- Donor-substituted CpCo-stabilized cyclobutadienes and superphanes
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RCpCoL2 complexes (L2 = (CO)2 or COD, R = H, CO2Me, TMS) were reacted with various alkynes substituted with chalcogen atoms adjacent to the triple bonds. These reactions yielded hetero-substituted CpCo-capped cyclobutadienes and superphanes dependent on the ring size of the corresponding cyclic diene used as starting material. Reactions in decaline afforded not only CpCo-capped cyclobutadieno superphanes, but also mixed cyclobutadieno cyclopentadienono superphanes. X-ray analyses do not indicate a significant amount of conjugation between the π systems and the lone pairs of the heteroatoms whereas cyclic voltammetry reveals an easier oxidation when increasing the number of electron-donating heteroatoms.
- Werz, Daniel B.,Schulte, J. Hilko,Gleiter, Rolf,Rominger, Frank
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- σ-delocalized hexakis(methylthio)benzene dication: A possible intermediate of pummerer-type rearrangement of monooxide of hexakis(methylthio)benzene
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The Pummerer-type rearrangement of monooxide of hexakis(methylthio)benzene with H2SO4 or (CF3SO2)2O gives the cyclic methylsulfonium salt. A σ-delocalized hexathia dication is proposed as an intermediate.
- Kobayashi, Kenji,Takahashi, Ohgi,Namatame, Kazuhiko,Kikuchi, Osamu,Furukawa, Naomichi
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- Highly Conductive 2D Metal-Organic Framework Thin Film Fabricated by Liquid-Liquid Interfacial Reaction Using One-Pot-Synthesized Benzenehexathiol
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Metal-organic frameworks (MOF) are studied extensively in applications like catalysts, gas storage, and sensors due to their various functional groups and structures. Two-dimensional (2D) MOFs such as triphenylene-based materials show excellent charge transport properties, but thin-film fabrication and organic ligand synthesis are difficult. In this work, we synthesize thiol-based organic ligand, benzenehexathiol (BHT), by a simple one-pot reaction. This facile method is safer and faster than conventional synthesis procedure that requires using liquid ammonia as solvent. Two novel 2D MOF materials, Ag3BHT2 and Au3BHT2, are fabricated by coordinating BHT with either silver (Ag) or gold (Au) ions through liquid-liquid interfacial reaction. The Ag3BHT2 thin film reaches a high electrical conductivity of 363 S cm-1, which has potential applications in electronic devices and sensors.
- Chen, Iu-Fan,Lu, Chun-Fu,Su, Wei-Fang
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p. 15754 - 15762
(2019/01/09)
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- A linear-chain copper(I) coordination polymer with hexakis(methylthio)benzene
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In the structure of catena-poly[copper(I)-μ-[hexakis-(methylthio)benzene-S1,S 2:S4,S5]] hexafluorophosphate, {[Cu(C12H18S6)]PF6}n, each Cu atom is coordinat
- Suenaga, Yusaku,Kuroda-Sowa, Takayoshi,Munakata, Megumu,Maekawa, Masahiko,Morimoto, Hiroshi
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p. 1566 - 1569
(2007/10/03)
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- AN ELECTRON SPIN RESONANCE INVESTIGATION OF THE RADICAL CATIONS FROM POLY(ALKYLTHIO)BENZENES
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The radical cations of some poly(methylthio)- and poly(isopropylthio)-benzenes have been investigated by e.s.r. spectroscopy.Discrimination between the couplings due to the aryl and alkyl protons, when the assignment is not straightforward, has been made
- Alberti, Angelo,Pedulli, Gian Franco,Tiecco, Marcello,Testaferri, Lorenzo,Tingoli, Marco
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p. 975 - 980
(2007/10/02)
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- Fragmentation of Aryl Alkyl Sulfides. A Simple, One-Pot Synthesis of Polymercaptobenzenes from Polychlorobenzenes
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A simple procedure is described which allows one to prepare polymercaptobenzenes starting from chlorobenzenes.The reactions of all the possible chlorobenzenes with Me2CHSNa in HMPA give the corresponding (isopropylthio)benzenes which can be cleaved by adding sodium to the reaction mixtures to give the arenethiolates in good yields.In some cases the polymercaptobenzenes were isolated after treatment with acid; in other cases methyl iodide was added to the reaction mixture and poly(methylthio)benzenes were obtained.It is suggested that the (isopropylthio)benzenes react with sodium to give the corresponding radical anions which fragment at the sulfur-alkyl bond to give the arenethiolates.
- Maiolo, Filippo,Testaferri, Lorenzo,Tiecco, Marcello,Tingoli, Marco
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p. 3070 - 3073
(2007/10/02)
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- Reactions of Polychlorobenzenes with Alkanethiol Anions in HMPA. A Simple, High-Yield Synthesis of Poly(alkylthio)benzenes
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Reactions of the isomeric trichlorobenzenes and tetrachlorobenzenes and of pentachloro- and hexachlorobenzene with an excess of the sodium salt of the isopropanethiol, in HMPA, afforded the products of complete displacement of all the chlorine atoms present in the molecule.Similar substitutions were also obtained with EtSNa.The reactions with MeSNa were in some cases complicated by the competitive nucleophilic attack at the methyl group of the initially formed aryl methyl thioethers which are thus demethylated to afford thiophenols.
- Testaferri, Lorenzo,Tingoli, Marco,Tiecco, Marcello
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p. 4376 - 4380
(2007/10/02)
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