trans-{Ru(H)2(C10H24P2)2} | 100352-64-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: trans-{Ru(H)2(C10H24P2)2}
• 英文别名: 2-diethylphosphanylethyl(diethyl)phosphane;ruthenium dihydride
• CAS: 100352-64-5；123932-02-5；134677-19-3
• 化学式: C₂₀H₅₀P₄Ru
• 分子量: 515.582
• InChiKey: FQEHJOQBXVWIEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.52
• 重原子数：
  25.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  trans-{Ru(H)2(C10H24P2)2} 以 solid matrix 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
• 作为产物：
  描述：

  cis-RuCl2(Et2PC2H4PEt2)2 在 sodium 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到trans-{Ru(H)2(C10H24P2)2}
  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

• Synthesis, characterisation and reactivity of ruthenium bis-bifluoride, ruthenium hydride bifluoride and ruthenium hydride fluoride complexes
  作者：Naseralla A. Jasim、Robin N. Perutz、Simon P. Foxon、Paul H. Walton

  DOI：10.1039/b101007g

  日期：——

  Bifluoride complexes, trans-[Ru(depe)2H(FHF)] (1), trans-[Ru(dppe)2H(FHF)] (2), trans-[Ru(dppp)2H(FHF)] (3) and cis-[Ru(PMe3)4(FHF)2] (4) (depe = Et2PCH2CH2PEt2, dppe = Ph2PCH2CH2PPh2, dppp = Ph2PCH2CH2CH2PPh2) were synthesised from the reactions of the corresponding cis-dihydride complexes with NEt3·3HF in THF. The characteristic features of the low temperature NMR spectra of the bifluoride complexes include

  双氟化物络合物，反式-[Ru（depe）2 H（FHF ）]（1），反式-[Ru（dppe）2 H（FHF ）]（2），反式-[Ru（dppp）2 H（FHF ）] （3）和顺式-[Ru（PMe 3）4（FHF ）2 ]（4）（depe = Et 2 PCH 2 CH 2 PEt 2，dppe由相应的顺式-二氢化物配合物与NEt 3 ·3HF在THF中的反应合成 = Ph 2 PCH 2 CH 2 PPh 2，dppp = Ph 2 PCH 2 CH 2 CH 2 PPh 2）。低温的特征核磁共振谱的二氟化物配合物在约3-6处具有19 F共振。δ- 300代表近端的氟，大约为。 远端氟的δ- 165。酸性的质子在大约共振。δ13 .远端氟的J（HF ）值在300–400 Hz的范围内。氟化氢配体表现出约20的特征振动。2300厘米-1和大约 2430厘米-1在红外光谱。所有复合物表现出动态
• Photochemical Oxidative Addition of Germane and Diphenylgermane to Ruthenium Dihydride Complexes
  作者：David P. Dickinson、Simon W. Evans、Mary Grellier、Hannah Kendall、Robin N. Perutz、Barbara Procacci、Sylviane Sabo-Etienne、Katharine A. Smart、Adrian C. Whitwood

  DOI：10.1021/acs.organomet.8b00770

  日期：2019.2.11

  DuPhos, R = Ph dppe, R = Et depe, R = Me dmpe) are reported. Reaction with GeH4 generates a mixture of cis and trans isomers of Ru(PP)2(GeH3)H except for the DuPhos complex which yields the product only in the cis form. In situ laser photolysis (355 nm) demonstrates that the initial product is the cis isomer that undergoes thermal isomerization to the trans isomer. The complex cis-[Ru(dppe)2(GeH3)H] crystallizes

  报告了锗烷和二苯基锗烷与Ru（PP）2 H 2（PP = R 2 PCH 2 CH 2 PR 2或DUPhOS，R = Ph dppe，R = Et depe，R = Me dmpe）的光化学反应。与GeH 4的反应生成Ru（PP）2（GeH 3）H的顺式和反式异构体的混合物，但DUPhOS复合物除外，后者仅以顺式形式生成产物。原位激光光解（355 nm）表明初始产物为顺式异构体，该异构体经历热异构化为反式异构体。复杂的顺式[[Ru（dppe）2（GeH 3）H]选择性结晶，从而可以确定其X射线结构为粗氢化物，Ru-H···Ge的长距离为2.64（3）Å，表明RuH和Ge之间没有残留的相互作用。DFT计算也与完全氧化加成一致。的结构的顺式- [茹（DUPHOS）2烷（GeH 3）H]揭示了从一个八面体几何显著失真。晶体中的主要物种（95％）显示出Ru–H···Ge距离为2.42（5）Å的结
• Photochemical oxidative addition of B–H bonds at ruthenium and rhodium
  作者：Philip L. Callaghan、Rodrigo Fernández-Pacheco、Naser Jasim、Sébastien Lachaize、Todd B. Marder、Robin N. Perutz、Eleonora Rivalta、Sylviane Sabo-Etienne

  DOI：10.1039/b312246h

  日期：——

  Metal phosphine hydrides of type RuP4H2 and RhP3H3 react photochemically with HB(pin) (pin = pinacolate) to form metal boryl hydride complexes via 16-electron intermediates generated by H2 loss; the second order rate constants for reaction of the intermediates with HB(pin) are even larger than those for reaction with Et3SiH.

  RuP4H2 和 RhP3H3 型金属氢化膦与 HB(pin) 发生光化学反应 (pin =频那醇)通过H2损失产生的16电子中间体形成金属硼基氢化物配合物；中间体与HB(pin)反应的二阶速率常数甚至比与Et3SiH反应的二阶速率常数还要大。
• Bautista, Maria T.; Cappellani, E. Paul; Drouin, Samantha D., Journal of the American Chemical Society, 1991, vol. 113, # 13, p. 4876 - 4887
  作者：Bautista, Maria T.、Cappellani, E. Paul、Drouin, Samantha D.、Morris, Robert H.、Schweitzer, Caroline T.、Sella, Andrea、Zubkowski, Jeffery

  DOI：——

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ru: SVol., 158, page 434 - 436
  作者：

  DOI：——

  日期：——