| 137540-19-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 137540-19-3
• 化学式: C₂₅H₄₂Br₂NNi₂P₃
• 分子量: 726.724
• InChiKey: HSNMPJGMEQOHLC-UHFFFAOYSA-L

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：

  在 CO 、 H⁽¹⁺⁾ 作用下， 以 丙酮 为溶剂， 生成 2-(2,6-Dimethylphenyl)isoquinolin-1(2H)-one
  参考文献：
  名称：

  镍的双核络合物，由烃配体桥接。异氰酸酯的插入化学和酰胺基和酰亚胺基官能团的分子内偶联形成酰胺

  摘要：

  Ni(cod)(PMe3)2 and the o-, m-, and p-bromobenzyl bromides react, under appropriate conditions, to afford the binuclear complexes Ni2(mu(2)-eta(3),eta(1)-CH2C6H4)Br2(PMe3)3 (1a-c) or Ni2(mu(2)-eta(1),eta(1)-CH2C6H4)Br2(PMe3)4 (2b,c). The reaction of the ortho eta(3)-benzylic derivative 1a with isocyanides, CNR, has been investigated, and three different isomeric species have been identified for R = Bu(t). The CNC6H3-2,6-Me2 insertion product, 4, reacts with CO to form a Ni(II)-vinyl complex 7 derived from the N-aryl-1-isoquinolone 8, which can be freed by hydrolytic cleavage of the Ni-vinyl bond.

  DOI：

  10.1021/om00037a006
• 作为产物：
  描述：

  2-溴溴苄 以 四氢呋喃 、 乙醚 为溶剂， 生成
  参考文献：
  名称：

  镍的双核络合物，由烃配体桥接。异氰酸酯的插入化学和酰胺基和酰亚胺基官能团的分子内偶联形成酰胺

  摘要：

  Ni(cod)(PMe3)2 and the o-, m-, and p-bromobenzyl bromides react, under appropriate conditions, to afford the binuclear complexes Ni2(mu(2)-eta(3),eta(1)-CH2C6H4)Br2(PMe3)3 (1a-c) or Ni2(mu(2)-eta(1),eta(1)-CH2C6H4)Br2(PMe3)4 (2b,c). The reaction of the ortho eta(3)-benzylic derivative 1a with isocyanides, CNR, has been investigated, and three different isomeric species have been identified for R = Bu(t). The CNC6H3-2,6-Me2 insertion product, 4, reacts with CO to form a Ni(II)-vinyl complex 7 derived from the N-aryl-1-isoquinolone 8, which can be freed by hydrolytic cleavage of the Ni-vinyl bond.

  DOI：

  10.1021/om00037a006

文献信息

• Isocyanide insertion chemistry. Synthesis and structural characterization of bridging imidoyl complexes of nickel and amide formation by intramolecular coupling of acyl and imidoyl functionalities
  作者：Juan Campora、Enrique Gutierrez、Angeles Monge、Manuel L. Poveda、Caridad Ruiz、Ernesto Carmona

  DOI：10.1021/om00034a039

  日期：1993.10

  The binuclear pseudoallyl complex trans-(Me3P)BrNi(mu2-eta3:eta1-CH2-o-C6H4)NiBr(PMe3)2 (1) inserts selectively 1 equiv of CNXy (Xy = 2,6-dimethylphenyl) into the Ni-benzylic bond with formation of the cyclic complex trans-(Me3P)2BrNi(C(NXy)CH2-o-C6H4)NiBr(PMe3) (2) that contains a bridging eta2-imidoyl ligand. The analogous reaction of 1 with CNBu(t) gives a related mu2,eta2-imidoyl species 3a which, in contrast to 2, exists in solution in thermodynamic equilibrium with its isomer tran-(Me3P)BrNi(eta2-C(NBut)CH2-o-C6H4)NiBr(PMe3)2 (3b), in which the imidoyl ligand is terminally bonded in a eta2 fashion to one of the nickel centers. Variable temperature NMR studies show 3b is the kinetic product of the insertion reaction and that the strongly solvent dependent equilibrium 3a half arrow right over half arrow left 3b is attained only at sufficiently high temperatures (ca. -20-degrees-C). At even higher temperatures (ca. 40-degrees-C), the 3a-3b mixtures convert into a third isomeric compound, trans-(Me3P)2Ni(C(NBut)C6H4-o-CH2)NiBr(PMe3) (4), in a process which formally corresponds to the deinsertion of CNBu(t) from the Ni-benzyl bond followed by reinsertion into the Ni-aryl moiety. In a rather complex reaction 2 interacts with CO to afford the mononuclear complex trans-Ni(C=CHC6H4C(O)NXy)Br(PMe3)2 (5) whose formation probably involves the intramolecular coupling of acyl and imidoyl functionalities. Hydrolytic cleavage of the Ni-C bond in 5 provides the corresponding N-aryl-1-isoquinolone 6. Compounds 2 and 3a, have been characterized by X-ray studies. 2 crystallizes in the monoclinic space group P2(1)/n with a = 12.437(3) angstrom, b = 16.025(2) angstrom, c = 16.015(2) angstrom, beta = 101.47(1)degrees, and Z = 4. Crystals of 3a are also monoclinic, space group P2(1)/n, with a = 26.05(1) angstrom, b = 10.226(1) angstrom, c = 12.013(2) angstrom, beta = 93.54(12)degrees, and Z = 4. The mu2,eta2-imidoyl functionalities of both complexes exhibit similar structural characteristics.