[η²-benzyne][bis(triethylphosphine)]nickel(0) | 161587-76-4

• 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: [η²-benzyne][bis(triethylphosphine)]nickel(0)
• 英文别名: [Ni(η²-benzyne)(PEt₃)₂]；[Ni(η²-benzyne)(triethylphosphine)₂]；[Ni((1,2-η)-benzyne)(triethylphosphine)2]；Ni((1,2-η)-C6H4)(PEt3)2；[Ni(η2-C6H4)(P(C2H5)3)2]；Cyclohexa-1,3-dien-5-yne;nickel;triethylphosphane
• CAS: 161587-76-4
• 化学式: C₁₈H₃₄NiP₂
• 分子量: 371.105
• InChiKey: RBANDGGLRURDML-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.34
• 重原子数：
  21
• 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：
  0

反应信息

• 作为反应物：
  描述：

  [η²-benzyne][bis(triethylphosphine)]nickel(0) 在 bromine 作用下， 以 正己烷 为溶剂， 生成 [Ni(1,4-dimethyl-2,3-naphthylenebis(diphenylphosphine))Br2]
  参考文献：
  名称：

  通过将（炔基）二苯基膦双插入镍（0）-苯炔配合物中来形成（二苯基膦基）萘

  摘要：

  （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 2{6,7-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

  DOI：

  10.1021/om990749m
• 作为产物：
  描述：

  2-(2-溴苯基)-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷 在 Zn 、 t-C₄H₉OK 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 [η²-benzyne][bis(triethylphosphine)]nickel(0)
  参考文献：
  名称：

  通过邻位金属苯硼酸酯的分子内 Suzuki 偶联制备第 10 族金属的苯炔配合物：第一个苯-钯 (0) 配合物的分子结构

  摘要：

  一系列镍 (II) 和钯 (II) 芳基配合物在芳环的邻位被（频哪醇）硼酸酯基团取代，[MBr[oC(6)H(4)B(pin)]L( 2)] (M = Ni, L(2) = 2PPh(3) (2a), 2PCy(3) (2b), 2PEt(3) (2c), dcpe (2d), dppe (2e), and dppb ( 2f); M = Pd, L(2) = 2PPh(3) (3a), 2PCy(3) (3b), and dcpe (3d)), 已经准备好了。许多这些配合物很容易与 KO(t)Bu 反应形成相应的苄配合物 [M(eta(2)-C(6)H(4))L(2)] (M = Ni, L(2) = 2PPh(3) (4a)、2PCy(3) (4b)、2PEt(3) (4c)、dcpe (4d)；M = Pd，L(2) = 2PCy(3) (5b))。该反应可视为 Suzuki 交叉偶

  DOI：

  10.1021/ja0264091

文献信息

• Preparation of Aryne–Nickel Complexes from <i>ortho</i>-Borylaryl Triflates
  作者：Yuto Sumida、Tomoe Sumida、Daisuke Hashizume、Takamitsu Hosoya

  DOI：10.1021/acs.orglett.6b02831

  日期：2016.11.4

  A facile method for preparing diverse aryne–nickel complexes from readily synthesized ortho-borylaryl triflates is described. Exploratory synthetic applications, including the synthesis of 1,2-difunctionalized arenes, based on the nucleophilic character of the aryne–nickel complexes are also demonstrated.

  描述了一种从容易合成的邻硼烷基芳基三氟甲磺酸酯制备各种芳烃-镍配合物的简便方法。还展示了基于芳烃-镍配合物亲核特性的探索性合成应用，包括1,2-双官能化芳烃的合成。
• Successive insertion of tetrafluoroethylene and CO and of tetrafluoroethylene and acetylenes into aryne–nickel(0) bonds
  作者：Martin A. Bennett、Margaret Glewis、David C. R. Hockless、Eric Wenger

  DOI：10.1039/a702375h

  日期：——

  Aryne–nickel complexes [Ni(η 2 -C 6 H 4 )L 2 ] [L 2 = 2PEt 3 or dcpe; dcpe = (C 6 H 11 ) 2 PCH 2 CH 2 P(C 6 H 11 ) 2 ] and [Ni(η 2 -C 10 H 6 )(PEt 3 ) 2 ] reacted readily with C 2 F 4 to form the corresponding five-membered tetrafluoro-substituted nickelacycles [Ni(C 6 H 4 CF 2 CF 2 -2)L 2 ] (L 2 = dcpe or 2PEt 3 ) and [Ni(2-C 10 H 6 CF 2 CF 2 -3)(PEt 3 ) 2 ], respectively. The complex [Ni(C 6 H 4 CF 2 CF 2 -2)(dcpe)] is very stable towards air, whereas the PEt 3 analogues react readily to give µ-aryloxo dimers. The naphthalene-based dimer [Ni(µ-2-OC 10 H 6 CF 2 CF 2 -3)(PEt 3 )} 2 ] has been structurally characterized. The complexes [Ni(C 6 H 4 CF 2 CF 2 -2)L 2 ] insert CO into their aryl–nickel bonds to form six-membered acyl complexes [NiC(O)C 6 H 4 CF 2 C F 2 -2}L 2 ] (L 2 = dcpe or 2PEt 3 ) and, after CO-induced reductive elimination, 2,2,3,3-tetrafluoroindanone. The dcpe acyl complex has also been shown to undergo reaction with air to form the carboxylato complex [NiOC(O)C 6 H 4 CF 2 C F 2 -2}(dcpe)], whose structure has been confirmed by X-ray crystallography. Some insertions of acetylenes into the aryl–nickel bonds of [Ni(C 6 H 4 CF 2 CF 2 -2)L 2 ] are also reported.

  Aryne–镍配合物 [Ni(η²-C6H4)L2] [L2 = 2PEt3或dcpe；dcpe = (C6H11)2PCH2CH2P( )2] 和 [Ni(η²-C10H6)(PEt3)2] 很容易与C2F4反应，形成相应的五元四氟取代镍环 [Ni( CF2CF2-2)L2] (L2 = dcpe或2PEt3) 和 [Ni(2- CF2CF2-3)(PEt3)2]。配合物 [Ni( CF2CF2-2)(dcpe)] 对空气非常稳定，而PEt3 的类似物则容易反应生成μ-芳氧二聚体。基于萘的二聚体 [Ni(μ-2-O CF2CF2-3)(PEt3)}2] 已被结构表征。配合物 [Ni( CF2CF2-2)L2] 将CO插入其芳基–镍键，形成六元酰基配合物 [NiC(O) CF2CF2-2}L2] (L2 = dcpe或2PEt3)，并在CO诱导下进行还原消除，生成2,2,3,3-四氟印酮。dcpe 酰基配合物也已被证明可以与空气反应形成羧酸盐配合物 [NiOC(O) CF2CF2-2}(dcpe)]，其结构已通过X射线晶体学确认。也有一些关于碳乙炔插入 [Ni( CF2CF2-2)L2] 中芳基–镍键的报道。
• 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.