8,12-Diphenyl-1,5-dithia-8,12-diphosphacyclotetradecane | 159858-75-0

• 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: 8,12-Diphenyl-1,5-dithia-8,12-diphosphacyclotetradecane
• 英文别名: meso-8,12-diphenyl-1,5-dithia-8,12-diphosphacyclotetradecane；meso-4,8-diphenyl-1,11-dithia-4,18-diphosphacyclotetradecane；4,8-diphenyl-1,11-dithia-4,8-diphosphacyclotetradecane
• CAS: 159858-75-0
• 化学式: C₂₂H₃₀P₂S₂
• 分子量: 420.56
• InChiKey: ZBSQMSSIGBQSEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.86
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  氯化铑(三水) 、 8,12-Diphenyl-1,5-dithia-8,12-diphosphacyclotetradecane 以 乙醇 、 水 为溶剂， 以84%的产率得到
  参考文献：
  名称：

  合成，结构和铂金属phosphathia络合物的氧化还原性质：晶体结构的顺式-将[RuCl 2（RSC 2 ħ 4 SR）]·0.75Et 2 O和顺- [的RhCl 2（RSC 2 ħ 4 RS）] PF 6 · CH 2 Cl 2（R = Ph 2 PCH 2 CH 2）

  摘要：

  [RuCl 2（py）4 ]（py =吡啶）与1摩尔当量的新四齿无环磷化合物RSC 2 H 4 SR（Ph 2 PCH 2 CH 2 SCH 2 CH 2 SCH 2 CH 2 PPh 2）或在氮气氛下，在回流的甲苯中，将大环内消旋-Ph 2 [14] aneP 2 S 2（4,8-二苯基-1,11 - dithia - 4.18-二磷环十四烷）制成钌（II）络合物[RuCl 2（RSC 2 H4 SR）]和将[RuCl 2（PH 2 [14] ANEP 2小号2）]分别为，为黄色固体。[RuCl 2（RSC 2 H 4 SR）]·0.75Et 2 O的晶体结构显示，RSC 2 H 4 SR通过所有四个供体原子配位，而两个P-供体在Ru II处占据了相互交叉的配位位点，和顺式-dichlorides完成整体八面体的立体化学，RU-S 2.294（1），2.292（1），RU-P 2.339（2），2

  DOI：

  10.1039/dt9960001261
• 作为产物：
  描述：

  1,3-双(苯基膦酰)丙烷 在 正丁基锂 、 caesium carbonate 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.5h， 生成 8,12-Diphenyl-1,5-dithia-8,12-diphosphacyclotetradecane
  参考文献：
  名称：

  Mixed phosphathia macrocyclic chemistry: synthesis and characterisation of [M(Ph2[14]ane P2S2)]2+(M = Pd or Pt) and [RhCl2(Ph2[14]ane P2S2)]+(Ph2[14]ane P2S2= 8, 12-diphenyl-1, 5-dithia-8, 12-diphosphacyclotetradecane)

  摘要：

  The new diphosphadithia macrocycle 8,12-diphenyl-1,5-dithia-8,12-diphosphacyclotetradecane (Ph(2)[14]aneP(2)S(2)) has been prepared and the meso isomer isolated as a white solid. Upon reaction with MCl(2), (M = Pd or Pt) in the presence of TlPF6 in refluxing MeCN this isomer gave [M(Ph(2)[14]aneP(2)S(2))][PF6](2). The crystal structure of [Pt(Ph(2)[14]aneP(2)S(2))][PF6](2).MeNO(2), shows tetradentate P2S2 co-ordination at Pt-II giving a distorted square-planar geometry with Pt-P 2.247(3), 2.252(3) Angstrom and Pt-S 2.343(3), 2.341(4) Angstrom. Phosphorus-31 and Pt-195 NMR spectroscopic data confirm retention of this P2S2 co-ordination in solution. Treatment of RhCl3.3H(2)O with Ph(2)[14]aneP(2)S(2) in refluxing aqueous EtOH followed by addition of an excess of NH4PF6 gave [RhCl2(Ph(2)[14]aneP(2)S(2))]PF6 as a yellow solid. The P-31 NMR spectrum indicates that the complex exists as the-trans-dichloro isomer exclusively, and a single-crystal X-ray structure determination confirms this. The crystal structure of [RhCl2,(Ph(2)[14]aneP(2)S(2))]PF6, shows the macrocyclic donor atoms occupying the four equatorial co-ordination sites around the central Rh-III ion, Rh-P 2.286(1), 2.300(1) Angstrom, Rh-S 2.374(1), 2.377(1) Angstrom, with trans-dichloro ligands, Rh-Cl 2.347(1), 2.354(1) Angstrom, giving a distorted octahedral geometry. Cyclic voltammetry shows that the complexes [M(Ph(2)[14]aneP(2)S(2))][PF6](2) (M = Pd or Pt) and trans-[RhCl2(Ph(2)[14]aneP(2)S(2))]PF6 each exhibit an irreversible reduction at Epc values of -1.40, -1.93 and -1.06 V vs. ferrocene-ferrocenium respectively.

  DOI：

  10.1039/dt9940003031

文献信息

• 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.