| 171235-38-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 171235-38-4；60105-80-8
• 化学式: C₅₂H₄₈P₄Ru
• 分子量: 897.918
• InChiKey: ZFYGGLFKMRSAPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.5
• 重原子数：
  57.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  cis-H2Ru(Ph2PCH2CH2PPh2)2 以 环己烷 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

文献信息

• Photochemical Pump and NMR Probe: Chemically Created NMR Coherence on a Microsecond Time Scale
  作者：Olga Torres、Barbara Procacci、Meghan E. Halse、Ralph W. Adams、Damir Blazina、Simon B. Duckett、Beatriz Eguillor、Richard A. Green、Robin N. Perutz、David C. Williamson

  DOI：10.1021/ja504732u

  日期：2014.7.16

  We report pump probe experiments employing laser-synchronized reactions of para-hydrogen (para-H-2) with transition metal dihydride complexes in conjunction with nuclear magnetic resonance (NMR) detection. The pump probe experiment consists of a single nanosecond laser pump pulse followed, after a precisely defined delay, by a single radio frequency (rf) probe pulse. Laser irradiation eliminates H-2 from either Ru-(PPh3)(3)(CO)(H)(2) 1 or cis-Ru(dppe)(2)(H)(2) 2 in C6D6 solution. Reaction with para-H-2 then regenerates 1 and 2 in a well-defined nuclear spin state. The rf probe pulse produces a high-resolution, single-scan H-1 NMR spectrum that can be recorded after a pump-probe delay of just 10 mu s. The evolution of the spectra can be followed as the pump probe delay is increased by micro- or millisecond increments. Due to the sensitivity of this para-H-2 experiment, the resulting NMR spectra can have hydride signal-to-noise ratios exceeding 750:1. The spectra of 1 oscillate in amplitude with frequency 1101 +/- 3 Hz, the chemical shift difference between the chemically inequivalent hydrides. The corresponding hydride signals of 2 oscillate with frequency 83 +/- 5 Hz, which matches the difference between couplings of the hydrides to the equatorial P-31 nuclei. We use the product operator formalism to show that this oscillatory behavior arises from a magnetic coherence in the plane orthogonal to the magnetic field that is generated by use of the laser pulse without rf initialization. In addition, we demonstrate how chemical shift imaging can differentiate the region of laser irradiation thereby distinguishing between thermal and photochemical reactivity within the NMR tube.