3,4-dimethyltetrathiafulvalene | 62024-60-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 英文名称: 3,4-dimethyltetrathiafulvalene
• 英文别名: o-3,4-dimethyltetrathiafulvalene；ortho-dimethyltetrathiafulvalene；2,3-dimethyltetrathiafulvalene；6,7-dimethyltetrathiafulvalene；4,5-dimethyl-[2,2']bi[1,3]dithiolylidene；Dimethyltetrathiafulvalene；2-(1,3-dithiol-2-ylidene)-4,5-dimethyl-1,3-dithiole
• CAS: 62024-60-6
• 化学式: C₈H₈S₄
• 分子量: 232.416
• InChiKey: BTQDPOVTMFCMKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-dimethyltetrathiafulvalene 在 正丁基锂 、 N,N-二异丙基乙胺 、 全氟己基碘烷 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.0h， 以53%的产率得到2,3-diiodo-6,7-dimethyltetrathiafulvalene
  参考文献：
  名称：

  通过点击化学分析四硫富瓦烯单和双1,2,3-三唑前体：结构多样性和反应性†

  摘要：

  按照钌催化的叠氮化物-炔烃环加成反应，通过点击化学合成了供体邻-二甲基-TTF-（Nn -Bu-1,2,3-三唑）1,5-异构体。单晶X射线分析表明，TTF和三唑单元之间呈平面构象，并且在固态下在超分子水平上发生了一系列分子间相互作用。相同的步骤允许制备相应的邻位-二甲基-TTF-双（三唑）也具有结构特征。由于空间位阻，三唑单元不再与TTF主链成平面。已经在质子化和烷基化反应中研究了三唑环的反应性，并通过紫外-可见光谱法进行了监测，这清楚地表明了分子内电荷转移带的红移。已分离出TTF-甲基-三唑鎓盐，并通过单晶X射线分析进行了分析。所有的TTF-三唑和三唑鎓盐都是自由基阳离子盐的有价值的前体，因为它们具有氧化电势和各种可能的分子间相互作用。

  DOI：

  10.1039/c4ob00148f
• 作为产物：
  描述：

  6,7-dimethyltetrathiafulvalene-6-carboxylic acid 在 双氧水 作用下， 以 硝基甲烷 、 乙腈 为溶剂， 生成 3,4-dimethyltetrathiafulvalene
  参考文献：
  名称：

  Kreitsberga, Ya. N.; Neiland, O. Ya., Journal of Organic Chemistry USSR (English Translation), 1986, vol. 22, # 11, p. 2131 - 2134

  摘要：

  DOI：

文献信息

• Sb⋯S and S⋯S interactions in the first neutral and oxidized diphenylstibino (Ph₂Sb–) derivatives of the redox active tetrathiafulvalene (TTF) core
  作者：Srinivasan S. Kuduva、Narcis Avarvari、Marc Fourmigué

  DOI：10.1039/b205594p

  日期：——

  The preparation of the monostibines o-Me2TTF–SbPh2 (1) and Me3TTF–SbPh2 (2), the ortho distibine o-Me2TTF(SbPh2)2 (3) and the tetrastibine TTF(SbPh2)4 (4) is described together with their electrochemical properties and the X-ray crystal structures of the neutral 1 and 3. In the former, one intermolecular Sb⋯S contact completes the co-ordination sphere of the antimony atom while in 3 the TTF moieties stack on top of each other with no evidence for Sb⋯S interactions. Electrocrystallisation of 2 in the presence of [n-Bu4N]2[Mo6O19] affords a 2 ∶ 1 salt, [2]2[Mo6O19] where the 2+˙ cation radical species are associated into diamagnetic [2]22+dyads through a strong HOMO⋯HOMO overlap interaction, separated from each other by the [Mo6O19]2− counter ions.

  本文描述了单锑化合物o-Me2TTF–SbPh2 (1) 和Me3TTF–SbPh2 (2)，邻二锑化合物o-Me2TTF(SbPh2)2 (3) 以及四锑化合物TTF(SbPh2)4 (4) 的制备，同时介绍了它们的电化学性质和中性化合物1和3的X射线晶体结构。在化合物1中，一个分子间的Sb–S接触完成了锑原子的配位球，而在3中，TTF部分相互堆叠，没有发现Sb–S相互作用的证据。在存在[n-Bu4N]2[Mo6O19]的条件下对化合物2进行电晶体化，可以得到盐 [2]2[Mo6O19]，其中2+·阳离子自由基通过强HOMO–HOMO重叠相互作用聚集成顺磁性的[2]22+二聚体，彼此之间由[Mo6O19]2−反离子隔开。
• Novel Bonding Modes between Tetrathiafulvalenes (TTFs) and Transition Metal Centers: π‐Bonding and Covalent TTFSiMe ₂ −ML _<i>n</i> Coordination to Platinum
  作者：Mathuresh N. Jayaswal、Harmel N. Peindy、Fabrice Guyon、Michael Knorr、Narcis Avarvari、Marc Fourmigué

  DOI：10.1002/ejic.200300930

  日期：2004.7

  [Pt(η2-C2H4)(PPh3)2] leads to the π complexes [Pt(η2-TTF)(PPh3)2] (1) and [Pt(η2-o-Me2TTF)(PPh3)2] (2), respectively. An X-ray crystallographic study performed on 2 confirmed, that TTFs act as a π acidic ligand. NMR studies revealed the existence, in solution, of an equilibrium between free and complexed TTF. Dilithiation of o-Me2TTF and subsequent silylation with ClSiMe2H afforded 3,4-dimethyl-3′,4′-(dime

  已经开发了两种将 TTF 与过渡金属中心协调的新策略。四硫富瓦烯 (TTF) 或 3,4-二甲基四硫富瓦烯 (o-Me2TTF) 与 [Pt(η2-C2H4)(PPh3)2] 反应生成 π 配合物 [Pt(η2-TTF)(PPh3)2] (1 ) 和 [Pt(η2-o-Me2TTF)(PPh3)2] (2)，分别。对 2 进行的 X 射线晶体学研究证实，TTF 充当 π 酸性配体。核磁共振研究揭示了在溶液中游离和复合 TTF 之间存在平衡。o-Me2TTF 的二锂化和随后的 ClSiMe2H 硅烷化得到 3,4-二甲基-3',4'-(二甲基甲硅烷基)四硫富瓦烯 (3)，其结构已被表征。3 通过跨 [Pt(η2-C2H4)(PPh3)2] 的氧化加成反应生成 [Ptη2-o-(SiMe2)2TTFMe2}(PPh3)2] (4)，其中 TTF 配体共价连接到铂通过 SiMe2 桥。已通过循环伏安法研究了
• (N-Methylthiocarbamoyl)tetrathiafulvalene derivatives and their radical cations: synthetic and X-ray structural studies
  作者：Adrian J. Moore、Martin R. Bryce、Andrei S. Batsanov、Julie N. Heaton、Christian W. Lehmann、Judith A. K. Howard、Neil Robertson、Allan E. Underhill、Igor F. Perepichka

  DOI：10.1039/a802037j

  日期：——

  Lithiation of 4,5-bis(methylsulfanyl)-TTF 9, 4,5-(ethylenedisulfanyl)-TTF 10, 4,5-dimethyl-TTF 11 and 4,5,5′-trimethyl-TTF 12 (TTF=tetrathiafulvalene) followed by reaction with methyl isothiocyanate affords the corresponding (N-methylthio-carbamoyl)-TTF derivatives 14–17, respectively, in 54–70% yields. These new TTF derivatives display a broad intramolecular charge-transfer band in their UV–VIS spectra arising from conjugation between the donor TTF ring and the acceptor N-methylthiocarbamoyl moiety. Steric hindrance between the adjacent N-methylthiocarbamoyl and methyl substituents in 17 causes a marked hyposchromic shift in this band (λmax 395 nm) compared to compounds 14–16 (lambda;max 435–467 nm). Consistent with the electron-withdrawing properties of the N-methylthiocarbamoyl substituent, its attachment to the TTF ring raises slightly the oxidation potential of the system. Charge transfer complexes of these donors and (N-methylthiocarbamoyl)-TTF 2 with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and salts with bromide anions are reported, some of which have high room temperature conductivity values. The X-ray crystal structures are presented for 16, 17 and the salts 2·Br, 14·TCNQ and (17)2·20. The structure of 16 comprises orthogonal dimers (kappa packing) while in the structure of 17 individual molecules are orthogonal to each other. There is weak intermolecular hydrogen bonding in both 16 and 17. In the structure of 2·Br, the radical cations 2+· are almost planar and they form an infinite stair-like stack of dimers, with bromide anions situated between the stacks, and linked with the cation by a strong N–H‥Br bond. The structure of 14·TCNQ comprises mixed ‥DDAADD‥ stacks; the N-methylthiocarbamoyl group engages in an interstack N–H‥N bond with a TCNQ anion. Analysis of the bond lengths in the structure suggests that there is partial charge transfer from 14 to TCNQ. In the structure of (17)2·20 molecules form mixed ‥DDADDA‥ stacks and analysis of bond lengths suggests that there is only a small degree of charge transfer from donor to acceptor. The geometries of compounds 2, 14, 16, 17 were optimised using the PM3 semi-empirical method and the results compare favourably with the X-ray structural data.

  将 4,5-双（甲硫基）-TTF 9、4,5-（亚乙基二硫基）-TTF 10、4,5-二甲基-TTF 11 和 4,5,5′-三甲基-TTF 12（TTF=四硫代富勒烯）进行锂化，然后与异硫氰酸甲酯反应，可分别得到相应的（N-甲硫基氨基甲酰基）-TTF 衍生物 14-17，收率为 54-70%。这些新的 TTF 衍生物在其紫外-可见光谱中显示出宽阔的分子内电荷转移带，这是由于供体 TTF 环和受体 N-甲基硫代氨基甲酰基之间的共轭作用产生的。与 14-16 号化合物（λmax 435-467 nm）相比，17 号化合物中相邻的 N-甲基硫代氨基甲酰基和甲基取代基之间的立体阻碍导致该波段（λmax 395 nm）出现明显的低色度偏移。与 N-甲基硫代氨基甲酰取代基的吸电子特性相一致，N-甲基硫代氨基甲酰取代基与 TTF 环的连接会略微提高体系的氧化电位。据报道，这些供体和（N-甲基硫代氨基甲酰基）-TTF 2 与 7,7,8,8-四氰基对二醌甲烷（TCNQ）以及溴阴离子盐的电荷转移配合物，其中一些具有很高的室温电导率值。本文介绍了 16、17 以及盐类 2-Br、14-TCNQ 和 (17)2-20 的 X 射线晶体结构。16 的结构由正交二聚体（卡帕堆积）组成，而在 17 的结构中，单个分子彼此正交。16 和 17 中都存在微弱的分子间氢键。在 2-Br 的结构中，自由基阳离子 2+- 几乎是平面的，它们形成一个无限阶梯状的二聚体堆栈，溴阴离子位于堆栈之间，并通过强 N-H‥Br 键与阳离子相连。14-TCNQ 的结构由混合的 ‥DDAADD‥ 堆栈组成；N-甲基硫代氨基甲酰基与 TCNQ 阴离子在堆间形成 N-H‥N 键。对结构中键长的分析表明，14 与 TCNQ 之间存在部分电荷转移。在 (17)2-20 的结构中，分子形成了混合的‥DDADDA‥堆栈，对键长的分析表明，从供体到受体只有少量的电荷转移。利用 PM3 半经验方法对化合物 2、14、16 和 17 的几何结构进行了优化，结果与 X 射线结构数据相比非常理想。
• Identification and Analysis of a 2:1 Monoclinic Phase for the Organic Donor–Acceptor Complex o-Me2TTF-TCNB: Structural and Spectroscopic Studies of a New Solid State Configuration
  作者：Steven P. Fisher、Eric W. Reinheimer

  DOI：10.1007/s10870-014-0497-3

  日期：2014.3

  In this communication, we present the single crystal X-ray structure and spectroscopic properties for a newly discovered 2:1 phase for the organic donor–acceptor complex o-Me2TTF-TCNB. This new phase crystallizes in the monoclinic space group P2 1 /n with a = 7.6846(17) Å, b = 19.8987(19) Å, c = 9.1844(8) Å and β = 91.955(7)°. Valence sensitive bond distances, specifically the central C=C bond and four ancillary C–S bonds in o-Me2TTF and the cyanide groups of TCNB were compared to those from the free components and suggested that both the donor and acceptor molecules remained neutral in the complex. Additionally, infrared spectroscopy measurements were conducted and the corresponding vibrational frequencies for selected bands from the donor and acceptor molecules further support the hypothesis that neutral molecules were present. Herein we present the structure and infrared spectroscopic properties for the 2:1 monoclinic phase of the donor–acceptor complex o-Me2TTF-TCNB (o-Me2TTF = o-3,4-dimethyltetrathiafulvalene; TCNB = 1,2,4,5-tetracyanobenzene), a complex which has already had its 1:1 triclinic form described.

  在本次通讯中，我们展示了新发现的有机供体-受体复合物 o-Me2TTF-TCNB 2:1 相的单晶 X 射线结构和光谱特性。这种新相在单斜空间群 P2 1 /n 中结晶，其中 a = 7.6846(17) Å、b = 19.8987(19) Å、c = 9.1844(8) Å 和 β = 91.955(7)°。价敏感键距，特别是 o-Me2TTF 中的中心 C=C 键和四个辅助 C-S 键以及 TCNB 的氰化物基团与游离组分的键距进行了比较，表明供体和受体分子在复杂的。此外，还进行了红外光谱测量，来自供体和受体分子的选定谱带的相应振动频率进一步支持了中性分子存在的假设。在此，我们介绍了供体-受体复合物 o-Me2TTF-TCNB (o-Me2TTF = o-3,4-二甲基四硫富瓦烯；TCNB = 1,2,4,5-) 2:1 单斜晶相的结构和红外光谱特性四氰基苯），一种已描述其 1:1 三斜晶型的络合物。
• Hybrid Material Based on the Lindquist Polyoxometalate [W6O19]2− and the organosulfur donor o-Me2TTF: A Combined Structural and Spectroscopic Study
  作者：Eric W. Reinheimer、Damian Jankowski、Roman Świetlik、Marc Fourmigué

  DOI：10.1007/s10870-013-0403-4

  日期：2013.4

  The synthesis, crystal structure and spectroscopic properties of the hybrid radical cation salt containing oxidized o-3,4-dimethyltetrathiafulvalene (o-Me2TTF) and the Lindquist polyoxometalate anion [W6O19]2− are reported. The title salt represents the first time a Lindquist polyoxometalate has been utilized as the counter anion with this unsymmetrical member of the TTF family of derivatives. The salt crystallizes in the triclinic space group $$ P\bar1} $$ with a = 7.6211(7) Å, b = 9.5231(9) Å, c = 12.2148(11) Å, α = 105.5870(10)°, β = 106.8340(10)° and γ = 95.6950(10)°. Resolution of the solid state structure revealed that the o-Me2TTF radical cations aggregate as isolated face-to-face dimers with intradimer interactions between neighboring sulfur atoms at distances <3.6 Å. Hydrogen bonding was also observed between hydrogen atoms bound to sp 2-hybridized carbon atoms of o-Me2TTF and bridging oxygen atoms of [W6O19]2−. Single crystal IR and Raman spectra were also collected and provide further evidence that the o-Me2TTF donors have been oxidized to their corresponding radical cationic states. Herein we present the structure and single crystal spectroscopic properties of the hybrid salt (o-Me2TTF)2[W6O19], which combines the unsymmetrical TTF derivative o-Me2TTF with the closed shell Lindquist polyoxometalate [W6O19]2−.

  报告了含有氧化邻-3,4-二甲基四硫杂戊烯（邻-Me2TTF）和林奎斯特多氧甲基阴离子 [W6O19]2- 的混合自由基阳离子盐的合成、晶体结构和光谱特性。该标题盐代表了林奎斯特多氧化金属酸盐首次被用作 TTF 衍生物家族中这种非对称成员的阴离子。该盐在三linic 空间群 $$ P\bar1} $$ 中结晶，a = 7.6211(7) 埃，b = 9.5231(9) 埃，c = 12.2148(11) 埃，α = 105.5870(10)°，β = 106.8340(10)°和γ = 95.6950(10)°。对固态结构的解析显示，o-Me2TTF 自由基阳离子以孤立的面对面二聚体形式聚集，相邻硫原子之间的距离为 3.6 Å 。在 o-Me2TTF 的 sp 2 杂化碳原子上结合的氢原子与 [W6O19]2- 的桥接氧原子之间也观察到了氢键。我们还收集了单晶红外光谱和拉曼光谱，进一步证明邻甲基 2TTF 给体已被氧化成相应的自由基阳离子状态。在此，我们介绍了混合盐 (o-Me2TTF)2[W6O19]的结构和单晶光谱特性，该混合盐结合了非对称 TTF 衍生物 o-Me2TTF 和闭壳林奎斯特多氧化金属盐 [W6O19]2-。