[Ni((1,2-η)-4,5-difluorobenzyne)(triethylphosphine)2] | 161587-83-3

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [Ni((1,2-η)-4,5-difluorobenzyne)(triethylphosphine)2]
• 英文别名: Ni((1,2-η)-4,5-F2C6H2)(PEt3)2；Ni(η2-C6H2F2)(PEt3)2；[(PEt3)2Ni(η2-C6H2-4,5-F2)]
• CAS: 161587-83-3
• 化学式: C₁₈H₃₂F₂NiP₂
• 分子量: 407.086
• InChiKey: GHYIDUJIVPSUGX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.62
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [Ni((1,2-η)-4,5-difluorobenzyne)(triethylphosphine)2] 在 B(C₆F₅)3 作用下， 以 正戊烷 为溶剂， 生成 [(PEt3)2Ni]2(μ-η1:η1-3,4-F2C6H2-3',4'-F2C6H2)
  参考文献：
  名称：

  双核Ni(I)联芳基配合物中的1,4-位移：单价镍活化C-H键的机理研究

  摘要：

  已知的芳炔配合物 (PEt3)2Ni(eta2-C6H2-4,5-F2) (1a) 与催化量的 Br2Ni(PEt3)2 在 1% Na/Hg 下反应，得到双核 Ni(I) 联芳基配合物。 (PEt3)2Ni]2(mu-eta1:eta1-3,4-F2C6H2-3',4'-F2C6H2) (2a)，由 CC 键形成和 CH 键重排的组合产生。双核苄基 [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) (3) 通过 1a 与化学计量的 Br2Ni(PEt3)2 在过量 1% Na 上反应获得/Hg 和 3 被发现催化 1a 到 2a 的转化。1a 与 B(C6F5)3 的反应产生了三核复合物 (PEt3)3Ni3(mu3:eta1:eta1:eta2-4,5-F2C6H2)(mu3:eta1:eta1:eta2-4,5-F2C6H2-4' ,5'-F2C6H2) (6)。将

  DOI：

  10.1021/ja067112w
• 作为产物：
  描述：

  NiBr(2-Br-4,5-F2C6H2)(PEt3)2 在 lithium 作用下， 以 乙醚 为溶剂， 以78%的产率得到[Ni((1,2-η)-4,5-difluorobenzyne)(triethylphosphine)2]
  参考文献：
  名称：

  苯炔-镍（0）配合物与乙炔的插入反应

  摘要：

  Complexes of nickel(0) containing eta(2)-4,5-difluorobenzyne, Ni((1,2-eta)-4,5-F2C6H2)(PEt(3))(2) (10) and Ni((1,2-eta)-4,5-F2C6H2)(dcpe) (11; dcpe = 1,2-bis(dicyclohexylphosphino)ethane, Cy(2)PCH(2)-CH(2)PCy(2)) have been synthesized by alkali-metal reduction of the appropriate (2-halo-genoaryl)nickel(II) halides. Spectroscopic measurements (C-13 NMR, FAB-MS) indicate that 10, 11, and the parent benzyne complex Ni((1,2-eta)-C6H4)(PEt(3))(2) (2) are monomeric, analogous to the structurally characterized species Ni((1,2-eta)-C6H4)(Cy(2)PCH(2)CH(2)PCy(2)). Complexes 2 and 10 undergo rapid intermolecular exchange with PEt(3) at room temperature and react with disubstituted acetylenes by double insertion into the metal-benzyne bond to form 1,2,3,4-tetrasubstituted naphthalenes. With electrophilic acetylenes (MeO(2)CC(2)CO(2)Me, MeC(2) . CO(2)Me, HC(2)CO(2)Me, and CF3C2CF3) an aromatic cyclotrimer is also formed; exceptionally, hexafluorobut-2-yne also gives with 10 a phenanthrene derived from two benzyne units and the acetylene. The unsymmetrical acetylenes tert-butylacetylene and methyl 2-butynoate give rise to good regioselectivity in the resulting naphthalenes, the favored isomers being very dependent on the steric and electronic influence of the substituents. The dcpe complexes react similarly but more slowly with acetylenes, and with MeO(2)CC(2)CO(2)Me the monoinsertion complexes Ni{C(CO(2)Me)=C(CO(2)Me)C(6)H(2)R(2)-o}(dcpe) (R = H, F) can be observed.

  DOI：

  10.1021/om00003a029

文献信息

• Nickel(0)-Catalyzed Isomerization of an Aryne Complex:  Formation of a Dinuclear Ni(I) Complex via C−H Rather than C−F Bond Activation
  作者：Alana L. Keen、Samuel A. Johnson

  DOI：10.1021/ja0572553

  日期：2006.2.1

  The reaction of the aryne complex (PEt3)2Ni(eta2-C6H2-4,5-F2) with a catalytic amount of Ni(PEt3)2 results in a dinuclear Ni(I) complex from the coupling of the isomer (PEt3)2Ni(eta2-C6H2-3,4-F2), obtained via rearrangement of the aromatic C-H bonds, which demonstrates that Ni(PEt3)2 is kinetically capable of C-H bond activation, even in the presence of C-F bonds. The intermediate [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4

  芳炔配合物 (PEt3)2Ni(eta2-C6H2-4,5-F2) 与催化量的 Ni(PEt3)2 反应生成来自异构体 (PEt3)2Ni 偶联的双核 Ni(I) 配合物(eta2-C6H2-3,4-F2)，通过芳族 CH 键的重排获得，这表明 Ni(PEt3)2 在动力学上能够激活 CH 键，即使在存在 CF 键的情况下。分离出中间体 [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) 并进行晶体学表征；观察到的 mu-eta2:eta2 键合模式在芳炔化学中是前所未有的。
• Formation of (Diphenylphosphino)naphthalenes by Double Insertion of (Alkynyl)diphenylphosphines into Nickel(0)−Benzyne Complexes
  作者：Martin A. Bennett、Christopher J. Cobley、A. David Rae、Eric Wenger、Anthony C. Willis

  DOI：10.1021/om990749m

  日期：2000.4.1

  nickel(0)−benzyne bond of the complexes [Ni(1,2-η)-4,5-X2C6H2}(PEt3)2] (X = H (1a), F (1b)) to give mixtures of nickel(0) complexes containing (diphenylphosphino)naphthalenes, which in some cases are formed with high regioselectivity. Bromination of the mixtures of nickel(0) complexes obtained from Ph2PC⋮CR (R = Me, Ph) and 1a or 1b gives in high yield the chelate NiBr2 complexes [NiBr26,7-X2C10H2-1,4-Y2-2

  （炔基）二苯基膦Ph 2 PC⋮CR（R = H，Me，Ph，PPh 2）两次插入配合物[Ni （1,2-η）-4,5 -X 2 C 6 H 2 }（PEt 3）2 ]（X = H（1a），F（1b））得到含有（二苯基膦基）萘的镍（0）配合物的混合物，在某些情况下，该配合物的生成量很高区域选择性。由Ph 2 PC⋮CR（R = Me，Ph）和1a或1b获得的镍（0）配合物的混合物进行溴化，可高收率地螯合NiBr 2配合物[NiBr 26,7-X 2 C 10 H 2 -1,4-Y 2 -2,3-（PPh 2）2 }]（X = H，Y = Me（6a），Ph（11a）; X = F ，Y = Me（6b），Ph（11b）），可以通过在60℃下在DMSO中用NaCN处理而释放出相应的1,4-二取代的2,3-萘撑双（二苯基膦）12a，13a，12b和13b。或室温下的二甲基乙二肟/氨气。仅其中一个磷原子被氧化的衍生物6
• Insertion Reactions of Benzyne-Nickel(0) Complexes with Acetylenes
  作者：Martin A. Bennett、Eric Wenger

  DOI：10.1021/om00003a029

  日期：1995.3

  Complexes of nickel(0) containing eta(2)-4,5-difluorobenzyne, Ni((1,2-eta)-4,5-F2C6H2)(PEt(3))(2) (10) and Ni((1,2-eta)-4,5-F2C6H2)(dcpe) (11; dcpe = 1,2-bis(dicyclohexylphosphino)ethane, Cy(2)PCH(2)-CH(2)PCy(2)) have been synthesized by alkali-metal reduction of the appropriate (2-halo-genoaryl)nickel(II) halides. Spectroscopic measurements (C-13 NMR, FAB-MS) indicate that 10, 11, and the parent benzyne complex Ni((1,2-eta)-C6H4)(PEt(3))(2) (2) are monomeric, analogous to the structurally characterized species Ni((1,2-eta)-C6H4)(Cy(2)PCH(2)CH(2)PCy(2)). Complexes 2 and 10 undergo rapid intermolecular exchange with PEt(3) at room temperature and react with disubstituted acetylenes by double insertion into the metal-benzyne bond to form 1,2,3,4-tetrasubstituted naphthalenes. With electrophilic acetylenes (MeO(2)CC(2)CO(2)Me, MeC(2) . CO(2)Me, HC(2)CO(2)Me, and CF3C2CF3) an aromatic cyclotrimer is also formed; exceptionally, hexafluorobut-2-yne also gives with 10 a phenanthrene derived from two benzyne units and the acetylene. The unsymmetrical acetylenes tert-butylacetylene and methyl 2-butynoate give rise to good regioselectivity in the resulting naphthalenes, the favored isomers being very dependent on the steric and electronic influence of the substituents. The dcpe complexes react similarly but more slowly with acetylenes, and with MeO(2)CC(2)CO(2)Me the monoinsertion complexes NiC(CO(2)Me)=C(CO(2)Me)C(6)H(2)R(2)-o}(dcpe) (R = H, F) can be observed.
• 1,4-Shifts in a Dinuclear Ni(I) Biarylyl Complex:  A Mechanistic Study of C−H Bond Activation by Monovalent Nickel
  作者：Alana L. Keen、Meghan Doster、Samuel A. Johnson

  DOI：10.1021/ja067112w

  日期：2007.1.1

  catalytic amount of Br2Ni(PEt3)2 over 1% Na/Hg to afford the dinuclear Ni(I) biarylyl complex [(PEt3)2Ni]2(mu-eta1:eta1-3,4-F2C6H2-3',4'-F2C6H2) (2a), which results from a combination of C-C bond formation and C-H bond rearrangement. The dinuclear benzyne [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) (3) was obtained by the reaction of 1a with a stoichiometric amount of Br2Ni(PEt3)2 over excess 1% Na/Hg, and

  已知的芳炔配合物 (PEt3)2Ni(eta2-C6H2-4,5-F2) (1a) 与催化量的 Br2Ni(PEt3)2 在 1% Na/Hg 下反应，得到双核 Ni(I) 联芳基配合物。 (PEt3)2Ni]2(mu-eta1:eta1-3,4-F2C6H2-3',4'-F2C6H2) (2a)，由 CC 键形成和 CH 键重排的组合产生。双核苄基 [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) (3) 通过 1a 与化学计量的 Br2Ni(PEt3)2 在过量 1% Na 上反应获得/Hg 和 3 被发现催化 1a 到 2a 的转化。1a 与 B(C6F5)3 的反应产生了三核复合物 (PEt3)3Ni3(mu3:eta1:eta1:eta2-4,5-F2C6H2)(mu3:eta1:eta1:eta2-4,5-F2C6H2-4' ,5'-F2C6H2) (6)。将