(2-oxo-1-naphthoyl)tris(trimethylphosphine)nickel | 156998-88-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (2-oxo-1-naphthoyl)tris(trimethylphosphine)nickel
• 英文别名: nickel(2+);1-(oxomethyl)naphthalen-2-olate;trimethylphosphane
• CAS: 156998-88-8
• 化学式: C₂₀H₃₃NiO₂P₃
• 分子量: 457.092
• InChiKey: YHWPXVJJFTWKBY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2-oxo-1-naphthoyl)tris(trimethylphosphine)nickel 、 碘甲烷 以 乙腈 为溶剂， 以51%的产率得到mer-trans-iodo(methyl)-(2-oxo-1-naphthoyl)bis(trimethylphosphine)nickel
  参考文献：
  名称：

  Oxidation–reduction exchange of 2-acylenolato and trimethylphosphane ligands between d6 and d8 complexes of nickel and cobalt

  摘要：

  A series of five (C:O)-dianionic 1-acyl-2-enolato ligands C(O)-C=C-O in a transmetallation reaction between 18-electron metal-d(6) complexes mer-trans-NiMe(X)[C(O)-C=C-O](PMe3)(2) [C=C=C6H4, X = I (1); C=C=3-CMe3-5-Me-C6H2, X=I (2); C=C=5,6-benzo-C6H2, X = I (3); C=C=3,4-benzo-cyclohexene, X = Br (4); C=C=1,2-diphenylethene, X = I (5)] and the 18-electron metal-d(8) compound CoMe(PMe3)(4) (1:2), undergo a reductive coupling of acyl and methylnickel functions involving the C(O)-C=C-O ligands. Subsequent migration of methyl groups between cobalt intermediates generates three products: mer-trans-CoMe2[MeC(O)-C=C-O](PMe3)(2) (6-10), Ni(PMe3)(4), and CoX(PMe3)(3). The X-ray crystal structure of compound 7 has been determined. The methyl ligands are found in positions opposite to the O-donor functions. Upon replacing the aromatic rings in salicylaldehyde derivatives C(O)-C=C-O by more flexible cyclohexene rings or acyclic systems the reduction of Ni(IV) complexes follows a different course. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00331-x
• 作为产物：
  描述：

  bis(μ-2-oxonaphthalene-1-carbaldehyde)bis[methyl(trimethylphosphine)nickel] 、 三甲基膦 以 乙醚 为溶剂， 以48%的产率得到(2-oxo-1-naphthoyl)tris(trimethylphosphine)nickel
  参考文献：
  名称：

  Ligand-Induced Fragmentation of Methylnickel Phenolates Containing a 2-Aldehyde Function: Structure of (3-tert-Butyl-5-methyl-2-oxobenzoyl)tris(trimethylphosphine)nickel

  摘要：

  O-bridging salicylaldehyde derivatives in dimeric methylnickel compounds NiMe(OR)(PMe3) showing equilibria of cis and trans forms (OR = 2-oxobenzaldehyde (1), 3-tert-butyl-5-methyl-2-oxobenzaldehyde (2), 3,5-di-tert-butyl-2-oxobenzaldehyde (3), 2-oxonaphthaldehyde (4)) spontaneously undergo, upon addition of trimethylphosphine, a fragmentation reaction forming 2-oxobenzoyl-C,O chelating ligands in 18-electron mononuclear complexes Ni(OC=O)(PMe3)3 (OC=O = 2-oxobenzoYl (5), 3-tert-butyl-5-methyl-2-oxobenzoyl (6), 3,5-di-tert-butyl-2-oxobenzoYl (7), 2-oxonaphthoyl (8)). The molecular structure of 6 contains pentacoordinate nickel with a chelate bite angle C-Ni-O = 85.5(1)-degrees. Dissociation of phosphine ligands in 5 gives Ni(OC=O)(PMe3)2 (9) and [Ni(OC)(PMe3)]2 (10), but no mobilization of carbonyl ligands could be observed in the presence of Ni(PMe3)4 as CO acceptor.

  DOI：

  10.1021/om00020a009