59065-21-3Relevant articles and documents
Characterization of a byproduct in the alkylation of DMIT: Alkylation on the least nucleophilic sulfur atom
Petersen, Bo M.,Bjernemose, Jens K.,Jeppesen, Jan O.
, p. 3099 - 3104 (2006)
It is generally accepted that the alkylation of (Et4N) 2-[Zn(DMIT)2] (1) is a very clean reaction that produces 4,5-bis(alkylthio)-1,3-dithiole-2-thiones 4 in very high yields. Although this procedure has been widely used, we have found that, in addition to the 4,5-bis(alkylthio)-1,3-dithiole-2-thione products 4, highly unexpected byproducts are formed during the alkylation reaction in which the thione functionalities of DMIT in (Et4N)2[Zn(DMIT)2] (1) are alkylated instead of the more reactive thiolate groups. These byproducts were identified as a novel type of compounds, namely bis(2-alkylthio-1,3- dithiol-1-ium-4,5-dithiolato)zinc compounds 3, being composed of two identical 2-alkylthio-1,3-dithiol-1-ium-4,5-dithiolate moieties coordinated to a single zinc(II) atom and were characterized by elemental analyses and different spectroscopic techniques as well as single-crystal X-ray structure analyses. A comparison of the physical properties of compounds 3 and (Et4N) 2[Zn(DMIT)2] (1) has been carried out. The outcome of these investigations revealed significant differences in the physical properties of these two systems. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Variable-Temperature Photoelectron Spectral Study of 1,3-Dithiol-2-one and 4,5-Disubstituted 1,3-Dithiol-2-ones. Thermal Generation of 1,2-Dithiete, 3,4-Disubstituted 1,2-Dithietes, and Dialkyl Tetrathiooxalates
Schulz, Reinhard,Schweig, Armin,Hartke, Klaus,Koester, Joachim
, p. 4519 - 4528 (1983)
The thermal fragmentation of 1,3-dithiol-2-one, its 4,5-dimethyl,dicyano, monocyclic 4,5-dialkylthio (R4 = R5 = SCH3, SC2H5, SCH(CH3)2), and bicyclic alkylthio derivatives (R4,5 = SCH2S, S(CH2)2S, S(CH2)3S) was investigated by variable-temperature photoelectron spectroscopy and in part by the matrix-isolation technique and infrared spectroscopy.The photoelectron spectra of the reactive intermediates 1,2-dithiete, 3,4-dimethyl-1,2-dithiete, and diethyl tetrathiooxalate are presented and interpreted.The new reactive species are unambiguously identified by photoelectron spectral and quantum chemical means.In addition, the photoelectron spectra of the stable (i.e., isolable at room temperature) compounds 3,4-bis(trifluoromethyl)-1,2-dithiete, and diethyl tetrathiooxalate are discussed.The influence of substituents on the relative stabilities of the 1,2-dithiete vs. the 1,2-dithione structures is studied using the MNDO method.The theoretical as well as the experimental results show that 1,2-dithiete and 3,4-dimethyl-1,2-dithiete are thermodynamically favored above their 1,2-dithione counterparts.
Tetrathiapentalene derivatives with long alkyl chains
Kimura, Shinya,Kurai, Hiroyuki,Mori, Takehiko,Mori, Hatsumi,Tanaka, Shoji
, p. 59 - 65 (2001)
Bis-fused π-electron donors having alkylthio chains, CnTET-TTP (2-[4,5-bis(alkylthio)-1,3-dithiol-2-ylidene]-5- (4,5-ethylenedithio-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene; n = 2-4) have been synthesized. C2TET-TTP (1a) forms radical-cation salts with BF4- and ClO4-, which are metallic (σπ = 900-2500 S cm-1) down to helium temperatures. The I3 salts of C3TET-TTP (1b) and C4TET-TTP (1c) are semiconductive from room temperature (σ π = 0.041 and 0.025 S cm-1, respectively). (C2TET-TTP)2ClO4 has uniform stacks of the donors, and has an elliptical Fermi surface characteristic of two-dimensional metals. (C4TET-TTP)I3 is dimeric, and can be regarded as a band insulator. These crystal structures demonstrate the tendency that the long alkyl chains increase the anion content, and stabilize the usual stacking structure as well as the dimerization.
Self-assembly of radially π-extended tetrathiafulvalene tetramers for visible and near infrared electrochromic nanofiber
Hasegawa, Masashi,Iyoda, Masahiko
supporting information, p. 154 - 162 (2020/02/11)
The self-assembly and electrochromic nanofiber formation of radially 7pi;-extended tetrathiafulvalene (TTF) tetramers anchored to 1,2,4,5-tetraethynylbenzene were investigated. The tetramer with SBu-substituents underwent self-assembly in solution. Cationic species of the tetramer, obtained by chemical oxidation with Fe(ClO4)3, exhibited a marked electrochromism in the solution. Their electronic spectra revealed absorption bands corresponding to intermolecular mixed-valence aggregation based on (TTF//TTF)+, and π-aggregation based on (TTF?+//TTF?+) due to the strong molecular association in the cationic species. Furthermore, the tetramer formed an entangled nanoscale fibrous material from CHCl3 hexane. Electrochemical oxidation of the nanofiber on an indium tin oxide electrode revealed a repeatable redox profile. The nanofiber displayed remarkable electrochromic behavior: The color of the fiber changed from purple (neutral) to brown/brownish green (dication and trication) and green (tetracation). These color changes of the nanofiber are similar to those in solution, and the electronic spectra of the oxidized nanofibers reflected the stacked TTF units in the cationic nanofibers.
Metal complexes of a tetrathiafulvalene 4,5-dithiolate. Synthesis, characterisation and properties of dianionic and neutral mercury complexes
Narvor, Nathalie Le,Robertson, Neil,Wallace, Emma,Kilburn, Jeremy D.,Underhill, Allan E.,et al.
, p. 823 - 828 (2007/10/03)
Dianionic mercury bis(tetrathiafulvalene dithiolate) complexes 2 (R = Et or Bu) and the corresponding oxidised neutral complex (R = Et) have been prepared.The crystal structure of 2 (R = Et) has been determined and shows that the tetrathiafulvalene dithiolate units are tetrahedrally co-ordinated around the central Hg atom.Cyclic voltammetry and ESR studies indicated that there is very little interaction between the two ligands.A compressed pellet of the powdered neutral complex exhibited an electrical conductivity of 1E-5 S cm-1 at room temperature.
Sequential functionalisation of bis-protected tetrathiafulvalene-dithiolates
Simonsen, Klaus B.,Svenstrup, Niels,Lau, Jesper,Simonsen, Ole,Mork, Pernille,Kristensen, Gitte J.,Becher, Jan
, p. 407 - 418 (2007/10/03)
The utilisation of the 2-cyanoethyl group as a versatile protecting group for 2-thioxo-1,3-dithiole-4,5-dithiolates and tetrathiafulvalene-thiolates is reported. Mono deprotection of bis-protected 2-thioxo-1,3-dithiole-4,5-dithiolate and of bis-protected
Fourier transform Raman spectroscopy of 1,3-dithiole-2-thione and related compounds
Dyer, C. D.,Kilburn, J. D.,Maddams, W. F.,Walker, P. A.
, p. 1225 - 1234 (2007/10/02)
The Raman spectra of 1,3-dithiole-2-thione and a series of related compounds wer recorded on a fourier transform Raman spectrometer using near-infrared laser excitation.The spectra proved, with limited exception, to be of high quality.With the help of measured depolarisation ratios it has proved possible to make assignments for the stronger peaks in the spectrum of 1,3-dithiole-2-thione, thereby resolving ambiguities and disagreements in the results of previous workers.These assignments have been used to aid in the interpretation of the very characteristic spectra of substituted thiones.The value of these spectra for analytical purposes is discussed.
Electrochemical Synthesis of Tetrathioethylenes
Falsig, Mogens,Lund, Henning
, p. 591 - 596 (2007/10/02)
Electrochemical reduction of 4,5-bis(alkylthio)-1,3-dithiol-2-ones (1a-d) in aprotic medium, followed by alkylation, gives tetrathioethylenes (2) in nearly quantitative yield.A similar reduction and alkylation of 1,3,4,6-tetrathiapentalene-2,5-dione (3) leads to 1 in almost quantitative yield. 4,5-Bis(alkylthio)-1,3-dithiole-2-thiones (4) gives tetrathiooethylenes under similar conditions in lower yield than 1.The mechanism of the reactions is discussed on the basis of the preparative and cyclic voltammetric results.
