| 171085-88-4

• CAS: 171085-88-4
• 化学式: C₂₁H₄₈OP₄Ru
• 分子量: 541.577
• InChiKey: MXXVBSNUFKHDLW-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  一氧化碳 、 trans-{Ru(H)2(C10H24P2)2} 以 正庚烷 为溶剂， 生成
  参考文献：
  名称：

  Laser Flash Photolysis and Matrix Isolation Studies of Ru[R2PCH2CH2PR2]2H2 (R = C2H5, C6H5, C2F5): Control of Oxidative Addition Rates by Phosphine Substituents

  摘要：

  The photochemistry of ruthenium hydrides Ru(depe)(2)H-2, cis-Ru(dppe)(2)H-2 and cis-Ru(dfepe)(2)H-2 [depe = Et(2)PCH(2)CH(2)PEt(2), dppe = Ph(2)PCH(2)CH(2)PPh(2), dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2)] has been studied by matrix isolation at 12 K and laser flash photolysis at ambient temperature. Both techniques yield the 4-coordinate 16-electron RuP4 species. The ethyl and phenyl species, Ru(depe)(2) and Ru(dppe)(2), exhibit very similar UV-visible spectra to Ru(dmpe)(2) [Ru(depe)(2) 475, 580, 735 nm; Ru(dppe)(2) 465, 550, 760 nm in solution]. The spectrum of Ru(dfepe)(2) is blue-shifted relative to the others (380, 450, 620 nm). The comparison of the spectra with that of [Rh(dppe)(2)](+) conclusively establishes a square-planar structure for Ru(depe)(2) and Ru(dppe)(2). The rates of reaction with added ligands are extremely sensitive to substituent. The rate constants for reaction with H-2 are Ru(dfepe)(2) 2.0 x 10(5), Ru(dppe)(2) 2.4(2) x 10(7), Ru(depe)(2) 4.0(4) x 10(8) dm(3) mol(-1) s(-1) compared to 6.8 x 10(9) dm(3) mol(-1) s(-1) for Ru(dmpe)(2). For reaction with CO, the rate constants are Ru(dfepe)(2) 1.1 x 10(4), Ru(dppe)(2) 1.0(2) x 10(7), Ru(depe)(2) 9.1(7) x 10(7) dm(3) mol(-1) s(-1) compared to 4.6 x 10(9) dm(3) mol(-1) s(-)1 for Ru(dmpe)(2). Thus reactivity increases in the order Ru(dfepe)(2) < Ru(dppe)(2) < Ru(depe)(2) < Ru(dmpe)(2) with an overall span of a factor of 34 000 for reaction with H-2 and 418 000 for reaction with CO. The rate constants for reaction of Ru(depe)(2) with C2H4 and Et(3)SiH, and for reaction of Ru(dppe)(2) with C2H4 have also been determined.

  DOI：

  10.1021/ja00145a016