Ni((1,2-η)-4,5-F2C6H2)(1,2-bis(dicyclohexylphosphino)ethane) | 161587-84-4

• 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-F2C6H2)(1,2-bis(dicyclohexylphosphino)ethane)
• 英文别名: Dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane;2,3-difluorocyclohexa-1,3-dien-5-yne;nickel
• CAS: 161587-84-4
• 化学式: C₃₂H₅₀F₂NiP₂
• 分子量: 593.383
• InChiKey: AFNICBNWEZXIOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.84
• 重原子数：
  37
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 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-F2C6H2)(1,2-bis(dicyclohexylphosphino)ethane) 、 一氧化碳 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  （苯炔）镍（0）配合物与一氧化碳插入反应：一个（Phthalato）镍的X射线结构（II）配合物形成由氧化的η的1：η 1 -Phthaloyl中间体

  摘要：

  （苯炔）镍（0）的反应复合物的Ni（η 2 -C 6 H ^ 4）（DCPE）（1）和Ni（（1,2-η）-4,5--F 2 C ^ 6 ħ 2）（ dcpe）（2）[dcpe = 1,2-双（二环己基膦基）乙烷，（C 6 H 11）2 PCH 2 CH 2 P（C 6 H 11）2 ]低浓度一氧化碳得到Ni（CO）2（dcpe）（3），以及作为主要有机产物的9 H -fluoren-9-one（4）和2,3,6,7-tetrafluoro-9H-芴-9-一（5），2,3,6,7-X 4 C 12 H 4 CO（X = H，F），分别是由于单插入镍-苄基键中所致。较高浓度的CO生成双（酰基）中间体，其中31 P和19观察到其中一种Ni（CO-4,5-F 2 C 6 H 2 CO-2）（dcpe）（9）。F NMR光谱。这些中间体可逆地形成3和相应的苯并环丁烯二酸酯OC-4,5-X 2 C 6

  DOI：

  10.1021/om950699v
• 作为产物：
  描述：

  NiBr(2-Br-4,5-F2C6H2)(1,2-bis(dicyclohexylphosphino)ethane) 在 lithium 作用下， 以 正己烷 、 甲苯 为溶剂， 以85%的产率得到Ni((1,2-η)-4,5-F2C6H2)(1,2-bis(dicyclohexylphosphino)ethane)
  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

• 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.
• Insertion Reactions of (Benzyne)nickel(0) Complexes with Carbon Monoxide:  X-ray Structure of a (Phthalato)nickel(II) Complex Formed by Oxidation of an η¹:η¹-Phthaloyl Intermediate
  作者：Martin A. Bennett、David C. R. Hockless、Mark G. Humphrey、Madeleine Schultz、Eric Wenger

  DOI：10.1021/om950699v

  日期：1996.2.6

  The reaction of (benzyne)nickel(0) complexes Ni(η2-C6H4)(dcpe) (1) and Ni((1,2-η)-4,5-F2C6H2)(dcpe) (2) [dcpe = 1,2-bis(dicyclohexylphosphino)ethane, (C6H11)2PCH2CH2P(C6H11)2] with carbon monoxide at low concentration gives Ni(CO)2(dcpe) (3) and, as the main organic products, 9H-fluoren-9-one (4) and 2,3,6,7-tetrafluoro-9H-fluoren-9-one (5), 2,3,6,7-X4C12H4CO (X = H, F), respectively, resulting from

  （苯炔）镍（0）的反应复合物的Ni（η 2 -C 6 H ^ 4）（DCPE）（1）和Ni（（1,2-η）-4,5--F 2 C ^ 6 ħ 2）（ dcpe）（2）[dcpe = 1,2-双（二环己基膦基）乙烷，（C 6 H 11）2 PCH 2 CH 2 P（C 6 H 11）2 ]低浓度一氧化碳得到Ni（CO）2（dcpe）（3），以及作为主要有机产物的9 H -fluoren-9-one（4）和2,3,6,7-tetrafluoro-9H-芴-9-一（5），2,3,6,7-X 4 C 12 H 4 CO（X = H，F），分别是由于单插入镍-苄基键中所致。较高浓度的CO生成双（酰基）中间体，其中31 P和19观察到其中一种Ni（CO-4,5-F 2 C 6 H 2 CO-2）（dcpe）（9）。F NMR光谱。这些中间体可逆地形成3和相应的苯并环丁烯二酸酯OC-4,5-X 2 C 6