[(1,3-(SiMe3)2-indenyl)Ni(PPh3)Cl] | 833483-56-0

• 英文名称: [(1,3-(SiMe3)2-indenyl)Ni(PPh3)Cl]
• 英文别名: (1,3-(SiMe3)2-Ind)Ni(PPh3)Cl；Ni(PPh3)Cl(1,3-(SiMe3)2C9H6)
• CAS: 833483-56-0
• 化学式: C₃₃H₃₈ClNiPSi₂
• 分子量: 615.952
• InChiKey: HXBVTNRPROYHRF-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：

  [(1,3-(SiMe3)2-indenyl)Ni(PPh3)Cl] 、 四苯硼钠 以 乙醚 为溶剂， 以25%的产率得到Ni2(PPh3)2(PPh2)(BPh4)
  参考文献：
  名称：

  四苯基硼酸酯是两性离子镍（I）二聚体中的新型桥连配体。

  摘要：

  DOI：

  10.1002/anie.200502905
• 作为产物：
  描述：

  bis(triphenylphosphine)nickel(II) chloride 、 {1,3-bis(trimethylsilyl)-indenyl}lithium 以 乙醚 为溶剂， 以60%的产率得到[(1,3-(SiMe3)2-indenyl)Ni(PPh3)Cl]
  参考文献：
  名称：

  Influence of SiMe₃ Substituents on Structures and Hydrosilylation Activities of ((SiMe₃)_1 or 2-Indenyl)Ni(PPh₃)Cl

  摘要：

  This report examines the effect of substituents R on structures and reactivities of the complexes (R-Ind)Ni(PPh3)Cl (R-Ind = 1-Me-indenyl, 1; 1-SiMe3-indenyl, 2; 1,3-(SiMe3)(2-) indenyl, 3). NMR studies indicate that a relatively facile dissociation of PPh3 takes place in solutions of complex 3 (DeltaG(double dagger) approximate to 10 kcal/mol in C6D6) but not those of complexes 1 and 2, implying that the presence of Ind substituents at the 1- and 3-positions can influence the kinetic lability of PPh3. X-ray analyses have also shown that the PPh3 ligand and the SiMe3 group adjacent to it in complex 3 experience some steric repulsion, which is manifested in angular deformations (out-of-plane bending of the SiMe3 group by about 0.56-0.65 Angstrom and 5 - 10degrees variations in the P-Ni-Cl and P-Ni-C3 angles) and a somewhat longer Ni-P bond (ca. 2.19 Angstrom). Reactivity studies have shown that complexes 1-3 are effective precatalysts for the addition of PhSiH3 to styrene in the presence of the cationic initiator NaBPh4; alpha-addition of the silyl moiety takes place regioselectively to give PhCH(Me)(SiPhH2). The catalytic activities depend on the styrene:PhSiH3 ratio but not the Ind substituents; thus, catalytic turnover numbers increase from ca. 75 with a 1:1 ratio to ca. 95 with a 1:1.5 ratio for all three precursors. The hydrosilylation can also proceed in the absence of initiator, but in this case the activities are strongly dependent on Ind substituents, increasing in the order I-Me-Ind much less than 1-SiMe3-Ind < 1,3-(SiMe3)(2)-Ind.

  DOI：

  10.1021/om0494420

文献信息

• Phenylsilane dehydrocoupling and addition to styrene catalyzed by (R-indenyl)Ni(phosphine)(methyl) complexes
  作者：Yaofeng Chen、Davit Zargarian

  DOI：10.1139/v08-132

  日期：2009.1.1

  This report describes the synthesis and characterization of the Ni–Me complexes (R-indenyl)Ni(PR′₃)Me (R = 1-i-Pr, 1-SiMe₃, and 1,3-(SiMe₃)₂; R′= Me, Ph) and outlines their catalytic reactivities in the dehydrogenative oligomerization of PhSiH₃ and its addition to styrene in the absence of initiators/activators. Observation of higher hydrosilylation activities for PPh₃-based compounds featuring bulky substituents on the indenyl ligand confirms earlier suggestions that phosphine dissociation is an important component of the catalytic cycle for this reaction. In contrast, oligomerization of PhSiH₃ is more facile with PMe₃-based precursors and independent of the steric bulk of the indenyl ligand, implying that this reaction does not involve phosphine dissociation. These conclusions are consistent with the variable-temperature ¹H NMR spectra of 1,3,-(SiMe₃)₂-indenyl}Ni(PR′₃)Me and various structural parameters observed in the solid-state structures of 1,3,-(SiMe₃)₂-indenyl}Ni(PPh₃)Me, 1,3,-(SiMe₃)₂-indenyl}Ni(PMe₃)Cl, and 1-SiMe₃-indenyl}Ni(PMe₃)Me.Key words: nickel-indenyl complexes, hydrosilylation, hydrosilane oligomerization.

  本报告描述了 Ni-Me 复合物 (R-indenyl)Ni(PR′3)Me 的合成和特性（R = 1-i-Pr、1-SiMe3 和 1,3-(SiMe3)2；R′= Me、Ph），并概述了它们在 PhSiH3 的脱氢低聚过程中的催化反应活性，以及在没有引发剂/活化剂的情况下与苯乙烯的加成反应。观察到茚基配体上具有大取代基的 PPh3 基化合物具有更高的氢硅化活性，这证实了之前的观点，即膦解离是该反应催化循环的重要组成部分。相比之下，PhSiH3 的低聚作用在使用 PMe3 前体时更为容易，且不受茚基配体立体体积的影响，这意味着该反应不涉及膦解离。这些结论与1,3,-(SiMe3)2-茚基}Ni(PR′3)Me 的变温 1H NMR 光谱以及在1,3,-(SiMe3)2-茚基}Ni(PPh3)Me、1,3,-(SiMe3)2-茚基}Ni(PMe3)Cl 和1-SiMe3-茚基}Ni(PMe3)Me 的固态结构中观察到的各种结构参数是一致的。关键词：镍-茚基配合物、氢硅化、氢硅烷低聚。