trans-[PdBr(C6H4SPh-2)(triphenylphosphine)2] | 760215-26-7

• 英文名称: trans-[PdBr(C6H4SPh-2)(triphenylphosphine)2]
• 英文别名: trans-[Pd(C6H4SPh-2)Br(PPh3)2]
• CAS: 760215-26-7
• 化学式: C₄₈H₃₉BrP₂PdS
• 分子量: 896.175
• InChiKey: FNWOHABBFMFDRR-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：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  trans-[PdBr(C6H4SPh-2)(triphenylphosphine)2] 、 2,6-二甲基苯基异腈 以 二氯甲烷 为溶剂， 以90%的产率得到SP-4-4-[Pd(C,N-C(N(C6H3Me2-2,6))C(N(C6H3Me2-2,6))C(N(C6H3Me2-2,6))C6H4SPh-2)Br(CN(C6H3Me2))]
  参考文献：
  名称：

  Palladated Oligophenylene Thioethers: Synthesis and Reactivity toward Isocyanides, Carbon Monoxide, and Alkynes

  摘要：

  Phenylene thioethers XC6H4(SC6H4R-4)-a (a = 2, 4; X = Br, I; R = H, OMe, NO2) react with Pd(dba)(2) and 2 equiv of PPh3 or 1 equiv of 2,2'-bipyridine (bpy) to afford trans-[PdBr{C6H4(SC6H4R-4)-a}(PPh3)(2)] (for example, a = 2, R = H (1)) or cis-[PdI{C6H4(SC6H4R-4}-a)(bpy)] (for example, a = 2, R = H (5)), respectively. Complex 1 (as well as some of its homologues) reacts (1) with 1 equiv of [PdCl2(NCPh)(2)] to give a mixture of isomers of [{PdBr(PPh3)}(2)(mu-C,S-C6H4SPh-2)(2)], (2) with 1 equiv of XyNC (Xy = C6H3Me2-2,6) to render SP-4-4-[PdBr{C,S-C(=NXy)C6H4-2-SPh}(PPh3)], (3) with XyNC and TlTfO (TfO = O3SCF3; 1:2:1 molar ratios) to give SP-4-3-[Pd{C,S-C(=NXy)C6H4-2-SPh}(CNXy)(PPh3)TfO, (4) with 4 equiv of XyNC to give SP-4-4-[Pd{C,N-C(=NXy)C(=NXy)C(=NXy)C6H4(SPh)-2}Br(CNXy)], or (5) with TlTfO (1:1 molar ratio) to afford a mixture of compounds from which a few single crystals of (Ph3PC6H4SPh-2)TfO could be obtained. Complexes with bpy ligands react with 2 equiv of PPh3 to give trans-[PdI{C6H4(SC6H4R-4)-4} (PPh3)(2)] or with 3 equiv of XyNC affording monoinserted complexes resulting from the replacement of the PdI(bpy) group by trans-{C(=NXy)}Pd(CNXy)(2). Dinuclear complexes are prepared by reacting diiodophenylene thioethers with Pd(dba)(2) and bpy. Complex 5 reacts with TlTfO and CO or various alkynes RC CR' to afford, respectively, [Pd{C,S-C(O)C6H4SPh-2)}bpy]TfO or [Pd{C,S-C(R')=C(R)C6H4SPh-2}bpy], the latter of which decompose thermally to give the benzothiophenes resulting from the C-S coupling. Crystal structures of some model complexes have been determined.

  DOI：

  10.1021/om200607h
• 作为产物：
  描述：

  2-bromophenyl phenyl sulfide 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 以 甲苯 为溶剂， 以76%的产率得到trans-[PdBr(C6H4SPh-2)(triphenylphosphine)2]
  参考文献：
  名称：

  Unexpected Formation of an ortho-Palladated Diphenylthioether

  摘要：

  The reaction of [Ph4P][BrC6H4S-2] with [Pd-2l(dba)(3)].dba (dba = dibenzylideneacetone) in the presence of PPh3 gives trans-[Pd(C6H4SPh-2)Br(PPh3)(2)]. A sequence of reactions consisting of oxidative addition of the tetraphenylphosphonium cation to palladium(0), reductive C-S coupling to give BrC6H4SPh-2, and, again, an oxidative addition of the latter to palladium(0) seems to constitute the pathway for the formation of the final palladium complex. Some experimental evidence supporting this pathway is provided. The crystal structure of trans-[Pd(C6H4SPh-2)Br(PPh3)(2)] has been solved by an X-ray diffraction study.

  DOI：

  10.1021/om0496683