2-diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);1-quinoxalin-2-ylethene-1,2-dithiolate | 189106-31-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 2-diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);1-quinoxalin-2-ylethene-1,2-dithiolate
• CAS: 189106-31-8
• 化学式: C₃₆H₃₀N₂P₂PdS₂
• 分子量: 723.147
• InChiKey: HOAWQRSOLRKZQF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  43.0
• 可旋转键数：
  5.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  25.78
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1,2,3,4,5,6,7,8-八硫杂环辛烷 、 2-diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);1-quinoxalin-2-ylethene-1,2-dithiolate 在 HBF₄ etherate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以48%的产率得到2-diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);thieno[3,2-b]quinoxaline-2,3-dithiolate
  参考文献：
  名称：

  Metallo 2,3-Disulfidothienoquinoxaline, 2,3-Disulfidothienopyridine, and 2-Sulfido-3-oxidothienoquinoxaline Complexes:  Synthesis and Characterization

  摘要：

  The 2,3-disulfidothienoquinoxaline complexes of Cp2Mo and dppePd and the 2,3-disulfidothienopyridine complexes of Cp2Mo were obtained as products from the S-8 oxidation of the corresponding metallo-1,2-enedithiolate complexes. The analogous 2-sulfido-3-oxidothienoquinoxaline complexes of Cp2Ti, Cp2Mo, dppPd, and dppePt were prepared from 1-(quinoxalin-2-yl)-2-bromoethanone and the corresponding polysulfido complex. Both Cp2Mo{S2C10H4N2S} and Cp2Mo{SOC10H4N2S} have been characterized crystallographically. These complexes contain an extended planar ring where the metal is bound to substituents at the 2- and 3-positions of the thiophene ring. The oxidation products of the Cp2Mo derivatives all have EPR g values near 1.98 and Mo-97/95 hyperfine of less than or equal to 8.5 G. All of the complexes have a visible band assigned to an intraligand transition (IL). The excitation of a room-temperature DMSO solution of dppePt{SOC10H4N2S} leads to an emission at 690 nm with a phi = 0.005. Lifetime measurements were best fit as the sum of two exponential decays with lifetimes of 6 and 0.3 ns.

  DOI：

  10.1021/ic961428v
• 作为产物：
  描述：

  ethylenebis(diphenylphosphine)dihydrogensulfidepalladium(II) 、 2-溴-1-(2-喹噁啉)乙酮 在 Et₃N 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以53%的产率得到2-diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);1-quinoxalin-2-ylethene-1,2-dithiolate
  参考文献：
  名称：

  Synthesis and Properties of Heterocyclic Substituted 1,2-Enedithiolates of Nickel, Palladium, and Platinum

  摘要：

  A convenient new synthetic route to metallo-1,2-enedithiolates was applied to the synthesis of (dppe)M{S2C2-(heterocycle)(H)}; dppe 1,2-bis(diphenyldiphosphino)ethane, hi Ni, Pd, and Pt, and heterocycle = 2-quinoxaline, 2-, 3-, and 4-pyridine, and 2-pyrazine. These complexes were prepared from the corresponding bis(hydrosulfido) complexes (dppe)M(SH)(2) and the alpha-bromo ketones, heterocycle-C(O)CH2Br. Zn the solid state, (dppe)Ni{S2C2(2-pyrazine)(H)} is a slightly distorted square plane with a planar five-membered metallo-1,2-enedithiolate ring. The metallo-l,2-dithiolate is approximate to 6 degrees from being coplanar with the pyrazine ring, These complexes all have a UV-visible band assignable to an intraligand transition (ILCT) that is best described as a 1,2-enedithiolate pi-->heterocycle pi* charge transfer transition. The energy of the ILCT transition tracks with the reduction potential of the appended aromatic heterocycle. The pK(a) of the protonated complexes is 1-3 units higher than that of the parent heterocycle, independent of the metal, and consistent with resonance stabilization of the protonated heterocycle by the 1,2-enedithiolate ligand.

  DOI：

  10.1021/ic970194s

文献信息

• Metallo 2,3-Disulfidothienoquinoxaline, 2,3-Disulfidothienopyridine, and 2-Sulfido-3-oxidothienoquinoxaline Complexes:  Synthesis and Characterization
  作者：Sharada P. Kaiwar、John K. Hsu、Anthony Vodacek、Glenn Yap、Louise M. Liable-Sands、Arnold L. Rheingold、Robert S. Pilato

  DOI：10.1021/ic961428v

  日期：1997.5.1

  The 2,3-disulfidothienoquinoxaline complexes of Cp2Mo and dppePd and the 2,3-disulfidothienopyridine complexes of Cp2Mo were obtained as products from the S-8 oxidation of the corresponding metallo-1,2-enedithiolate complexes. The analogous 2-sulfido-3-oxidothienoquinoxaline complexes of Cp2Ti, Cp2Mo, dppPd, and dppePt were prepared from 1-(quinoxalin-2-yl)-2-bromoethanone and the corresponding polysulfido complex. Both Cp2MoS2C10H4N2S} and Cp2MoSOC10H4N2S} have been characterized crystallographically. These complexes contain an extended planar ring where the metal is bound to substituents at the 2- and 3-positions of the thiophene ring. The oxidation products of the Cp2Mo derivatives all have EPR g values near 1.98 and Mo-97/95 hyperfine of less than or equal to 8.5 G. All of the complexes have a visible band assigned to an intraligand transition (IL). The excitation of a room-temperature DMSO solution of dppePtSOC10H4N2S} leads to an emission at 690 nm with a phi = 0.005. Lifetime measurements were best fit as the sum of two exponential decays with lifetimes of 6 and 0.3 ns.
• Synthesis and Properties of Heterocyclic Substituted 1,2-Enedithiolates of Nickel, Palladium, and Platinum
  作者：Sharada P. Kaiwar、John K. Hsu、Louise M. Liable-Sands、Arnold L. Rheingold、Robert S. Pilato

  DOI：10.1021/ic970194s

  日期：1997.9.1

  A convenient new synthetic route to metallo-1,2-enedithiolates was applied to the synthesis of (dppe)MS2C2-(heterocycle)(H)}; dppe 1,2-bis(diphenyldiphosphino)ethane, hi Ni, Pd, and Pt, and heterocycle = 2-quinoxaline, 2-, 3-, and 4-pyridine, and 2-pyrazine. These complexes were prepared from the corresponding bis(hydrosulfido) complexes (dppe)M(SH)(2) and the alpha-bromo ketones, heterocycle-C(O)CH2Br. Zn the solid state, (dppe)NiS2C2(2-pyrazine)(H)} is a slightly distorted square plane with a planar five-membered metallo-1,2-enedithiolate ring. The metallo-l,2-dithiolate is approximate to 6 degrees from being coplanar with the pyrazine ring, These complexes all have a UV-visible band assignable to an intraligand transition (ILCT) that is best described as a 1,2-enedithiolate pi-->heterocycle pi* charge transfer transition. The energy of the ILCT transition tracks with the reduction potential of the appended aromatic heterocycle. The pK(a) of the protonated complexes is 1-3 units higher than that of the parent heterocycle, independent of the metal, and consistent with resonance stabilization of the protonated heterocycle by the 1,2-enedithiolate ligand.