[PtCl(4-C6H4OMe)(bipy)] | 1352613-65-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [PtCl(4-C6H4OMe)(bipy)]
• 英文别名: [PtCl(4-C6H4OMe)(2,2'-bipyridine)]；methoxybenzene;platinum(2+);2-pyridin-2-ylpyridine;chloride
• CAS: 1352613-65-0
• 化学式: C₁₇H₁₅ClN₂OPt
• 分子量: 493.852
• InChiKey: VGBGIVUUZWHPOK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.64
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  35
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [PtCl(4-C6H4OMe)(bipy)] 以 四氢呋喃 为溶剂， 生成 [Pt(OTf)₂(2,2′-bipyridine)]
  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：

  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