1,2-bis(diphenylphosphinothioyl)ethane | 7615-76-1

• 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: 1,2-bis(diphenylphosphinothioyl)ethane
• 英文别名: Bis-(diphenylphosphino)-ethan-disulfid；Ethane-1,2-diylbis(diphenylphosphane) disulfide；2-diphenylphosphinothioylethyl-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 7615-76-1
• 化学式: C₂₆H₂₄P₂S₂
• 分子量: 462.556
• InChiKey: ZCRRZJNBRXYUKB-UHFFFAOYSA-N

物化性质

• 熔点：
  224-225 °C(Solv: acetone (67-64-1))
• 沸点：
  220-235 °C(Press: 0.002 Torr)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,2-bis(diphenylphosphinothioyl)ethane 在 Raney-Ni 作用下， 以 乙醇 、 苯 为溶剂， 反应 3.0h， 以97%的产率得到1,2-双(二苯基膦)乙烷
  参考文献：
  名称：

  硫化膦的 Raney-Ni 还原

  摘要：

  图形摘要 摘要 多种叔膦硫化物已被 Raney-Ni 还原，在温和的条件下高效地生成相应的膦。烷基、芳基、无环、环状以及空间拥挤的硫化膦用相同的设备还原。光学活性的 P-立体异构膦硫化物被立体定向​​地还原，并在 P 处保持构型的清洁。不饱和硫化膦的还原不是完全化学选择性的，并且伴随着双键的部分还原而发生。通过在 H2 气氛（气球）下进行还原，可以一步实现将不饱和膦硫化物完全还原为相应的完全饱和膦。

  DOI：

  10.1080/10426507.2016.1225052
• 作为产物：
  描述：

  1,2-bis(diphenylphosphino)ethane bis(borane) 在 辛烯 、 sulfur 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以86%的产率得到1,2-bis(diphenylphosphinothioyl)ethane
  参考文献：
  名称：

  Chemo-, regio- and stereoselective conversion of P-chirogenic phosphorus borane complexes into their PO or PS derivatives

  摘要：

  Chiral and achiral organophosphorus borane complexes are readily transformed into their corresponding phosphoryl or thiophosphoryl compounds in high yields using one-pot procedures with stereoselectivities reaching 100% in many cases. Both oxidation and sulfuration were performed under neutral or mild conditions and were applied to various organophosphorus borane complexes (phosphines, phosphinates, chlorophosphines, aminophosphines, etc.). In the case of the dissymmetric diphosphine or aminophosphine phosphinite ligands, the reaction of their diborane complexes proceeds regiospecifically to a single phosphorus group, affording the corresponding hybrid derivatives. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00236-1

文献信息

• Mechanism of Catalytic Chalcogen Atom Replacement of Phosphine Chalcogenides and Separation of the Intermediate Phosphine
  作者：Sen-ichi Aizawa、Arpi Majumder、Daisuke Maeda、Akina Kitamura

  DOI：10.1246/cl.2009.18

  日期：2009.1.5

  The reaction mechanism of the chalcogen atom replacement of phosphine chalcogenides has been revealed to be dissociative from a kinetic investigation for the reaction of phosphine selenide with sulfur. The dissociation is enthalpically promoted by the catalysis of Pd0. For a bidentate phosphine chalcogenide, the intermediate phosphine was separated as the PdII complex by the catalysis and oxidative addition of Pd0 complex. The novel catalytic replacement and dissociation of chalcogen atom are applicable to regeneration of phosphines from their oxides via the phosphine sulfides.

  通过研究膦硒化物与硫反应的动力学，揭示了膦硒化物中硫族原子替代反应的机理为解离性反应。Pd0的催化作用在热力学上促进了这种解离。对于双齿膦硒化物，催化作用和Pd0配合物的氧化加成可以分离出作为PdII配合物的中介膦。这种新颖的催化替代和硫族原子解离作用，可应用于通过膦硫化物从膦氧化物中再生膦的过程中。
• Sulphur-ligand–metal complexes. Part 7. The interaction of some diphosphine dichalcogenides and tetra-alkylthiuram disulphides with halogens and some first-row transition-metal salts
  作者：Eric W. Ainscough、Andrew M. Brodie

  DOI：10.1039/dt9770000565

  日期：——

  are each thought to produce cyclised dications similar to (A). With the appropriate copper(II) salts (in excess) and L′ in acetone, the copper(III) derivatives [CuCl2(S2CNR2)] and [Cu(S2CNR2)2][BF4](R = Me or Et) have been isolated. In the first two cases when the solvent is changed to chloroform–ethanol the copper(II) derivatives [CuCl(S2CNR2)] are found. With Ni[BF4]2·6H2O and NiCl2·6H2O in excess

  碘与R 2 P（X）·[CH 2 ] n ·（X）PR 2相互作用[R = Ph，X = S，n = 1（L'）; R = Ph，X = S，n = 2（L 2）；或R = Me中，X = S，Ñ = O（L 4）]，得到式L·2升的电荷转移的加合物2或LL 2，而其中R相应的反应2 N·CS·S 2 ·CS ·NR 2 [R = Me（L 5）或Et（L 6）]给出类型L'·l 6的产品，其中L'可能被氧化，从而给出带有环化结构的指示剂（未显示图形）2+（A）（L 8，R = Et； L 9，R = Me），带有两个[l 3 ] –作为抗衡离子。在乙醚或丙酮-氯仿中，L'与FeCl 3，CO [BF 4 ] 2 ·6H 2 O和CoCl 2 ·6H 2 O（全部过量）的相互作用也产生了以下含有（A）物质的产物配合物; [L 9 ] [FeCl 4 ] 2，[L 8 ] [FeCl 4 ]
• Sulphur-ligand–metal complexes. Part IV. Copper complexes with bidentate tertiary-phosphine sulphide and selenide ligands and the crystal structure of a three-co-ordinate copper(<scp>I</scp>) complex
  作者：Eric W. Ainscough、Helen A. Bergen、Andrew M. Brodie、Kevin A. Brown

  DOI：10.1039/dt9760001649

  日期：——

  tetrahedral arrangement of ligands). Similar species [CuL2Cl2](L = Me2PhPS or MePh2PS, L2= bdte or tmdpds) are detected in solution and have the same tetrahedral stereochemistry. Related complexes of AgI, HgII, ZnII, PtII, and PdIIare reported. Crystals of [Cu(bdtm)Cl]·Me2CO are orthorhombic, space group Pna21with a= 17.185(2), b= 13.640(3), c= 12.058(1)Å, Z= 4. The structure was determined by the heavy-atom

  描述了以下化合物的制备：[CuL 2 ] [ClO 4 ] [L =双（二苯基膦基硫代酰基）甲烷（bdte），或双（二苯基膦基硫代硒酰基）甲烷（bdsm）]，[ CuLX] a [L = bdtm，bdte，bdtm或四甲基二膦二硫化物（tmdpds）；n = 1或2]和[Cu（bdtm）Cl 2 ]（其中光谱证据表明配体的四面体结构变形）。在溶液中检测到相似的物种[CuL 2 Cl 2 ]（L = Me 2 PhPS或MePh 2 PS，L 2 = bdte或tmdpds），并且具有相同的四面体立体化学。Ag I的相关配合物报道了Hg II，Zn II，Pt II和Pd II。[Cu（bdtm）Cl]·Me 2 CO晶体是正交晶体，空间群Pna 2 1，a = 17.185（2），b = 13.640（3），c = 12.058（1）Å，Z =4。结构用重原子法测定了R 2，并用最小二乘法将衍射仪测得的2
• Alkylidenverbrückte diphosphane und dichlalkogenodiphosphorane als liganden in kationischen cyclopentadienyleisencarbonyl-komplexen
  作者：Hans Schumann

  DOI：10.1016/s0022-328x(00)98971-x

  日期：1987.2

  of the FeFe bond in [C5H5Fe(CO)2]2 in the presence of alkylide-bridged diphosphanes LL (LL = (C6H5)2P(CH2)n(P(C6H5)2; n = 1–3), (C6H5)2PCH2As(C6H5)2 and dichalcogenodiphosphoranes (X)LL(X) ((X)LL(X) = (C6H5)2P(X)(CH2)n(X)P(C6H5)2; X  O, S, Se; n = 1–3) yields the complexes [C5H5Fe(CO)2L′]BF4 (L′ = LL, (X)LL(X); X  S, Se) in high yield. the complexes react with Ni(CO)4 under photochemical conditions

  [C 5 H 5 Fe（CO）2 ] 2中的FeFe键的氧化裂解，存在烷基桥联的二膦LL（LL=（C 6 H 5）2 P（CH 2）n（P（C 6 H 5）2；n = 1-3），（C 6 H 5）2 PCH 2 As（C 6 H 5）2和二氢二氟膦（X）LL（X）（（X）L L（X）=（C 6 H 5）2 P（X）（CH2）n（X）P（C 6 H 5）2；XO，S，Se; n = 1-3）产生高浓度的[C 5 H 5 Fe（CO）2 L'] BF 4（L'=LL，（X）LL（X）; XS，Se）屈服。络合物在光化学条件下与Ni（CO）4反应以定量收率形成[C 5 H 5 Fe（CO）2（μ-L'）Ni（CO）3 ] BF 4，并在辐照下失去一个CO基团（ λ最大> 300纳米），以形成螯合物[C 5 H ^ 5的Fe（CO）L'] BF 4，可用于L'LL（P，As配体）和（X）LL（X）（X
• Photochemical Reactions of Re(CO)₅Br with Ph₂P(S)(CH₂)_nP(S)Ph₂ (n = 1,2,3)
  作者：Elif Subasi、Ozan Sanlı Sentürk、Fadime Ugur (Sarikahya)

  DOI：10.1515/znb-2004-0715

  日期：2004.7.1

  The complexes fac-[Re(CO)₃BrPh₂P(S)(CH₂)_nP(S)Ph₂}] [1a, n = 1; 2a, n = 2; 3a, n = 3] and [Re₂(CO)₈Br₂μ- Ph₂P(S)(CH₂)_nP(S)Ph₂}] [1b, n = 1; 2b, n = 2; 3b, n = 3] have been prepared by the photochemical reaction of Re(CO)₅Br with Ph₂P(S)(CH₂)_nP(S)Ph₂. The products have been characterized by elemental analysis, mass spectroscopy, FT-IR and ³¹ P-[¹H]-NMR spectrometry. The results suggest cis-chelate bidentate coordination of the ligand in fac-1a - 3a and cis-bridging bidentate coordination of the ligand between two metals in 1b - 3b.

  通过Re(CO)5Br与Ph2P(S)(CH2)nP(S)Ph2的光化学反应制备了配合物fac-[Re(CO)3BrPh2P(S)( )nP(S)Ph2}] [1a，n = 1; 2a，n = 2; 3a，n = 3]和[Re2(CO)8Br2μ-Ph2P(S)( )nP(S)Ph2}] [1b，n = 1; 2b，n = 2; 3b，n = 3]。通过元素分析、质谱、FT-IR和31P-[1H]-NMR光谱对产物进行了表征。结果表明，fac-1a - 3a中配体以顺式螯合双齿配位，1b - 3b中配体以顺式桥联双齿配位。