trans-[Pt(p-anisyl)Cl(SMe2)2] | 195623-61-1

• 英文名称: trans-[Pt(p-anisyl)Cl(SMe2)2]
• 英文别名: trans-[PtCl(4-C6H4OMe)(SMe2)2]
• CAS: 195623-61-1
• 化学式: C₁₁H₁₉ClOPtS₂
• 分子量: 461.936
• InChiKey: WCCFYFVDJKUGSI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  trans-[Pt(p-anisyl)Cl(SMe2)2] 以 二氯甲烷-D2 为溶剂， 生成 [PtCl(4-C6H4OMe)(bipy)]
  参考文献：
  名称：

  Activation of Anisole by Organoplatinum(II) Complexes: Evidence for Rate-Determining C–H Activation

  摘要：

  A study of the basis of selectivity of C-H bond activation of anisole by electrophilic methylplatinum(II) complexes is reported. Anisole reacts with [PtXMe(NN)] in trifluoroethanol solvent to give methane and [PtXAr(NN)], Ar = 2-, 3-, and 4-anisyl, in 90:8:2 ratio when X = HOB(C6F5)(3) and NN = (2-C5H4N)(2)CO (DPK) but not when NN = 2,2'-bipyridine. Similar results are obtained when X = triflate or when NN = (2-C5H4N)(2)NH. Competition between reaction of anisole and anisole-d(8) with [PtXMe(NN)], X = HOB(C6F5)(3) and NN = DPK, in trifluoroethanol gave an isotope effect k(H)/k(D) = 3.6. Several 4-anisyl complexes, [PtClAr(NN)], [PtAr2(NN)], and [PtMeAr(NN)], NN = DPK, DPA, or bipy, were prepared and reacted with HX [X = Cl, OTf, or HOB(C6F5)(3)]. Reaction of [PtMeAr(NN)], NN = DPK or bipy, with HX gave a detectable hydride [PtXHMeAr(NN)] when X = Cl, followed by loss of methane to give [PtClAr(NN)], but only [Pt(OTf)Ar(NN)] was detected when X = OTf. Reaction with more HOTf gave anisole and [PtX2(NN)], X = OTf, and no isomerization of the 4-anisyl group to the more favored 2-anisyl group was observed at any stage. The similar reaction of [PtMeAr(NN)] and HOTf in CD3OD/CD2Cl2 gave CHnD4-n (n = 0-4) and mostly 4-MeOC6H4D. It is argued that the anisole C-H bond cleavage step in anisole activation, or the anisyl-H bond forming step in protonolysis, is responsible for the observed selectivity in these reactions.

  DOI：

  10.1021/om200922a
• 作为产物：
  描述：

  dichlorobis(dimethylsulfide)platinum(II) 、 (4-methoxyphenyl)trimethylstannane 以 丙酮 为溶剂， 以79%的产率得到trans-[Pt(p-anisyl)Cl(SMe2)2]
  参考文献：
  名称：

  Activation of Anisole by Organoplatinum(II) Complexes: Evidence for Rate-Determining C–H Activation

  摘要：

  A study of the basis of selectivity of C-H bond activation of anisole by electrophilic methylplatinum(II) complexes is reported. Anisole reacts with [PtXMe(NN)] in trifluoroethanol solvent to give methane and [PtXAr(NN)], Ar = 2-, 3-, and 4-anisyl, in 90:8:2 ratio when X = HOB(C6F5)(3) and NN = (2-C5H4N)(2)CO (DPK) but not when NN = 2,2'-bipyridine. Similar results are obtained when X = triflate or when NN = (2-C5H4N)(2)NH. Competition between reaction of anisole and anisole-d(8) with [PtXMe(NN)], X = HOB(C6F5)(3) and NN = DPK, in trifluoroethanol gave an isotope effect k(H)/k(D) = 3.6. Several 4-anisyl complexes, [PtClAr(NN)], [PtAr2(NN)], and [PtMeAr(NN)], NN = DPK, DPA, or bipy, were prepared and reacted with HX [X = Cl, OTf, or HOB(C6F5)(3)]. Reaction of [PtMeAr(NN)], NN = DPK or bipy, with HX gave a detectable hydride [PtXHMeAr(NN)] when X = Cl, followed by loss of methane to give [PtClAr(NN)], but only [Pt(OTf)Ar(NN)] was detected when X = OTf. Reaction with more HOTf gave anisole and [PtX2(NN)], X = OTf, and no isomerization of the 4-anisyl group to the more favored 2-anisyl group was observed at any stage. The similar reaction of [PtMeAr(NN)] and HOTf in CD3OD/CD2Cl2 gave CHnD4-n (n = 0-4) and mostly 4-MeOC6H4D. It is argued that the anisole C-H bond cleavage step in anisole activation, or the anisyl-H bond forming step in protonolysis, is responsible for the observed selectivity in these reactions.

  DOI：

  10.1021/om200922a

文献信息

• Synthesis, Structure, and Reactivity of Arylchlorobis(dialkyl sulfide)platinum(II) Complexes
  作者：Ola F. Wendt、Åke Oskarsson、Johann G. Leipoldt、Lars I. Elding

  DOI：10.1021/ic970189o

  日期：1997.9.1

  bond-weakening. Comparison of the reaction rates of the present series of complexes with their bis(phosphine) analogues and with related cyclometalated compounds shows that the triethylphosphine complexes are 2-3 orders of magnitude less reactive than the thioether complexes, which in turn are a factor 10-20 less reactive than the cyclometalated ones. This reactivity increase can be rationalized mainly

  已合成反式-[PtRCl（SR'（2））（2）]的配合物，其中R = Ph，甲磺酰基和对茴香基，R'= Me或Et，并确定了它们的晶体和分子结构。反式[PtPhCl（SEt（2））（2）]（2）的晶体是三斜晶（P＆onemacr;），a = 10.112（6）Å，b = 13.158（2）Å，c = 14.714（5）Å alpha = 102.48（2）度，beta = 94.394（4）度，γ= 90.22（3）度，Z =4。反式-[Pt（mesityl）Cl（SMe（2））（2）]的晶体4）是单斜晶（P2（1）/ c），a = 13.158（2）Å，b = 9.170（1）Å，c = 16.013（3）Å，beta = 120.93（2）度，Z = 4，并且[Pt（对茴香基）Cl（SMe（2））（2）]（5）的晶体是单斜晶（P2（1）/ n），a = 9.879（4）Å，b = 8.128（2）Å