RuCl(SiMe2Cl)(η6-C8H10)(PCy3) | 945859-34-7

• 英文名称: RuCl(SiMe2Cl)(η6-C8H10)(PCy3)
• CAS: 945859-34-7
• 化学式: C₂₈H₄₉Cl₂PRuSi
• 分子量: 616.732
• InChiKey: KQANQQNNNTYLRB-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  苯乙烯 、 RuCl(SiMe2Cl)(η2-H2)(PCy3)2 以 甲苯 为溶剂， 以95%的产率得到RuCl(SiMe2Cl)(η6-C8H10)(PCy3)
  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