[(η5-1-methylindenyl)Ni(Cl)(PMe3)] | 329359-80-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: [(η5-1-methylindenyl)Ni(Cl)(PMe3)]
• 英文别名: 1-methyl-2H-inden-2-ide;nickel(2+);trimethylphosphane;chloride
• CAS: 329359-80-0
• 化学式: C₁₃H₁₈ClNiP
• 分子量: 299.403
• InChiKey: ITVMHABZISDCKZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.23
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  [(η5-1-methylindenyl)Ni(Cl)(PMe3)] 、 三环己基膦 以 乙醚 为溶剂， 以59%的产率得到[(η5-1-methylindenyl)Ni(II)(Cl)(P(cyclohexyl)3)]
  参考文献：
  名称：

  Solid State Structures and Phosphine Exchange Reactions of (1-Me-Indenyl)(PR₃)Ni−Cl

  摘要：

  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.

  DOI：

  10.1021/om010608w
• 作为产物：
  描述：

  1-methyl-indenyllithium 、 dichlorobis(trimethylphosphine)nickel 以 四氢呋喃 为溶剂， 以90%的产率得到[(η5-1-methylindenyl)Ni(Cl)(PMe3)]
  参考文献：
  名称：

  Solid State Structures and Phosphine Exchange Reactions of (1-Me-Indenyl)(PR₃)Ni−Cl

  摘要：

  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.

  DOI：

  10.1021/om010608w

文献信息

• Dehydrogenative Oligomerization of PhSiH₃ Catalyzed by (1-Me-Indenyl)Ni(PR₃)(Me)
  作者：Frédéric-Georges Fontaine、Davit Zargarian

  DOI：10.1021/om010757e

  日期：2002.1.1

  The complexes (1-Me-Ind)Ni(PR3)Me (Ind = indenyl; R = Ph, 1; Cy, 2; Me, 3) can act as single-component precatalysts for the dehydrogenative oligomerization of PhSiH3 to (PhSiH)(n) with M-w up to 1.6 x 10(3) in the case of 3. The catalytic Si-Si bond formation is initiated by a second-order, concerted reaction between the Ni-Me precursor and PhSiH3 which releases CH4. Kinetic studies of this Si-H bond activation step gave the following activation parameters for the reaction of 3 with PhSiH3: DeltaH(double dagger) = 10.7 +/- 0.7 kcal-mol(-1); DeltaS(double dagger) = -42 +/- 2 eu;k(H)/k(D) (for reaction with PhSiD3 at 313 K) = 9.8 +/- 0.5. The Ni-SiPhH2 species presumed to form in this reaction was not detected directly, but the presence of 1-SiPhH2-3-Me-Ind in the reaction mixtures, coupled with the fact that Ni(PMe3)(4) is an active precatalyst for the oligomerization of PhSiH3, suggests that the silyl intermediate undergoes a reductive elimination to generate Ni(O) species which might be involved in the catalysis.