[RuCl(SiMeCl2)(η2-H2)(PCy3)2] | 945859-32-5

• 英文名称: [RuCl(SiMeCl2)(η2-H2)(PCy3)2]
• 英文别名: RuCl(SiMeCl2)(η2-H2)(PCy3)2
• CAS: 945859-32-5
• 化学式: C₃₇H₇₁Cl₃P₂RuSi
• 分子量: 813.433
• InChiKey: OMUGVKRWWBKYRS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  氯代二环己基硼烷 以 四氢呋喃 、 正己烷 、 正戊烷 为溶剂， 生成 [RuCl(SiMeCl2)(η2-H2)(PCy3)2]
  参考文献：
  名称：

  Activation of Chlorosilanes at Ruthenium:  A Route to Silyl σ-Dihydrogen Complexes

  摘要：

  The hydrido sigma-dihydrogen complex RuClH(eta(2)-H-2)(PCy3)(2) ( 2) reacts with the chlorosilanes HSiMe3-nCln (n = 1-3) to form the corresponding silyl sigma-dihydrogen complexes RuCl(SiMe3-nCln)(eta(2)-H-2)(PCy3)(2) (3Me(3-n)Cl(n)). These complexes display a 16-electron configuration, as shown by NMR, by X-ray data in the case of 3MeCl(2), and by theoretical calculations. The sigma-H-2 ligand in 3MeCl(2) has been located by X-ray diffraction, and the H-H distance of 1.05(3) angstrom compares well with the value obtained by DFT/ B3PW91 (1.073 angstrom) as well as with the value of 1.08 +/- 0.01 angstrom derived from the measurement of the J(HD) coupling constant of 17.5 Hz for the deuterated isotopomer RuCl(SiMeCl2)(eta(2)-HD)(PCy3)(2). The series of model complexes RuCl(SiMe3-nCln)(eta(2)-H-2)(PMe3)(2) (S3Me(3-n)Cl(n)) was investigated by DFT at the B3PW91 level. The most stable isomers have a structure that resembles the X-ray structure of 3MeCl(2): i.e., a silyl sigma-dihydrogen formulation. In the case of S3Me(2)Cl and S3MeCl(2) a second minimum very close in energy was optimized and formulated as a hydrido sigma-silane species. The influence of the number of Cl substituents on Si and their location have been analyzed. The difference between 3Me(2)Cl on one side and 3MeCl(2) and 3Cl(3) on the other side is highlighted both by NMR and DFT data and by their reactivity toward ethylene. No reaction was observed for the latter complexes, whereas reaction with 3Me(2)Cl produces the hydrido eta(2)-ethylene complex RuClH(C2H4)(PCy3)(2) (4). In the case of styrene, the arene complex RuCl(SiMe2Cl)(eta(6)-C8H10)(PCy3) (5) was isolated.

  DOI：

  10.1021/om700295g

文献信息

• Silyl and σ-silane ruthenium complexes: Chloride substituent effects on the catalysed silylation of ethylene
  作者：Sébastien Lachaize、Laure Vendier、Sylviane Sabo-Etienne

  DOI：10.1039/c0dt00065e

  日期：——

  σ-silane complexes RuH2(η2-H2)(η2-HSiMe2Cl)(PCy3)2 (2Me2Cl), RuH2(η2-HSiMe2Cl)2(PCy3)2 (3Me2Cl) and the silyl complex RuCl(SiMe2Cl)(η2-H2)(PCy3)2 (4Me2Cl), all characterised by multinuclear NMR spectroscopy. Complexes 2Me2Cl and 3Me2Cl adopt a cis configuration for the two bulky phosphine ligands as a result of stabilising SISHA (Secondary Interactions between Silicon and Hydrogen Atoms) interactions. Complex

  氯硅烷使乙烯硅烷化 HSiMe 2 Cl 和 HSiMeCl 2由二（二氢）催化的复杂期RuH 2（η 2 -H 2）2（PCY 3）2（1）。导致形成相应的乙烯基硅烷的脱氢甲硅烷基化与氢化硅烷化竞争。反应的速率和选择性受氯取代基的数目和乙烯压力的影响。进行了比较机理研究甲苯-d 8与两种氯硅烷。1与过量的反应HSiMe 2 Cl（10当量）中产生的σ-硅烷络合物期RuH 2（η 2 -H 2）（η 2 -HSiMe 2 Cl）的（PCY 3）2（2Me 2氯），期RuH 2（η 2 -HSiMe 2 Cl）的2（PCY 3）2（3Me 2氯）和甲硅烷复合的RuCl（森达2 Cl）的（η 2 -H 2）（PCY 3）2（4Me 2氯），均以多核NMR光谱为特征。复合体2Me 2氯 和 3Me 2氯两个都采用顺式配置膦 稳定的配体 西莎 （之间的二次交互 硅 和 氢原子）相互作用。复杂的4Me