3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene | 141858-24-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene
• 英文别名: [2-(4,5-dimethyl-1,3-dithiol-2-ylidene)-5-diphenylphosphanyl-1,3-dithiol-4-yl]-diphenylphosphane
• CAS: 141858-24-4
• 化学式: C₃₂H₂₆P₂S₄
• 分子量: 600.77
• InChiKey: FDDZKMPWYBARSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  38
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 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-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene 以 二氯甲烷 、 氯仿 为溶剂， 生成 dichloro[dimethylbis(diphenylphosphino)tetrathiafulvalene]palladium(II) thallium(I) triflate adduct*diethyl ether
  参考文献：
  名称：

  Unexpected Reactivity of PdCl₂ and PtCl₂ Complexes of the Unsaturated Diphosphine o-Me₂TTF(PPh₂)₂ toward Chloride Abstraction with Thallium Triflate

  摘要：

  Attempted thallium triflate abstraction of chloride anions from the MCl2 complexes of the unsaturated chelating diphosphines o-dimethyl-bis(diphenylphosphino)tetrathiafulvalene (P2) (M = Pd, Pt) and cis-1,2-bis(diphenylphosphino)ethylene (dppen) (M = Pd) affords, surprisingly, a TI(OTf) adduct in the case of (P2)PdCl2 and (P2)PtCl2, with no chloride abstraction, and a dicationic bis(palladium) bis(triflate) salt in the case of (cis-dppen)PdCl2, in which only one Cl anion was removed. The crystal structures of these complexes were determined by X-ray analysis, which established the formulations (P2)MCl2.TI(OTf) (M = Pd, Pt) and [(dppen)PdCl](2)(OTf)(2), respectively. These compounds can be seen as possible intermediates in the general chloride abstraction process between (P-P)MCl2 (M = Pd, Pt) and thallium triflate.

  DOI：

  10.1021/ic035447y
• 作为产物：
  描述：

  3,4-dimethyltetrathiafulvalene 、 二苯基氯化膦 在 lithium diisopropyl amide 作用下， 生成 3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene
  参考文献：
  名称：

  Fourmigue, M.; Batail, P., Bulletin de la Societe Chimique de France, 1992, # 1, p. 29 - 36

  摘要：

  DOI：

文献信息

• Structural and electrochemical study of metal carbonyl complexes with chelating bis- and tetrakis(diphenylphosphino)tetrathiafulvalenes
  作者：Narcis Avarvari、David Martin、Marc Fourmigué

  DOI：10.1016/s0022-328x(01)01249-9

  日期：2002.2

  and bimetallic complexes involving organometallic fragments such as M(CO)4 (M=Mo, W), Re(CO)3Cl and Fe(CO)3 coordinated to the chelating diphosphine 3,4-dimethyl-3′,4′-bis(diphenylphosphino)tetrathiafulvalene (P2) or tetraphosphine tetrakis(diphenylphosphino)tetrathiafulvalene (P4) have been synthesized and characterized. X-ray diffraction structures have been determined for P4[W(CO)4]2, P2Re(CO)3Cl

  几种涉及有机金属片段的单金属和双金属配合物，例如M（CO）4（M = Mo，W），Re（CO）3 Cl和Fe（CO）3与螯合的二膦3,4-二甲基-3'配位，合成并表征了4'-双（二苯基膦基）四硫富瓦烯（P2）或四膦四（二苯基膦基）四硫富瓦烯（P4）。已确定P4 [W（CO）4 ] 2，P2 Re（CO）3 Cl，P2 Fe（CO）3和P4 [Fe（CO）3 ] 2的X射线衍射结构。钨和rh的配合物在金属中心周围观察到八面体的几何形状，后者的配体以fac排列，而铁的两个对应部分都发现了稍微变形的三角双锥体。尽管如通过循环伏安法测量所证明的那样，该配合物比相应的游离膦更难于氧化，但第一氧化电位仍保持在通常范围内，从而提供了产生稳定的自由基阳离子盐的机会。在Fe络合物的情况下，第一个氧化波对应于顺磁性d 7 Fe（I）物质的形成，而在Mo，W和Re络合物中，金属中心比TTF核更难氧化。
• Redox bifunctionality in a Pt(ii) dithiolene complex of a tetrathiafulvalene diphosphine ligand
  作者：Kyong-Soon Shin、YounJung Jung、Su-Kyung Lee、Marc Fourmigué、Frédéric Barrière、Jean-François Bergamini、Dong-Youn Noh

  DOI：10.1039/b812797b

  日期：——

  The Pt(II) dithiolene complex of a tetrathiafulvalene diphosphine ligand exhibits two reversible redox systems at close potentials, localized on the weakly interacting TTF (tetrathiafulvalene) and Pt(dmit) moieties.

  四硫富瓦烯二膦配体的 Pt(II) 二硫醇络合物在接近电位下表现出两个可逆氧化还原系统，位于弱相互作用的 TTF（四硫富瓦烯）和 Pt(dmit) 部分上。
• Reaction of Octachlorodirhenate with a Redox-Active Tetrathiafulvalene Phosphine Ligand:  Spectroscopic, Magnetic, and Structural Characterization of the Unusual Paramagnetic Salt [ReCl₂(<i>o</i>-P2)₂][Re₂Cl₆(<i>o</i>-P2)] (<i>o</i>-P2 = <i>o</i>-{P(C₆H₅)₂}₂(CH₃)₂TTF)
  作者：Calvin E. Uzelmeier、Stuart L. Bartley、Marc Fourmigué、Robin Rogers、Giulio Grandinetti、Kim R. Dunbar

  DOI：10.1021/ic9808192

  日期：1998.12.1

  combination of infrared spectroscopy, mass spectrometry, and cyclic voltammetric measurements. Variable temperature dc susceptibility studies of [ReCl(2)(o-P2)(2)][Re(2)Cl(6)(o-P2)] (1.2) revealed classical Curie paramagnetic behavior (with a Curie constant equal to 0.395) and a large temperature independent paramagnetic contribution (chi(TIP) = 9.64 x 10(-)(3) emu/mol). The EPR spectrum of 1.2 consists

  [（n-Bu）（4）N]（2）[Re（2）Cl（8）]与四硫富瓦烯膦配体o- P（C（6（H）（5））（2）}（）的反应2）（CH（3））（2）TTF（o-P2）在回流的乙醇中产生混合核盐[ReCl（2）（o-P2）（2）] [Re（2）Cl（6）（ o-P2）]（1.2），由单核Re（III）配合物（1）和混合价Re（II）-Re（III）双核阴离子（2）组成。该复合物结晶为三斜空间群P＆onemacr;中的CH（2）Cl（2）溶剂化物，a = 13.4559（1）Å，b = 20.4015（3）Å，c = 21.5538（1）Å，alpha = 88.261（ 1）度，β= 72.987（1）度，γ= 84.933（1）度，Z =2。分子阳离子由赤道平面中的两个反式o-P2配体和轴向氯化物配体组成。双核阴离子对两个金属原子采用不对称配位环境的偏光几何形状。一个Re（II）中心与一个螯
• A series of complexes of the phosphorus-based TTF ligand o-P2 with the metal ions FeII, CoII, NiII, PdII, PtII, and AgI
  作者：Calvin E. Uzelmeier、Bradley W. Smucker、Eric W. Reinheimer、Mikhail Shatruk、Amanda W. O'Neal、Marc Fourmigu?、Kim R. Dunbar

  DOI：10.1039/b610659e

  日期：——

  Reactions of 3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene, o-P2, with [BF(4)](-) salts of Fe(ii), Co(ii), Ni(II), Pd(II), and Pt(II) yield complexes of general formula [M(o-P2)(2)][BF(4)](2). Similar reactions between o-P2 and AgSbF(6) or AgPF(6) produced the salts [Ag(o-P2)(2)][X] where X = [SbF(6)](-) or [PF(6)](-). The resulting compounds were fully characterized by (1)H and (31)P(1)H}

  3,4-二甲基-3'，4'-双（二苯基膦基）四硫富瓦烯，o-P2与Fe（ii），Co（ii），Ni（II）的[BF（4）]（-）盐的反应，Pd（II）和Pt（II）产生通式为[M（o-P2）（2）] [BF（4）]（2）的配合物。o-P2与AgSbF（6）或AgPF（6）之间的类似反应产生了盐[Ag（o-P2）（2）] [X]，其中X = [SbF（6）]（-）或[PF（6） ）]（-）。所得化合物通过（1）H和（31）P （1）H} NMR，红外和电子吸收光谱，循环伏安法，FAB-MS和单晶X射线衍射充分表征。顺磁性Co（II）化合物在较高温度下表现出S = 3/2状态，具有较大的自旋轨道耦合贡献，在20 K以下时有效S'= 1/2状态。
• Hybrid Organic/Inorganic Complexes Based on Electroactive Tetrathiafulvalene-Functionalized Diphosphanes Tethered to C₃-Symmetrized Mo₃Q₄ (Q = S, Se) Clusters
  作者：Narcis Avarvari、Kaplan Kiracki、Rosa Llusar、Victor Polo、Ivan Sorribes、Cristian Vicent

  DOI：10.1021/ic902244m

  日期：2010.2.15

  three-electron oxidized [Mo3S4Cl3(o-P2)3]4+ (14+) and [Mo3Se4Cl3(o-P2)3]4+ (24+) cations. These 14+ and 24+ cations represent still rare examples of complexes with oxidized TTF-ligands that are remarkably stable either toward diphosphane dissociation or phosphane oxidation. Polycrystalline samples of compound [1](PF6)4 were obtained by oxidation of compound [1]PF6 using NOPF6 which were analyzed by solid

  基于电活性四硫富富瓦烯（TTF）-官能化的邻-P 2二膦烷（邻-P 2 = 3,4-二甲基-3,4-双（二苯基膦基）四硫富富瓦烯）和无机碳的混合步骤的两步制备方法3对称的Mo 3 Q 4（Q = S，Se）簇，即[Mo 3 S 4 Cl 3（o -P 2）3 ] PF 6（[ 1 ] PF 6）和[Mo 3 Se 4 Cl 3（o -P2）3 ] PF 6（[ 2 ] PF 6）被报道。还基于X射线衍射实验和密度泛函理论（DFT）计算来描述它们的分子和电子结构，旨在理解有机部分和无机部分之间建立的相互作用。化合物[ 1 ] PF 6和[ 2 ] PF 6的循环伏安图显示归因于Mo 3 Q 4核的还原特征和由于TTF骨架引起的氧化特征。[ 1 ] PF 6和[ 2 ] PF的氧化化学还通过原位电喷雾电离（ESI）质谱，UV-vis和电子顺磁共振（EPR）测量研究了溶液中的6。当添加增加量的NOPF