coefficient (in the order of 103 M-1 cm-1) for the RuIIFeIII mixed-valence species, signify strong electronic communication between the two metal termini. The electronic coupling constant (Hab) has been estimated to be 492 and 444 cm-1 for the structurally characterized complexes 6 and 7, respectively. The redox and NIR absorption features indicate that the mixed-valence system of the heterobinuclear dyads belongs to a Robin and Day "class II" system.
Structure, reactivity, and electronic properties of [4]ferrocenophanes and [4]ruthenocenophanes prepared via a novel heteroannular cyclization reaction
Pudelski, John K.,Callstrom, Matthew R.
, p. 3095 - 3109 (1994)
The reactions of 1,1′-bis((trimethylsilyl)ethynyl)ferrocene and 1,1′-bis((trimethylsilyl)ethynyl)ruthenocene with catalytic quantities of alkali-metal methoxides in methanol directly afforded the highly unsaturated [4]metallocenophanes 1,1′-d-methoxy-1,3-butadienylene)-ferrocene and 1,1′-(1-methoxy-1,3-butadienylene)ruthenocene, respectively, in high yields via a novel desilylation/heteroannular cyclization sequence. Analogously, 1,1′-bis((trimethylsilyl)ethynyl)octamethylferrocene reacted to give 1,1′-(1-methoxy-1,3-butadienylene)octamethylferrocene in high yield. The reactions of ((trimethylsilyl)ethynyl)ferrocene and ((trimethylsilyl)ethynyl)ruthenocene under identical conditions afforded ethynylferrocene and ethynylruthenocene, respectively. Synthetic elaboration of the heteroannular bridge of the cyclization products provided a route to additional [4]metallocenophanes. Treatment of 1,1′-(1-methoxy-1,3-butadienylene)ferrocene with acidic silica gel afforded 1,1′-(4-oxo-1-butenylene)ferrocene. Reaction of 1,1′-(4-oxo-1-butenylene)ferrocene with alane provided 1,1′-(1-butenylene)ferrocene, while reaction with sodium borohydride gave 1,1′-(4-hydroxy-1-butenylene)ferrocene. Dehydration of 1,1′-(4-hydroxy-1-butenylene)ferrocene on activated alumina provided 1,1′-(1,3-butadienylene)ferrocene. Similar synthetic transformations were carried out to yield the analogous series of ruthenocenophanes and octamethylferrocenophanes. Voltammetric half-wave oxidation potentials were measured for all of the metallocenophanes in order to evaluate the electronic effect of the heteroannular bridges. X-ray crystal structure analyses were carried out on 1-1′-(1-methoxy-1,3-butadienylene)ferrocene and 1,1′-(1-methoxy-1,3-butadienylene)ruthenocene. 1,1′-(1-Methoxy-1,3-butadienylene)ferrocene, C15H14FeO, crystallized in the orthorhombic space group Pcnb with a = 26.997(5) ?, b = 5.981(2) ?, c = 28.962(3) ?, Z = 16, and R = 0.072. 1,1′-(1-Methoxy-1,3-butadienylene)ruthenocene, C15H14RuO, crystallized in the monoclinic C2/c space group with a = 20.590(3) ?, b = 9.023(2) ?, c = 13.940(2) ?, β= 111.296(8)°, Z = 8, and R = 0.021.
A practical synthesis of ethynylferrocene from ferrocene carboxaldehyde: Structure of 1,4-diferrocenyl-1,3-butadiyne
Rodriguez, Jose-Gonzalo,Onate, Antonio,Martin-Villamil, Rosa M.,Fonseca, Isabel
, p. 71 - 76 (1996)
Ethynylferrocene was satisfactoryly obtained by a Wittig reaction between ferrocene carboxaldehyde and chloromethylentriph-enylphosphonium ylid to give an E/Z mixture of 2-chloro-1-ferrocenylethene. Both isomers were isolated pure by chemical methods. Reaction of the isomers mixture with n-butyllithium allowed ethynylferrocene to be obtained in good yield. The method was applied in one pot giving the ethynylferrocene and (E/Z)-1,4-diferrocenyl-but-1-en-3-yne as a secondary product. Oxidative coupling to 1,4-diferrocenyl-1,3-butadiyne has been carried out in quantitative yields. A single-crystal analysis of the diyne was carried out, but the compound is unreactive in solid state.
New ferrocene-based 2-thio-imidazol-4-ones and their copper complexes. Synthesis and cytotoxicity
Guk,Krasnovskaya,Dashkova,Skvortsov,Rubtsova,Dyadchenko,Yudina,Kosarev,Soldatov,Shapovalov,Semkina,Vlasova,Pergushov,Shafikov,Andreeva,Melnikov,Zyk,Majouga,Beloglazkina
, p. 17357 - 17366 (2018)
Synthesis, characterization (HRMS, NMR, EPR, XANES, UV-Vis spectroscopy, and electrochemistry), DNA and BSA binding and in vitro biological screening of two new ferrocene-incorporated thiohydantoin derivatives (5 and 6) and their copper coordination compounds are reported. The ferrocene-based thiohydantoin derivatives were prepared by copper-catalyzed azide alkyne cycloaddition reactions between alkynyl ferrocenes and 5-(Z)-3-(2-azidoethyl)-2-(methylthio)-5-(pyridin-2-ylmethylene)-1H-imidazol-4H-one. Alkynyl ferrocenes necessary for these syntheses were prepared by new procedures. Intermolecular redox reactions between the ferrocene fragment and copper(+2) coordinated ions were studied by different methods to determine the mechanism and kinetic constants of redox processes. Ferrocene-containing imidazolones (5 and 6) and their copper complexes were also tested for their in vitro cytotoxic activity against MCF-7 and A-549 carcinoma cells, and also against the noncancerous cell line Hek-293. The results showed modest cytotoxicity against the subjected cancer cell line compared with cisplatin. The ability of the obtained compounds to cause DNA degradation and cell apoptosis was investigated, and the distribution of cytosol/pellets was studied by AAS.
Synthesis and some reactions of ferrocenylacetylenes
Doisneau, G.,Balavoine, G.,Fillebeen-Khan, T.
, p. 113 - 117 (1992)
The conversion of acetylferrocene or diacetylferrocene into ethynylferrocene 1 or diethynylferrocene 4, respectively, is achieved in good yield in a one-pot synthesis using Negishi's reagent.The diethynylferrocene is isolated as its trimethylsilylderivative 5.The complexes 1 and 5 undergo various nucleophilic substitution reactions, resulting in new ferrocenyl derivatives.
Synthesis of a diferrocenylvinylidene complex by migration of a ferrocenyl substituent
Korb, Marcus,Moggach, Stephen A.,Low, Paul J.
supporting information, p. 4251 - 4254 (2021/05/05)
An unusual 1,2-ferrocenyl migration has been observed following reactions of [Ru(dppe)Cp][BArF4] with diferrocenylacetylene, extending the scope of group rearrangments beyond methyl (Wagner-Meerwein) and phenyl entities. Ferrocene-containing bis(alkynes) RCCArCCR (R = Fc, Ar = 1,4-phenylene; R = Ph, Ar = 1,1′-ferrocenylene) gave bimetallic bis(vinylidene) complexes following two consecutive rearrangements.
METAL-ORGANIC POLYHEDRAL INCLUDING METALLOCENE STRUCTURE AND METHOD FOR PREPARING THE SAME
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Paragraph 0136, (2021/06/22)
Disclosed are a metal-organic polyhedron including a metallocene structure and a method for manufacturing the same. Since the metal-organic polyhedron including the metallocene structure has high porosity and excellent electrical conductivity, when metal-organic polyhedron is used for electrodes such as supercapacitors or secondary batteries and the like, energy density and output characteristics of a device can be improved.
Novel ferrocene-labeled propargyl amines via CuI multicomponent amination/alkynylation
Srivastava, Suman
supporting information, p. 6469 - 6471 (2019/05/04)
An efficient synthesis of ferrocene-tagged propargyl amine derivatives via one-pot three-component domino amination/alkynylation in water is reported. The synthesis involves a single Cu(i) catalyst without addition of a ligand, has broad substrate applicability and gives excellent yields.
Synthesis and Characterization of Diferrocenyl Conjugates: Varying π-Conjugated Bridging Ligands and its Consequence on Electrochemical Communication
Roy, Sourav Saha,Patra, Sanjib K.
supporting information, p. 2193 - 2201 (2019/04/17)
Organometallic wire-like complexes with ferrocenyl termini, conjugated with one and two units of thienylethynyl (M1 and M2) and thienyl (M3 and M4) groups, have been synthesized with a general formula of [Fc-C≡C-(Th-C≡C)1-2-Fc] and [Fc-(Th)1-2-Fc] (Fc = ferrocenyl, Th = thienyl) respectively. The diferrocenyl organometallic complexes have been characterized by various spectroscopic tools such as multinuclear NMR, FTIR, elemental analysis, and mass spectrometry. The electrochemical properties of these compounds have been investigated by cyclic (CV) and differential pulse voltammetry (DPV). The single reversible oxidation wave in diferrocenyl complexes with thienylethynyl spacers (M1 and M2) indicates the absence of intramolecular electrochemical communication between the two ferrocenyl termini. Interestingly, the diferrocenyl complexes with one and two thienyl spacers (M3 and M4) show two successive reversible one-electron oxidation waves, indicating electronic coupling between the two ferrocenyl (Fc) termini. The potential difference (ΔE1/2) between the two redox centers is 160 mV and 130 mV, respectively, with the corresponding comproportionation constants (Kc) of 6.2 × 102 and 1.5 × 102. Upon mono-oxidation of M3 by [Cp2Fe][BF4], a broad and weak intervalence charge-transfer (IVCT) transition is observed in the NIR region of 1200–2200 nm.
