| 154676-72-9

• 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
• CAS: 154676-72-9
• 化学式: C₂₄H₂₃IN₂Pd
• 分子量: 572.785
• InChiKey: JCTMXAHAFSVAKS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  以 氘代丙酮 为溶剂， 生成 PdI(CH₂Ph)(2,2'-bipyridyl)
  参考文献：
  名称：

  苯基钯（IV）化学：从钯（IV）络合物还原消除中的选择性以及烷基卤化物从钯（IV）到钯（II）的转移

  摘要：

  Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-bipyridyl) in acetone at 0-degrees-C to form the isolable fac-triorganopalladium(IV) complexes PdIMe2Ph(bpy) (3) and PdXMePh(CH2Ph)(bpy) [X = Br (4), I (5)]. Complex 3 occurs as a mixture of isomers in a ca. 1:1 ratio, involving the phenyl group in a position trans either to bpy (3a) or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal bonded to three different groups could be studied for the first time. The complexes undergo facile reductive elimination in (CD3)2CO at 0-degrees-C, in which PdIMe2Ph(bpy) gives a mixture of ethane and toluene in a 4:1 molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh(CH2Ph)(bpy) (X = Br, I) gives exclusively toluene and PdX(CH2Ph)(bpy). The analogous tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts more slowly than PdMePh(bpy) with alkyl halides. Methyl iodide reacts cleanly with PdMePh(tmeda) (tmeda) at 0-degrees-C in (CD3)2CO to form ethane and PdIPh(tmeda), but the expected palladium(IV) intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda) below the decomposition temperature of the latter under these conditions (50-degrees-C, (CD3)2CO), while benzyl iodide reacts at 40-degrees-C to give a complicated mixture of products of which ethane, diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified. Benzyl iodide reacts with PdMe2(tmeda) at -30-degrees-C in (CD3)2CO to form PdlMe2(CH2Ph)(tmeda), for which H-1 NMR spectra showed the benzyl group to be trans to one of the N-donor atoms. However, PdIMe2(CH2Ph)(tmeda) is unstable and undergoes facile reductive elimination to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-(IV) to palladium(II) complexes occurs in (CD3)2CO at low temperatures for several reaction systems in which the resulting palladium(IV) complex is known to be more stable than the palladium(IV) reagent. There is a strong preference for benzyl group transfer from PdXMePh(CH2Ph)(bpy) to PdMe2(L2) (X = Br, I; L2 = bpy, phen). The mechanism of the transfer reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from palladium(IV) to platinum(II), palladium(II) to palladium(0), cobalt(III) to cobalt(I), and rhodium(III) to rhodium(I). These reaction systems involve nucleophilic attack by the lower oxidation state reagent at an alkyl group attached to tbe higher oxidation state reagent.

  DOI：

  10.1021/om00017a071
• 作为产物：
  描述：

  Pd(Me)(Ph)(2,2'-bipyridyl) 、 苄基碘 以 丙酮 为溶剂， 以83%的产率得到
  参考文献：
  名称：

  苯基钯（IV）化学：从钯（IV）络合物还原消除中的选择性以及烷基卤化物从钯（IV）到钯（II）的转移

  摘要：

  Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-bipyridyl) in acetone at 0-degrees-C to form the isolable fac-triorganopalladium(IV) complexes PdIMe2Ph(bpy) (3) and PdXMePh(CH2Ph)(bpy) [X = Br (4), I (5)]. Complex 3 occurs as a mixture of isomers in a ca. 1:1 ratio, involving the phenyl group in a position trans either to bpy (3a) or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal bonded to three different groups could be studied for the first time. The complexes undergo facile reductive elimination in (CD3)2CO at 0-degrees-C, in which PdIMe2Ph(bpy) gives a mixture of ethane and toluene in a 4:1 molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh(CH2Ph)(bpy) (X = Br, I) gives exclusively toluene and PdX(CH2Ph)(bpy). The analogous tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts more slowly than PdMePh(bpy) with alkyl halides. Methyl iodide reacts cleanly with PdMePh(tmeda) (tmeda) at 0-degrees-C in (CD3)2CO to form ethane and PdIPh(tmeda), but the expected palladium(IV) intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda) below the decomposition temperature of the latter under these conditions (50-degrees-C, (CD3)2CO), while benzyl iodide reacts at 40-degrees-C to give a complicated mixture of products of which ethane, diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified. Benzyl iodide reacts with PdMe2(tmeda) at -30-degrees-C in (CD3)2CO to form PdlMe2(CH2Ph)(tmeda), for which H-1 NMR spectra showed the benzyl group to be trans to one of the N-donor atoms. However, PdIMe2(CH2Ph)(tmeda) is unstable and undergoes facile reductive elimination to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-(IV) to palladium(II) complexes occurs in (CD3)2CO at low temperatures for several reaction systems in which the resulting palladium(IV) complex is known to be more stable than the palladium(IV) reagent. There is a strong preference for benzyl group transfer from PdXMePh(CH2Ph)(bpy) to PdMe2(L2) (X = Br, I; L2 = bpy, phen). The mechanism of the transfer reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from palladium(IV) to platinum(II), palladium(II) to palladium(0), cobalt(III) to cobalt(I), and rhodium(III) to rhodium(I). These reaction systems involve nucleophilic attack by the lower oxidation state reagent at an alkyl group attached to tbe higher oxidation state reagent.

  DOI：

  10.1021/om00017a071