| 161843-76-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 161843-76-1
• 化学式: C₂₀H₃₆P₂PtS
• 分子量: 565.599
• InChiKey: WBIPLCGYUVPAQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  24.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  三乙基硅烷 、 以 氘代甲苯 为溶剂， 以50%的产率得到trans-[PtH(PEt3)2(SH)]
  参考文献：
  名称：

  Equilibria of the Thiametallacycles with Tris(triethylphosphine)platinum(0) and Dibenzothiophene, Benzothiophene, or Thiophene: The Hydrodesulfurization Reaction

  摘要：

  The thiaplatinacycles, [(PtSC12H8)(PEt(3))(2)], 1, [(PtSC8H6)(PEt(3))(2)], 2, and [(PtSC4H4)(PEt(3))(2)], 3, in which Pt(PEt(3))(2) has inserted into one C-S bond of dibenzothiophene (DBT), benzothiophene (BT), and thiophene (T), respectively, are formed by the reversible reaction of tris(triethylphosphine)platinum(O) with the thiophene. The structure of complex [(PtSC8H6)(PEt(3))(2)] (2) was confirmed by an X-ray determination that showed a square-planar Pt(II) bound to two cis PEt(3) ligands, and to the S and the CH=, in a six-membered Pt-S-C-C-C-C ring [Pt-S(1), 2.315(5) Angstrom; Pt-C(4), 2.035(19) Angstrom; Pt-P(1), 2.301(5) Angstrom, trans to S(1); and Pt-P(2), 2.386(5) Angstrom, trans to C(4); P(1)-Pt-P(2), 97.6(2)degrees; S(1)-Pt-P(2), 87.0(2)degrees; S(1)-Pt-C(4), 88.6(6)degrees; P(1)-Pt-C(4), 86.8(6)degrees]. The adducts 1 and 3, derived from DBT and T, have been shown to have similar structures spectroscopically. The free thiophenes and Pt(PEt(3))(3) are regenerated on heating complexes 1-3 with Et(3)P; [(PtSCaHb)(PEt(3))(2)] + Et(3)P reversible arrow [Pt(Et(3)P)(3)] + SCaHb. K-eqm = [Pt(Et(3)P)(3)] [SCaHb]/[PtSCaHb)(PEt(3))(2)] [Et(3)P] and is 10 for 1 (DBT) and 3 (T) and 1 for 2 (BT) at 100 degrees C. The complexes 1-3 undergo a variety of cleavage reactions; thus, the Pt-C bond in 1 is cleaved by HCl to give 2-phenylthiophenol and [Pt(PEt(3))(2)Cl-2], and all three complexes are degraded by hydride reagents to give the completely desulfurized hydrocarbons: biphenyl from 1, styrene and ethylbenzene from 2, and butadiene and butenes from 3. When the reactions are carried out with Et(3)SiH as reducer, the complex [Pt(SH)(H)(PEt(3))(2)] is identified among the products, together with [Pt(Et(3)Si)(H)(PEt(3))(2)]. The former is a coproduct of the desulfurization, while the latter arises from addition of Et(3)SiH to [Pt(PEt(3))(2)] (from reversal of the formation of [(PtSCaHb)(PEt(3))(2)]) and is accompanied by the formation of the free thiophene. Under comparable conditions, the amount of desulfurization decreases in the order BT complex 2 (73%) > DBT complex 1 (50%), T complex 3 (ca. 4%). These hydride reactions show the novel feature that the C-S bond is cleaved as well as the Pt-C bond; possible mechanisms for the platinum and for the known nickel- and hydride-promoted hydrodesulfurization (HDS) reactions are discussed.

  DOI：

  10.1021/ja00113a007
• 作为产物：
  描述：

  [Pt(PEt₃)₃] 、 苯并噻吩 以 甲苯 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Equilibria of the Thiametallacycles with Tris(triethylphosphine)platinum(0) and Dibenzothiophene, Benzothiophene, or Thiophene: The Hydrodesulfurization Reaction

  摘要：

  The thiaplatinacycles, [(PtSC12H8)(PEt(3))(2)], 1, [(PtSC8H6)(PEt(3))(2)], 2, and [(PtSC4H4)(PEt(3))(2)], 3, in which Pt(PEt(3))(2) has inserted into one C-S bond of dibenzothiophene (DBT), benzothiophene (BT), and thiophene (T), respectively, are formed by the reversible reaction of tris(triethylphosphine)platinum(O) with the thiophene. The structure of complex [(PtSC8H6)(PEt(3))(2)] (2) was confirmed by an X-ray determination that showed a square-planar Pt(II) bound to two cis PEt(3) ligands, and to the S and the CH=, in a six-membered Pt-S-C-C-C-C ring [Pt-S(1), 2.315(5) Angstrom; Pt-C(4), 2.035(19) Angstrom; Pt-P(1), 2.301(5) Angstrom, trans to S(1); and Pt-P(2), 2.386(5) Angstrom, trans to C(4); P(1)-Pt-P(2), 97.6(2)degrees; S(1)-Pt-P(2), 87.0(2)degrees; S(1)-Pt-C(4), 88.6(6)degrees; P(1)-Pt-C(4), 86.8(6)degrees]. The adducts 1 and 3, derived from DBT and T, have been shown to have similar structures spectroscopically. The free thiophenes and Pt(PEt(3))(3) are regenerated on heating complexes 1-3 with Et(3)P; [(PtSCaHb)(PEt(3))(2)] + Et(3)P reversible arrow [Pt(Et(3)P)(3)] + SCaHb. K-eqm = [Pt(Et(3)P)(3)] [SCaHb]/[PtSCaHb)(PEt(3))(2)] [Et(3)P] and is 10 for 1 (DBT) and 3 (T) and 1 for 2 (BT) at 100 degrees C. The complexes 1-3 undergo a variety of cleavage reactions; thus, the Pt-C bond in 1 is cleaved by HCl to give 2-phenylthiophenol and [Pt(PEt(3))(2)Cl-2], and all three complexes are degraded by hydride reagents to give the completely desulfurized hydrocarbons: biphenyl from 1, styrene and ethylbenzene from 2, and butadiene and butenes from 3. When the reactions are carried out with Et(3)SiH as reducer, the complex [Pt(SH)(H)(PEt(3))(2)] is identified among the products, together with [Pt(Et(3)Si)(H)(PEt(3))(2)]. The former is a coproduct of the desulfurization, while the latter arises from addition of Et(3)SiH to [Pt(PEt(3))(2)] (from reversal of the formation of [(PtSCaHb)(PEt(3))(2)]) and is accompanied by the formation of the free thiophene. Under comparable conditions, the amount of desulfurization decreases in the order BT complex 2 (73%) > DBT complex 1 (50%), T complex 3 (ca. 4%). These hydride reactions show the novel feature that the C-S bond is cleaved as well as the Pt-C bond; possible mechanisms for the platinum and for the known nickel- and hydride-promoted hydrodesulfurization (HDS) reactions are discussed.

  DOI：

  10.1021/ja00113a007