trans-[PdBrC(N(C6H3Me2-2,6))(C6H4CHCH2-2))(CN(C6H3Me3-2,6))2] | 474832-76-3

• 英文名称: trans-[PdBrC(N(C6H3Me2-2,6))(C6H4CHCH2-2))(CN(C6H3Me3-2,6))2]
• 英文别名: trans-[Pd(C(NC6H3Me2)C6H4CHCH2-2)(CNC6H3Me2)2Br]
• CAS: 474832-76-3
• 化学式: C₃₅H₃₄BrN₃Pd
• 分子量: 682.999
• InChiKey: NKPZHYQHPHZTJZ-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：

  trans-[PdBrC(N(C6H3Me2-2,6))(C6H4CHCH2-2))(CN(C6H3Me3-2,6))2] 、 三氟甲磺酸铊 在 一氧化碳 、 水 作用下， 以 丙酮 为溶剂， 生成 thallium(I) bromide 、 钯
  参考文献：
  名称：

  Depalladation Reactions of Iminoacyl- and 2-Acetylarylpalladium(II) Complexes

  摘要：

  Reaction with Tl(TFO)) (TfO = triflate, CF3SO3), in some cases in the presence of CO or EtOH, causes the depalladation of complexes trans-[Pd{C(=NR)C6H4{C(O)Me}-2}Br(CNR)(2)} [R = 2,6-dimethylphenyl (Xy) (1a), R = Bu-t (1a')], trans-[Pd{C(=NXy)C6H(OMe)(3)-2,3,4{C(O)Me}-6}JBr(CNXy)(2)} (1b), trans- [Pd{C(=NR)C6H4(CH=CH2)-2}Br(CNR)(2)] [R = Xy (2), Bu-t (2')], trans-[Pd{C(=NXy)C(NHXy)=CC(6)H(4)f{C(O)NXy}-2}Br(CNR)(2)](3), trans-[Pd{C6H4-{C(O)Me}-2}Br(PPh3)(2)] (4), and [Pd{C6H4{C(O)Me}-2Br(bpy)] (bpy = 2,2'-bipyridine) (5) to give organic compounds. Complexes 1a, 1a', and 1b react with Tl(TfO) in Me2CO or CH2Cl2 to give the isoindolinones 2-(2,6-dimethylphenyl)-3-methylene-2,3-dihydroisoindol-1-one (6a), 2-tert-butyl-3-methylene-2,3-dihydroisoindol-1-one (6a'), and 2-(2,6-dimethylphenyl)-5,6,7trimethoxy-3-methylene-2,3-dihydroisoindol-1-one (6b), respectively. When the reaction with 1a' is carried out in the presence of a small amount of EtOH, in addition to 6a', the isoindolinone 2-tert-butyl-3-ethoxy-3-methyl-2,3-dihydroisoindol-1-one (7) and 2-acetyl-Ntert-butylbenzamide (8) are obtained. Complex 2 reacts with Tl(TfO) in the presence of CO to give N-(2,6-dimethylphenyl)-2-vinylbenzamide (9); however, the analogous compound 2' reacts with Tl(TFO)) to give a mixture containing ortho-cyanostyrene (10). Complex 3 reacts with Tl(TfO) to give a separable mixture of N-(2,6-dimethylphenyl)-2-(2,6-dimethylphenylamino)-2-[2-(2,6-dimethylphenyl)-3-oxo-2,3-dihydroisoindol-1-ylidene]acetamide (11) and N-(2,6-dimethylphenyl)-2-(2,6-dimethylphenylamino)-2-[2-(2,6-dimethylphenyl)-3-oxo-2,3-di- hydroisoindol-1-ylidenelacetamidic acid (12). When this reaction is carried out in the presence of a small amount of EtOH, 11, 12, and its ethyl ester 13 are obtained. Complex 4 or 5 reacts with CO and Tl(TfO) in Me2CO to give 3-methylenephthalide (14) or a complex mixture, respectivel'. Complexes 4 and 5 react with Tl(TFO)) in CH2Cl2 in the presence of a y small amount of EtOH, affording 3-ethoxy-3-methyl-3H-isobenzofuran-1-one (15). The crystal and molecular structures of 6a, 6b, 8(.)0.11H(2)O, 9, 11(.)0.5Et(2)O 13, and 14 have been determined by X-ray diffraction studies.

  DOI：

  10.1021/om030045j
• 作为产物：
  描述：

  trans-(Pd(C6H4(CHCH2)-2)Br(PPh3)2) 、 2,6-二甲基苯基异腈 以 二氯甲烷 为溶剂， 以75%的产率得到trans-[PdBrC(N(C6H3Me2-2,6))(C6H4CHCH2-2))(CN(C6H3Me3-2,6))2]
  参考文献：
  名称：

  Study of the Reactivity of 2-Acetyl-, 2-Cyano-, 2-Formyl-, and 2-Vinylphenyl Palladium(II) Complexes. Mono- and Triinsertion of an Isocyanide into the Pd−C Bond. A 2-Cyanophenyl Palladium Complex as a Ligand

  摘要：

  We have studied the reactivity of the complexes [Pd(C6H4X-2)Br(bpy)] (bpy = 2,2'-bipyridine; X = C(O)Me (1a), CN (1b), CHO (1c)), [Pd{C6H4CH=CH2-2}(PPh3)(bpy)](TfO) (TfO = CF3SO3; 2d), trans-[Pd(C6H4X-2)Br(PPh3)(2)] (X = C(O)Me (3a), CN (3b), CH=CH2 (3d)), and [Pd(mu-Br)(C6H4X-2)(PPh3)]2(X = C(O)Me (4a), CN (4b)). Their reactions with XyNC (Xy = 2,6-dimethylphenyl) depend on the nature of X and the other ligands and on the reaction conditions. The products of these reactions are mono- and triinserted complexes. Among the former are [Pd{C(=NXy)C6H4X-2}Br(L-2)] (L-2 = bpy, X = C(O)Me (5a), CN (5b); L = CNXy, X = C(O)Me (6a), CN (6b), CH=CH2 (6d)) and trans- [Pd{C(=Nxy)C6H4CH= CH2-2}(CNxy)(2)(PPh3)](TfO) (7d). The reaction of 1c with XyNC (1:5 molar ratio) gives 10, a product resulting after substitution of bpy, coordination of two molecules of XyNC, triinsertion of XyNC, and a cyclization resulting after the attack of the nitrogen of the first inserted molecule at the carbon atom of the formyl group. The complexes [Pd{kappa(2)C(1),N-3-C(= NXy)C(=NXy)C(=NXy)C6H4X-2}Br(CNXy)] (X = C(O)Me (8a), CN (8b)) were obtained by reacting (i) 3a or 3b with XyNC (1:4 molar ratio) or (ii) Pd(dba)(2) (dba = dibenzylideneacetone) with BrC6H4X-2 and XyNC (1:1:4 molar ratio). When this oxidative addition reaction was carried out with BrC6H4CHO-2, the resulting product decomposed to give the Pd(l) complex [Pd2Br2(CNXy)(4)] (9). Tl(TfO) was reacted with (1) 8a and 8b (11 molar ratio) to give the corresponding triflato complexes 11a and 11b, (ii) 4a (1:2 molar ratio) in the presence of moisture to give the cyclopalladated aquo complex [Pd{kappa(2)C,O-C6H4{C(O)Me-2}(OH2)(PPh3)]-(TfO) (12a), and (iii) 4b (3:1 molar ratio) to give [Pd(C6H4CN-2)(kappa(2)NN-4b)(PPh3)](TfO) (13b), in which 4b behaves as a ligand through the two cyano groups. The crystal structures of 5b, 6b, 7d, 8a,b, 9, 10, 11a,b, 12a, and 13b have been determined by X-ray diffraction studies.

  DOI：

  10.1021/om020380s