| 137540-20-6

• CAS: 137540-20-6
• 化学式: C₁₆H₃₃Br₂Ni₂P₃
• 分子量: 595.547
• InChiKey: SQZNWSGCXVLJRE-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：

  、 三甲基膦 在 CO 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以50%的产率得到
  参考文献：
  名称：

  Binuclear σ- and η³-benzylic derivatives of nickel

  摘要：

  The stepwise reaction of the dibromides m- and p-BrCH2C6H4Br with [Ni(cod)(PMe3)2] (cod = cycloocta-1,5-diene) affords the sigma-benzylic derivatives trans-[Ni(CH2C6H4Br)Br(PMe3)2] 1a (meta) or lb (para) and the binuclear species trans,trans-[(Me3P)2BrNi(mu-sigma:sigma-CH2C6H4)NiBr(PMe3)2] 2a (meta) or 2b (para). If the second oxidative addition is carried out using equimolar amounts of [Ni(cod)2] and PMe3 the pseudo-allyl complexes trans-[(Me3P)BrNi(mu-eta-3:sigma-CH2C6H4)NiBr(PMe3)2] 5a (meta) or 5b (para) are obtained instead. Carbonylation of the binuclear compounds 2 yields the stable bis(acyl) derivatives trans,trans-[(Me3P)2BrNi(mu-COCH2C6H4CO)NiBr(PMe3)2] 3a (meta) or 3b (para) while excess of PMe3 induces a reductive elimination process that furnishes the bis(aryl) species trans,trans-[(Me3P)2BrNi-(mu-C6H4CH2CH2C6H4)NiBr(PMe3)2] 4a (meta) or 4b (para). A crystal structure determination of complex 2b has been undertaken: monoclinic, space group P2(1)/c, with cell dimensions a = 11.241 (1), b = 8.866(2), c = 29.323(8) angstrom, beta = 90.22(1)-degrees and Z = 4. The geometry around both nickel atoms is distorted square planar, with a dihedral angle between the two co-ordination planes of 103.77(9)-degrees.

  DOI：

  10.1039/dt9920001769
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 3-溴苄溴 、 三甲基膦 以 乙醚 、 甲苯 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  Binuclear σ- and η³-benzylic derivatives of nickel

  摘要：

  The stepwise reaction of the dibromides m- and p-BrCH2C6H4Br with [Ni(cod)(PMe3)2] (cod = cycloocta-1,5-diene) affords the sigma-benzylic derivatives trans-[Ni(CH2C6H4Br)Br(PMe3)2] 1a (meta) or lb (para) and the binuclear species trans,trans-[(Me3P)2BrNi(mu-sigma:sigma-CH2C6H4)NiBr(PMe3)2] 2a (meta) or 2b (para). If the second oxidative addition is carried out using equimolar amounts of [Ni(cod)2] and PMe3 the pseudo-allyl complexes trans-[(Me3P)BrNi(mu-eta-3:sigma-CH2C6H4)NiBr(PMe3)2] 5a (meta) or 5b (para) are obtained instead. Carbonylation of the binuclear compounds 2 yields the stable bis(acyl) derivatives trans,trans-[(Me3P)2BrNi(mu-COCH2C6H4CO)NiBr(PMe3)2] 3a (meta) or 3b (para) while excess of PMe3 induces a reductive elimination process that furnishes the bis(aryl) species trans,trans-[(Me3P)2BrNi-(mu-C6H4CH2CH2C6H4)NiBr(PMe3)2] 4a (meta) or 4b (para). A crystal structure determination of complex 2b has been undertaken: monoclinic, space group P2(1)/c, with cell dimensions a = 11.241 (1), b = 8.866(2), c = 29.323(8) angstrom, beta = 90.22(1)-degrees and Z = 4. The geometry around both nickel atoms is distorted square planar, with a dihedral angle between the two co-ordination planes of 103.77(9)-degrees.

  DOI：

  10.1039/dt9920001769

文献信息

• Binuclear complexes of nickel bridged by hydrocarbon ligands. Isocyanide insertion chemistry and amide formation by intramolecular coupling of acyl and imidoyl functionalities
  作者：Juan Campora、Ernesto Carmona、Enrique Gutierrez、Pilar Palma、Manuel L. Poveda、Caridad Ruiz

  DOI：10.1021/om00037a006

  日期：1992.1

  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.