1,3-bis[(mercaptoethyl)phenylphosphino]propane

• 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: 1,3-bis[(mercaptoethyl)phenylphosphino]propane
• 英文别名: H2meppp；2-[Phenyl-[3-[phenyl(2-sulfanylethyl)phosphanyl]propyl]phosphanyl]ethanethiol
• 化学式: C₁₉H₂₆P₂S₂
• 分子量: 380.495
• InChiKey: XGZKUDSVIUMXBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-二溴丙烷 、 1,3-bis[(mercaptoethyl)phenylphosphino]propane 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 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
• 作为产物：
  描述：

  环硫乙烷 、 1,3-双(苯基膦酰)丙烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以82%的产率得到1,3-bis[(mercaptoethyl)phenylphosphino]propane
  参考文献：
  名称：

  具有MM'（μ-meppp）中心的系统异核复合物，可调节嵌套氢化物的性质（M = Ni，Pd，Pt; M'= Rh，Ir; H 2 meppp = meso -1,3-Bis [（巯基乙基） ）苯基膦基]丙烷）

  摘要：

  具有P 2 S 2配体[M（meppp）]（M = Ni（1a），Pd（1b），Pt（1c）； H 2 meppp =中观-1,3-双[（巯基乙基）苯基膦基]丙烷），用[* M'Cp氯处理2 ] 2或[M'Cp *（NO 3）2 ]（CP * =η 5 -五甲基），得到一系列bisthiolate桥连中号II M' III异核复合物，[M（μ-meppp）M'Cp * X] X'（M = Ni，Pd，Pt; M'= Rh，Ir; X = Cl，NO 3 ; X'= Cl，PF 6，NO 3）。硝酸盐络合物[M（μ-meppp）-M'Cp *（NO 3）] NO 3（M'= Rh（[ 4a – c ] NO 3），Ir（[ 5a – c ] NO 3）; M = Ni（a），Pd（b），Pt（c））进一步与甲酸钠在水或甲醇中反应，转化为双硫醇盐和氢化物桥接的配合物[M（μ-meppp）（μ-H）M'

  DOI：

  10.1021/om500410f

文献信息

• Systematic Heterodinuclear Complexes with MM′(μ-meppp) Centers That Tune the Properties of a Nesting Hydride (M = Ni, Pd, Pt; M′ = Rh, Ir; H₂meppp = <i>meso</i>-1,3-Bis[(mercaptoethyl)phenylphosphino]propane)
  作者：Bunsho Kure、Mikie Sano、Takayuki Nakajima、Tomoaki Tanase

  DOI：10.1021/om500410f

  日期：2014.8.11

  and PtIIRhIII ([6c]NO3) complexes, the hydrides were extremely unstable and were likely to undergo an unusual metal-to-Cp* ring hydrogen transfer, resulting in η4-C5Me5H MIIRhI complexes, [M(μ-meppp)Rh(η4-C5Me5H)]NO3 (M = Pd ([7b]NO3), Pt ([7c]NO3)). The property of the hydride was drastically switched by varying the anchoring metal ions of the M′ site (Rh, Ir); that of [6a]NO3 (M′ = Rh) is not protic

  具有P 2 S 2配体[M（meppp）]（M = Ni（1a），Pd（1b），Pt（1c）； H 2 meppp =中观-1,3-双[（巯基乙基）苯基膦基]丙烷），用[* M'Cp氯处理2 ] 2或[M'Cp *（NO 3）2 ]（CP * =η 5 -五甲基），得到一系列bisthiolate桥连中号II M' III异核复合物，[M（μ-meppp）M'Cp * X] X'（M = Ni，Pd，Pt; M'= Rh，Ir; X = Cl，NO 3 ; X'= Cl，PF 6，NO 3）。硝酸盐络合物[M（μ-meppp）-M'Cp *（NO 3）] NO 3（M'= Rh（[ 4a – c ] NO 3），Ir（[ 5a – c ] NO 3）; M = Ni（a），Pd（b），Pt（c））进一步与甲酸钠在水或甲醇中反应，转化为双硫醇盐和氢化物桥接的配合物[M（μ-meppp）（μ-H）M'
• 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)
  作者：Neil R. Champness、Christopher S. Frampton、Gillian Reid、Derek A. Tocher

  DOI：10.1039/dt9940003031

  日期：——

  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.