(1-Me-Ind)(PPh3)Ni-Cl | 186262-50-0

• 英文名称: (1-Me-Ind)(PPh3)Ni-Cl
• 英文别名: [NiCl(1-methyl-indenyl)(triphenylphospine)](1+)；[(η5-1-methylindenyl)Ni(II)(Cl)(PPh3)]；[(1-methylindenyl)Ni(PPh3)Cl]
• CAS: 186262-50-0
• 化学式: C₂₈H₂₄ClNiP
• 分子量: 485.615
• InChiKey: CSGKQFRAFYCYKE-UHFFFAOYSA-M

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：

  (1-Me-Ind)(PPh3)Ni-Cl 以 四氢呋喃 、 乙醚 、 氘代苯 为溶剂， 生成 (1-methylindenyl)Ni(PPh3)Br
  参考文献：
  名称：

  茚基镍基咪唑配合物：合成，表征和反应性。

  摘要：

  制备了配合物（1-Me-茚基）Ni（PPh 3）（邻苯二甲酰亚胺酸酯），并通过IR和1 H，13 C { 1 H}和31 P { 1 H} NMR光谱和单晶X进行了全面表征射线衍射。还已经制备了类似的4，5-二氯邻苯二甲酰亚胺，马来酰亚胺和琥珀酰胺基络合物，并进行了光谱表征。与无法制备的类似Ni-酰胺基物质相比，这些配合物具有热稳定性。反应性研究表明，Ni-imidato键在插入和亲核反应以及VT 1中相当无反应。H NMR研究表明，马来酰亚胺络合物中Ni-N键周围的旋转受ca. 11 kcal / mol。邻苯二甲酰亚胺衍生物的固态结构表明，P，N，C1和C3原子在扭曲的方平面配位环境中排列在Ni原子周围，而C2原子在主方平面上方的键距内。所述phthalimidato配体为η 1（N）配位的成Ni; Ni-N键相对较短（1.895（4）Å），且酰亚胺配体的取向应使带有原子P，Ni，N和

  DOI：

  10.1021/om980653c
• 作为产物：
  描述：

  bis(triphenylphosphine)nickel(II) chloride 、 3-methylindenyllithium 以 乙醚 为溶剂， 以60%的产率得到(1-Me-Ind)(PPh3)Ni-Cl
  参考文献：
  名称：

  Structural and NMR Studies of Indenyl Hapticity and Rotational Barriers in the Complexes (η-1-R-Indenyl)Ni(PPh₃)(X) (R = H, Me; X = Cl, Me)

  摘要：

  The relative trans influences of Cl and Me in the complexes (1-Me-indenyl)Ni(PPh3)Cl and (1-Me-indenyl)Ni(PPh3)Me lead to different solid state hapticities for the 1-Me-indenyl ligands. Comparing the solution NMR data for these complexes and the energy barriers to the rotation of the indenyl ligands in their unsubstituted analogues demonstrates that solid state hapticities are preserved in solution.

  DOI：

  10.1021/om970715j
• 作为试剂：
  描述：

  苯乙烯 、 苯硅烷 在 (1-Me-Ind)(PPh3)Ni-Cl 四苯硼钠 作用下， 以 苯 为溶剂， 反应 5.0h， 生成 1-phenyl-2-(phenylsilyl)ethane 、 phenyl(1-phenylethyl)silane
  参考文献：
  名称：

  Hydrosilylation of alkenes and ketones catalyzed by nickel(II) indenyl complexes

  摘要：

  将复合物(indenyl)Ni(PPh3)Cl中的Cl-抽象生成了阳离子物种，这些物种是一些烯烃和酮的有效前催化剂。例如，(1-Me-indenyl)Ni(PPh3)Cl和NaBPh4（或甲基铝氧烷）的混合物在室温下与大约100当量的PhSiH3和苯乙烯反应，产生[1-苯基-1-乙基](苯基)硅烷，PhCH(CH3)(SiPhH2)，收率为50%-80%。相同的体系还可以催化1-己烯和去氧茂烷的氢硅烷化反应，但这些底物产生的产物是位置异构体和立体异构体的混合物。另一方面，酮的氢硅烷化是位置特异的，产物是相应的硅醚，收率很高。许多实验观察表明，最初生成的基于镍的阳离子不是催化活性物种。事实上，阳离子引发剂可以被LiAlH4或AlMe3取代，它们分别生成相应的Ni-H或Ni-Me衍生物。此外，对于PhSiH3与苯乙烯的加成的观察到的位置选择性（即，矽烷基片段主要加到α-C）与如果反应机制涉及碳正离子中间体时所预期的相反。提出了一种新的机制，其中活性物种是来自PhSiH3向最初生成的Ni阳离子转移的Ni-H物种。关键词：氢硅烷化，镍茚基复合物，阳离子复合物，氢化物中间体。

  DOI：

  10.1139/v03-133

文献信息

• Me₂AlCH₂PMe₂: A New, Bifunctional Cocatalyst for the Ni(II)-Catalyzed Oligomerization of PhSiH₃
  作者：Frédéric-Georges Fontaine、Davit Zargarian

  DOI：10.1021/ja048911m

  日期：2004.7.1

  (t(1/2) ca. 12 h) but accelerates the Si-H bond activation and Si-Si bond formation reactions. The catalysis promoted by 2a/3 proceeds even faster in the presence of NEt3 or THF (TOF > 1600 h(-1)), because these Lewis bases favor the monomeric form of 3, which in turn favors the formation of 4. On the other hand, the much more nucleophilic base quinuclidine suppresses the catalysis (TOF < 300 h(-1)) by hindering

  已经研究了甲基铝氧烷 (MAO) 在 Ni 催化的 PhSiH3 脱氢同系化中的作用，以设计具有明确定义的化学成分和结构的新型助催化剂。这些研究表明，双功能试剂 (Me2PCH2AlMe2)2, 3 等物质应作为 Si-Si 键形成反应的助催化剂。因此，发现 (1-Me-茚基)Ni(PPh3)Me、2a 和 3（Ni/Al 比率为 1:1）的组合将 PhSiH3 转化为具有转换频率的环状低聚物 (PhSiH)n（ TOF) > 500 h(-1)，比单独使用 2a 快 50 倍。详细的 NMR 研究表明，这种加速是由于中间体 (1-Me-茚基)Ni(Me)(Me2PCH2AlMe2), 4 的形成。该复合物中的 PMe2 部分与 Ni 中心的协调允许系留的 AlMe2 部分与 Ni-Me 部分相互作用，从而促进相当缓慢的 Al-Me/Ni-CD3 交换 (t(1/2) ca。 12 h) 但加速了
• Preparation, characterization, and reactivities of thienyl nickel complexes bearing indenyl ligands
  作者：Ruiping Wang、Laurent F Groux、Davit Zargarian

  DOI：10.1016/s0022-328x(02)01798-9

  日期：2002.10

  5×104 Da. NMR studies have revealed that MAO methylates these complexes without ionizing the Nithienyl bond; this implies that the polymerization reactions likely follow a non-cationic mechanism similar to that catalyzed by the corresponding NiCCPh complexes studied previously. Complexes 1–5 reacted with CF3SO3H to produce the corresponding NiOSO2CF3 compounds by protonation at the α-C of the thienyl

  配合物（1-R，2-R'-茚基）NiPPh 3（噻吩基）（R'= H，R = Me（1）; Et（2）; i -Pr（3）; CH 2 Ph（4） ; R'=苯基，R =我（5））已经被制备和表征通过光谱技术和，在的情况下1，2和5，通过X射线晶体学研究。当与MAO结合，这些化合物催化苯乙炔聚合顺-transoidal聚（苯基乙炔）与中号瓦特在5-7.5×10的范围内4那里。NMR研究表明，MAO可以使这些络合物甲基化，而不会电离Niththenyl键。这表明聚合反应可能遵循类似于先前研究的相应NiCCPh配合物催化的非阳离子机理。配合物1 - 5与CF反应3 SO 3 H至产生相应NiOSO 2 CF 3个通过质子在噻吩基部分的α-C的化合物。已经分离出化合物（1-Bz茚基）Ni（PPh 3）（OSO 2 CF 3）（9）并对其进行了充分表征。
• Solid State Structures and Phosphine Exchange Reactions of (1-Me-Indenyl)(PR₃)Ni−Cl
  作者：Frédéric-Georges Fontaine、Marc-André Dubois、Davit Zargarian

  DOI：10.1021/om010608w

  日期：2001.11.1

  The complexes (1-Me-Ind)(PR3)Ni-Cl (Ind = indenyl; R = Me (2), Cy (3), Bu (4), and (CH2)(2)(CF2)(5)CF3 (5)) have been prepared by the direct reaction of the corresponding (PR3)(2)NiCl2 with Li(1-Me-Ind) or via phosphine exchange reactions with (1-Me-Ind)(PR ' (3))Ni-CI (R ' = Ph (1) and Me). Solution NMR and single-crystal X-ray diffraction studies of the structures of 2 and 3 have allowed an analysis of the mode of coordination of the 1-Me-Ind ligand both in the solid state and in solution. Kinetic studies have shown that the substitution of PPh3 in (1-Me-Ind)(PPh3)Ni-Cl by PCy3 follows a second-order rate (associative mechanism) with the following kinetic parameters. K-2 (x 10(-2) M-1 s(-1)) = 1.1 +/- 0.1 at 233 K, 1.9 +/- 0.4 at 245 K, 15 +/- 2 at 284 EC, 21 +/- 2 at 293 K, and 34 +/- 7 at 303 K, DeltaH double dagger = 6.40 +/- 0.07 kcal/mol; DeltaS double dagger = -40 +/- 4 eu. The implications of these results for the mechanisms of the polymerization reactions catalyzed by these complexes have been discussed.
• Preparation and Characterization of (1-Me-indenyl)Ni(PR₃)(CC−Ph) (R = Cy, Ph) and Alkyne Polymerization Catalysis
  作者：Ruiping Wang、Francine Bélanger-Gariépy、Davit Zargarian

  DOI：10.1021/om990600a

  日期：1999.12.1

  The complexes (1-Me-Ind)(PR3)Ni-CC-Ph (R = Ph and Cy) have been prepared and characterized spectroscopically and by means of single-crystal structural analyses. These compounds are inert toward the insertion of alkynes, but when combined with methylaluminoxane (MAO), they form active catalysts for the homogeneous polymerization of phenylacetylene. cis-Poly(Ph-CC-H) is thus obtained with M-w values in the range of 10(4) and relatively narrow polydispersities. The combination of the corresponding Ni-Cl complexes with MAO gives similar results with Ph-CC-H and also polymerizes 1-hexyne and 3-hexyne, but the degree of polymerization is much lower. Optimization studies have shown that the polymerization reactions give the best results with THF as solvent and a 1:10 ratio of Ni to MAO. Evidence is presented for the involvement in the catalytic cycle of bimetallic species with a Ni(mu-X)(mu-Me)Al core.
• Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺
  作者：Rainer Vollmerhaus、Francine Bélanger-Gariépy、Davit Zargarian

  DOI：10.1021/om970169u

  日期：1997.10.1

  The cationic complexes [(1-Me-Ind)Ni(PPh3)(L)](+) (1-Me-Ind = 1-methylindenyl; L = PPh3, PMe3, or MeCN) have been prepared and characterized spectroscopically and by nt ans of single-crystal X-ray structural analysis in the case of [(1-Me-Ind)Ni(PPh3)(PMe3)]AlCl4. The in-situ-generated cations dimerize ethylene.