trans-[PtH(PEt3)2(SH)] | 61459-92-5

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: trans-[PtH(PEt3)2(SH)]
• 英文别名: trans-PtH(SH)(PEt3)2；platinum(1+) monohydride;sulfanide;triethylphosphane
• CAS: 61459-92-5
• 化学式: C₁₂H₃₂P₂PtS
• 分子量: 465.48
• InChiKey: NYRLBARHSWSHQL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.17
• 重原子数：
  16.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  trans-[PtH(PEt3)2(SH)] 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 生成 trans-chlorohydridobis(triethylphosphine)platinum(II) 、 cis,cis,trans-[PtH2Cl2(PEt3)2]
  参考文献：
  名称：

  结合有硫化氢和硒化氢配体的铂（II）和铂（IV）的氢化物

  摘要：

  复合物的反式- [PTH（EH）（PET 3）2 ]和反式- [PT（EH）2（PET 3）2 ]（E = S或Se）已经制备和表征。H 2 Se氧化成反式-[PtH（X）（PEt 3）2 ]（X = Cl Br，I，SH，SeH或CN）生成六配位的二氢化铂金（IV）。在某些情况下，X和EH配体会重新分布，其机理已借助31 P nmr光谱学推论。HY（Y = Cl或I）加至反式-[PtH（SH）（PEt 3）2 ]也已被调查。二氢化铂（ IV）的分解导致形成硫化氢-和硒代氢硒基的铂（ II）复合物。

  DOI：

  10.1039/dt9780000753
• 作为产物：
  描述：

  [Pt(PEt₃)₃] 在 NaBH₄ 作用下， 以 四氢呋喃 、 异丙醇 、 甲苯 为溶剂， 生成 trans-[PtH(PEt3)2(SH)]
  参考文献：
  名称：

  Garcia, Juventino J.; Maitlis, Peter M., Journal of the American Chemical Society, 1993, vol. 115, # 25, p. 12200 - 12200

  摘要：

  DOI：

文献信息

• Silyl and germyl complexes of platinum and palladium. Part 3. Reactions between silyl and germyl derivatives of Group 6 and four-co-ordinate halogenohydridobis(triethylphosphine)platinum(II) complexes
  作者：E. A. V. Ebsworth、Joyce M. Edward、David W. H. Rankin

  DOI：10.1039/dt9760001667

  日期：——

  and trans-[PtCl(PEt3)2(SiClH2)]; for M = Ge, the reactions are complicated and the products thermally unstable. Reaction between SiH3(SH) and trans-[PtH(I)(PEt3)2] gives trans-[PtI(PEt3)2(SiH2SH)]; with trans-[PtCl(H)(PEt3)2], trans-[PtCl(PEt3)2(SiClH2)] and trans-[PtCl(PEt3)2(SH)] are formed. The complexes have been characterised by 1H and 31P n.m.r. spectra: 195Pt, and in some cases 29Si, 77Se, and

  Y（MH 3）2（Y = O，S或Se； M = Si或Ge）与反式-[PtX（H）（PEt 3）2 ]（X = Cl，Br或I）之间的反应通过核磁共振光谱研究。当X ＝ Br或I且M ＝ Si时，形成反-[ PtX （PEt 3）2（H 2 SiYSiH 3）]和反-[PtX（PEt 3）2（SiH 2）} 2 Y]。对于M = Ge，反应相似，但产物是热不稳定的。当X ＝ Cl时，S（SiH 3）2和Se（SiH 3）2给出反式-[PtH（PEt 3）2（YSiH 3）]和反式-[PtCl （PEt 3）2（SiClH 2）]；当M = Ge时，反应复杂且产物热不稳定。SiH 3（SH）与反式-[PtH（I）（PEt 3）2 ]之间的反应得到反式-[PtI（PEt 3）2（SiH 2 SH）]。与反式-[PtCl（H）（PEt 3）2 ]，反式-[PtCl（PEt 3）2形成（SiClH
• Equilibria of the Thiametallacycles with Tris(triethylphosphine)platinum(0) and Dibenzothiophene, Benzothiophene, or Thiophene: The Hydrodesulfurization Reaction
  作者：Juventino J. Garcia、Brian E. Mann、Harry Adams、Neil A. Bailey、Peter M. Maitlis

  DOI：10.1021/ja00113a007

  日期：1995.3

  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.