tetrakis(diphenylphosphino)tetrathiafulvalene | 153261-10-0

• 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: tetrakis(diphenylphosphino)tetrathiafulvalene
• 英文别名: tetrakis(diphenylphosphine)-tetrathiafulvalene；tetrakis(diphenylphosphanyl)tetrathiofulvalene；(PPh2)4TTF；[2-[4,5-Bis(diphenylphosphanyl)-1,3-dithiol-2-ylidene]-5-diphenylphosphanyl-1,3-dithiol-4-yl]-diphenylphosphane
• CAS: 153261-10-0
• 化学式: C₅₄H₄₀P₄S₄
• 分子量: 941.071
• InChiKey: XFCJTVXOUPIWKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.1
• 重原子数：
  62
• 可旋转键数：
  12
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  [Au(mesityl)(AsPh3)] 、 tetrakis(diphenylphosphino)tetrathiafulvalene 以 二氯甲烷 为溶剂， 以55%的产率得到[(AuMes)4(PPh2)4TTF]
  参考文献：
  名称：

  Tetrathiafulvalene-functionalized phosphine as a coordinating ligand. X-Ray structures of (PPh2)4TTF and [(AuCl)4{(PPh2)4TTF}]

  摘要：

  膦 (PPh2)4TTF (P4) (1) 与金（I）配合物 [AuX(tht)] （X = Cl、C6F5；tht = 四氢噻吩）或 [Au(Mes)(AsPh3)] （Mes = 2,4,6-Me3C6H2）反应，得到四核衍生物 [(AuX)4P4]（X = Cl，2；C6F5，3；Mes，4）。以[Au(Trip)(AsPh3)]（Trip = 2,4,6-Pri3C6H2）为起点的类似反应可得到二核衍生物[(AuTrip)2P4] (5)。当膦类化合物 P4 与 [Cu(MeCN)4]PF6、AgCF3SO3 或 [Au(tht)2]CF3SO3 以 2∶1 的摩尔比反应时，络合物 [M(P4)2]A （A = PF6，M = Cu，6；A＝CF3SO3，M＝Ag，7，Au，8），或者使用 1∶1 摩尔比时得到{[M2P4](CF3SO3)2}n（M＝Ag，9；Au，10）。报告了对这些新络合物的可见紫外光和电化学研究。与游离 P4 (1) 配体的两种可逆氧化作用相比，络合物 2-10 在更正的电位下会发生两种单电子氧化作用，生成单阳离子和双阳离子。X 射线分析证实了 1 和 2 的结构。

  DOI：

  10.1039/b106310n
• 作为产物：
  描述：

  二苯基氯化膦 在 lithium diisopropyl amide 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 336.0h， 生成 tetrakis(diphenylphosphino)tetrathiafulvalene
  参考文献：
  名称：

  1,3-二硫代-2-硫酮的P-官能化四硫富瓦烯？

  摘要：

  提出了合成单-和双-膦酰基化的1，3-二硫代-2-硫酮2和3的方案。的反应2或3与过氧化氢-尿素或导致相应的P（元素硫V）硫属化物1,3-二硫-2-硫酮4-7。所有化合物均通过31 P，1 H和13 C NMR，IR光谱和元素分析进行​​表征。另外，通过单晶X射线衍射分析来分析化合物3和4。3与P（OEt）3的反应通过还原性的C 2，C 2偶联反应选择性地导致四烷基膦酰基化的四硫富瓦烯衍生物II。对亚磷酸酯介导的1，3-二硫代-2-硫酮的还原二聚机理进行了全面的计算分析。

  DOI：

  10.1039/d0nj02984j

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。
• Homoleptic complexes of Ag(I), Cu(I), Pd(II) and Pt(II) with tetrathiafulvalene-functionalized phosphine ligands †
  作者：Bradley W. Smucker、Kim R. Dunbar

  DOI：10.1039/a908559i

  日期：——

  Homoleptic complexes of the type [M(L–L)2]+/2+ where L–L is a chelating tetrathiafulvalene-based phosphine ligand have been synthesized and fully characterized by X-ray crystallography, 31P1H} NMR spectroscopy and electrochemistry. In this study, square-planar cations of Pd(II) and Pt(II) with tetrakis(diphenylphosphino)-tetrathiafulvalene (P4) and tetrahedral cations of Ag(I) and Cu(I) with 3,4-dimethyl-3′

  [M（L–L）2 ] + / 2 +类型的同质络合物，其中L–L为基于四硫富瓦烯的螯合膦配体 已合成并具有以下特征 X射线晶体学，31 P 1 H}核磁共振波谱和电化学。在这项研究中，正方形平面阳离子Pd（II）和Pt（II）的四（二苯基膦基）-四硫富瓦烯 （P4）和四面体 阳离子分离了具有3,4-二甲基-3'，4'-双（二苯基膦基）四硫富瓦烯（o-P2）的Ag（I）和Cu（I）。对六种不同结晶化合物的X射线研究表明，TTF（四硫富瓦烯）取代基在很大程度上受晶体堆积力的影响。根据每个Pd / Pt或Cu / Ag对的显着相似性判断，固态结构与金属的身份无关。电化学研究表明，TTF氧化还原集中在不同的膦 配体 在这些化合物中被电子隔离。
• Fourmigue, Marc; Jarshow, Sylvia; Batail, Patrick, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 175 - 178
  作者：Fourmigue, Marc、Jarshow, Sylvia、Batail, Patrick

  DOI：——

  日期：——
• Bis- and tetrakis-(diphenylphosphino) tetrathiafulvalenes as precursors of redox-active organic—inorganic polymeric networks
  作者：M. Fourmigué、C.E. Uzelmeier、K. Boubekeur、S.L. Bartley、K.R. Dunbar

  DOI：10.1016/s0022-328x(96)06637-5

  日期：1997.2

  Lithiation of the (Z)-, (E)-dimethyltetrathiafulvalene mixture and subsequent reaction with ClPPh2 afford (Z)- and (E)-dimethyl-bis(diphenylphosphino)tetrathiafulvalene which are separated by fractional recrystallization. The identity of(Z)-P-2 has been ascertained by its X-ray crystal structure determination. By similar methods, tetrakis(diphenylphosphino)tetrathiafulvalene (P-4) is obtained from the tetrathiafulvalene tetralithium derivative. Cyclic voltammetry experiments reveal that the new compounds oxidize reversibly in two one-electron steps to the radical cation and dication. Reaction of o-P-2 with the dinuclear complex [Rh-2(NCCH3)(10)](BF4)(4) has been investigated and found to produce the square-planar Rh(I) compound [(o-P-2)(2)Rh][BF4]. The identity of the product has been confirmed by X-ray crystallography, FAB-MS, elemental analysis, and NMR spectroscopy. Several reactions of solvated cations were also performed, all of which appear to lead to products with o-P-2 and P-4 ligands.
• Analysis of Transition-Metal Compounds Containing Tetrathiafulvalene Phosphine Ligands by Fast Atom Bombardment Mass Spectrometry:  Limitations and the Development of Matrix Additives for the Desorption of Multiply Charged Complexes
  作者：John M. Asara、Calvin E. Uzelmeier、Kim R. Dunbar、John Allison

  DOI：10.1021/ic971123w

  日期：1998.4.20

  A series of new complexes incorporating the functionalized tetrathiafulvalene (TTF) ligands ortho-(CH3)(2)(P(C6H5)(2))(2)TTF (o-P2) and (P(C6H5)(2))(4)TTF (P4) have been prepared and studied by fast atom bombardment mass spectrometry (FABMS). The mononuclear o-P2 complexes [M(o-P-2)(2)](BF4)(2) (M = Fe, Pd, Pt) and [Co(o-P2)(2)(NCCH3)(2)](BF4)(2) were synthesized from reactions of the free ligand with the fully solvated BF4- salts [M(NCCH3)(n)](BF4)(2) (M = Fe, Co, n = 6; M = Pd, Pt, n = 4). The dinuclear P4 complex, [Pt-2(P4)(NCCH3)(4)](BF4)(4), was produced by reacting the free ligand with PtCl2(NC7H5)(2) followed by abstraction of the chlorides with AgBF4 in acetonitrile. Reaction of [Pd(NCCH3)](BF4)(2) with 1 equiv of P4 produces the polynuclear compound formulated as [Pd(P4)](n)(BF4)(2n), which was characterized by infrared, H-1, and P-31H-1} NMR spectroscopies and elemental analysis. The use of FABMS in this study was undertaken in order to elucidate the chemical options of multiply charged cations in the desorption process from the liquid matrix to the gas phase. The use of additives to the FAB matrix (m-nitrobenzyl alcohol) was demonstrated for the P4 complexes which do not give spectra in this medium due to a high positive net charge. The addition of triflic acid (HOTf or CF3SO3H) to the FAB matrix/analyte solution was shown to assist in the MS analysis of cationic complexes with up to six charges and a mass range up to m/z 4000. When HOTf is added, bound OTf- anions are formed and are attached to the cationic complex, lowering the net charge to +1. The method of using matrix additives as opposed to chemically synthesizing the OTf- compounds is a convenient in situ method which produces species that are capable of being analyzed by FABMS.