[Pd(C(NC6H3Me2)C6H4C(O)Me-2)(2,2'-bipyridine)Br] | 474832-72-9

• 英文名称: [Pd(C(NC6H3Me2)C6H4C(O)Me-2)(2,2'-bipyridine)Br]
• CAS: 474832-72-9
• 化学式: C₂₇H₂₄BrN₃OPd
• 分子量: 592.831
• InChiKey: NONFVYVJYMTIDJ-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  [Pd(C6H4(C(O)Me)-2)Br(2,2'-bipyridine)] 、 2,6-二甲基苯基异腈 以 二氯甲烷 为溶剂， 以84%的产率得到[Pd(C(NC6H3Me2)C6H4C(O)Me-2)(2,2'-bipyridine)Br]
  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