1,9-bis-(diphenylphosphino)-3,7-dithianonane | 146234-60-8

• 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: 1,9-bis-(diphenylphosphino)-3,7-dithianonane
• 英文别名: 4,8-Dithia-1,11-diphosphaundecane, 1,1,11,11-tetraphenyl-；2-[3-(2-diphenylphosphanylethylsulfanyl)propylsulfanyl]ethyl-diphenylphosphane
• CAS: 146234-60-8
• 化学式: C₃₁H₃₄P₂S₂
• 分子量: 532.69
• InChiKey: WSWJCXQFPIYXGG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  35
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,9-bis-(diphenylphosphino)-3,7-dithianonane 在 selenium 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以72%的产率得到2-[3-(2-diphenylphosphinoselenoylethylsulfanyl)propylsulfanyl]ethyl-diphenyl-selanylidene-λ5-phosphane
  参考文献：
  名称：

  磷脂混合配体及其硫族化物衍生物的铜，银和金配合物的结构和光谱研究

  摘要：

  [Cu（MeCN）4 ] PF 6或AgBF 4与1摩尔当量的Ph 2 P（E）（CH 2）2 SZS（CH 2）2（E）PPh 2 [Z =（CH 2）2， E = S（L 1b）或Se（L 1c）; Z ＝（CH 2）3，E ＝无（L 2a），S（L 2b）或Se（L 2c）；Z = o -C 6 H 4，E =无（L 3a），S（L 3b）或Se（L 3c）]在脱气的丙酮，接着加入乙醚，得到单核配合物[ML]×（M =铜，X - = PF 6 - ; M =银，X - = BF 4 -中高收率）。金（我）物种[AUL] PF 6分别用L的反应得到（= L 1B，L 1C，L 2B，L 2C或L 3a中-L图3c）与[AUCL（THT）]（THT的1个摩尔当量的＝四氢噻吩）和TlPF 6。所有这些产品的特征是1 H，31 P- { 1 H}（在某些情况下77 Se- { 1 H}和109

  DOI：

  10.1039/dt9960004099

文献信息

• Lightinduced sulfur-dealkylation of phosphino-thioether nickel(0) complexes
  作者：Jang Sub Kim、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1016/s0020-1693(96)05237-1

  日期：1996.9

  redox events assigned to Ni 11 1 and Ni 1 0 . The one-electron reduction product produced by stoichiometric amounts of Cp2Co can be characterized by EPR. At 100 K rhombic signals show hyperfine coupling to two phosphorus atoms. Complete bulk chemical reduction of complexes 1, 2, 3 and 4 with Na/Hg amalgam provided the corresponding nickel(0) complexes 1R, 2R, 3R and 4R which were isolated as red solutions

  摘要在光化学条件下观察到（Ph2P（o-C6H4）SCH3）2Ni0中SCH3键的裂解，促使进一步研究镍（0）配合物及其稳定性。四齿P2S'2供体配体（S'=硫醚型S供体），其芳香环并入P至S链中，Ph2P（o-C6H4）S（CH2）3S（o-C6H4）PPh2（arom-PSSP），或S对S链Ph2P（CH2）2SCH2（o-C6H4）CH2S（CH2）2PPh2（PS-xy-SP）已用于形成四坐标方形方形镍（II）络合物，[（arom- PSSP）Ni]（BF4）2（2）和[（PS-xy-SP）Ni]（BF4）2（3）。双齿和四齿配体Ph2P（o-C6H4）SCH2CH3（arom-PSEt）和Ph2P（CH2）2S（CH2）3S（CH2）2PPh2（PSSP）得到类似的络合物[[（arom-PSEt）2Ni]（BF4 ）2（1）和[（PSSP）Ni]（BF4）2（4）。CH3CN中
• Connolly, Julie; Forder, Robin J.; Reid, Gillian, Inorganica Chimica Acta, 1997, vol. 264, # 1-2, p. 137 - 144
  作者：Connolly, Julie、Forder, Robin J.、Reid, Gillian

  DOI：——

  日期：——
• Organometallic chemistry of sulfur/phosphorus donor ligand complexes of nickel(II) and nickel(0)
  作者：Yui May Hsiao、Stephen S. Chojnacki、Pamela Hinton、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/om00027a041

  日期：1993.3

  The X-ray crystal structures and electrochemical properties as well as chemical reactivity o the thioether complexes [Ni(Ph2PCH2CH2SEt)2][BF4]2 (5) and [Ni(Ph2PCH2CH2SCH2CH2CH2SCH2CH2PPh2)][BF4]2 (6), [Ni(PSSP)]2+, are compared with the thiolate Ni(Ph2PCH2CH2S)2 (4). Complex 4 crystallized in the orthorhombic space group Pbca (No. 61) with a 9.204(2) angstrom, b = 15.766(3) angstrom, c = 17.177(3) angstrom, V = 2492.6(8) angstrom3 Z = 4, and fin R = 0.050 (R, = 0.050) for 2212 unique reflections. Complex 5 crystallized in the monoclinic space group P2(1)/c, with a = 10.267(2) angstrom, b = 13.102(2) angstrom, c = 13.263(2) angstrom, beta = 93.750(10)-degrees, V = 1780.3(5) angstrom3, Z = 2, and final R = 0.076 (R(w) = 0.072) for 1777 unique reflections. The square-planar structures of 4 and 5 have sulfur donors in a trans arrangement and show a 0.04-angstrom lengthening of both the Ni-S and Ni-P bonds on going from the thiolate to the thioether complex. Within the CH3CN solvent window, the cyclic voltammograms of 5 and 6 show two reversible redox events assigned to Ni(II/I) and Ni(I/0), whereas the thiolate 4 shows only a sulfur-based irreversible oxidation and no reduction. Complexes 5 and 6 can be chemically reduced to Ni0 species, 5R and 6R, with Na/Hg amalgam. The H-1 NMR spectra of the reduced complexes indicate loss of one thioether donor for 5R and both for 6 . Protonation of the reduced species produced a Ni-H and reaction with both CH3I or CH3C(=O)Cl gave rise to Ni-CH3 and NiC(O)CH3 functionalities, respectively. The tetradentate derivatives [HNi(PSSP)]+ and [CH3Ni(PSSP)]+ are more stable than their bidentate analogues and show loss of reversible redox activity; i.e., the cyclic voltammograms find no evidence for stable Ni(I)-H or Ni(I)-CH3, or for Ni(III)-H or Ni(III)-CH3 species. The NiC(O)CH3 compounds rapidly and reversibly decarbonylate in solution (at temperatures >-30-degrees-C). A contrast of the abilities of structurally analogous P-SR vs N-SR ligands to stabilize subvalent nickel and organonickel functionalities is made.
• Co(III) and Cr(III) complexes of diphosphadithia ligands and the crystal structure of [CoCl2(L3)]PF6·CH2Cl2 (L3=Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2)
  作者：Julie Connolly、Robin J. Forder、Geoffrey W. Goodban、Simon J.A. Pope、Martin Predel、Gillian Reid

  DOI：10.1016/s0277-5387(99)00285-5

  日期：1999.11

  [CrX3(thf)(3)] (X = Cl or Br) reacts with L (L=L-1-L-3 or Ph-2[14]aneP(2)S(2)) (L-1=Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2, L-2= Ph2P(CH2)(2)S(CH2)(3)S(CH2)(2)PPh2, L-3=Ph2P(CH2)(2)S(o-C6H4)S(CH2)(2)PPh2, Ph-2[14]aneP(2)S(2)=4,8-diphenyl-1,11-dithia-4,8-diphosphacyclotetradecane) and TlPF6 in MeNO2 solution to yield the distorted octahedral complexes [CrX2(L)]PF6 as green coloured solids in high yield. UV/visible spectroscopy suggests that these are cis-dihalo species and they have also been characterised by IR spectroscopy, electrospray mass spectrometry and microanalyses. The Co(III) analogues [CoX2(L)](+) are readily prepared in a two-stage reaction, involving treatment of CoX2. 6H(2)O with L (L=L-1-L-3) and NH4PF6 in EtOH solution to give a green/brown solid, followed by halogen oxidation of this product in CH2Cl2 solution using X-2/CCl4, to give the final products as brown coloured solids. A mixture of PF6- and [CoX4](2-) anions are present in the final Co(III) compounds in varying ratios. Crystal structures of [CoCl2(L-2)](2)[CoCl4]. 4H(2)O and [CoCl2(L-3)]PF6. CH2Cl2 confirm tetradentate P2S2 coordination of L in each case, with mutually cis halogens completing the distorted octahedral geometry. In both cases the complex cation adopts the cis-ol form in the solid state and this is also consistent with the solution P-31H-1} NMR spectroscopic data. Co-59 NMR spectroscopy reveals a very broad single resonance at approximate to 3200 ppm for these species. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis and characterisation of mono- and di-nuclear mixed phosphathia complexes of gold(<scp>I</scp>): crystal structures of [Au(RSC₂H₄SR)]PF₆, [Au(RSC₃H₆SR)]PF₆and [Au₂(RSC₂H₄SR)₂]Cl₂·4CH₂Cl₂(R = Ph₂PC₂H₄)
  作者：Alexander M. Gibson、Gillian Reid

  DOI：10.1039/dt9960001267

  日期：——

  Mononuclear gold(I) complexes of two linear P2S2 donor ligands, [AuL]PF6 [L = RSC(2)H(4)SR or RSC(3)H(6)SR (R = Ph(2)PC(2)H(4))] have been prepared by reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with L and TIPF6 in MeCN solution. The crystal structure of [Au(RSC(2)H(4)SR)](+) shows a primary P-2-donor set with additional long-range thioether interactions giving a distorted linear geometry around Au-1 in the solid state; Au-P 2.284(7), 2.302(7), Au ... S 2.899(6), 3.190(7) Angstrom. The structure of [Au(RSC(3)H(6)SR)](+) shows a very similar arrangement; Au-P 2.279(6), 2.287(6) Angstrom, Au ... S 3.097(5), 3.101(6) Angstrom. The non-conducting binuclear species [Au(2)Cl(2)L] were obtained by reaction of [AuCl(tht)] with L in a 2: 1 molar ratio in CH2Cl2 solution, while a 1.1 [AuCl(tht)]: RSC(2)H(4)SR ratio yielded the unusual species [Au-2(RSC(2)H(4)SR)(2)]Cl-2, the crystal structure of which shows a linear P-2-donor set at each Au, giving a helical cavity which contains a Cl- anion. All complexes have been characterised by IR, H-1 and P-31 NMR spectroscopies, FAB mass spectrometry and microanalyses.