[1,2-双(二苯基膦基)乙烷]三羰基钌 | 58201-22-2

• 中文名称: [1,2-双(二苯基膦基)乙烷]三羰基钌
• 英文名称: [1,2-bis(diphenylphosphino)ethane]tricarbonylruthenium
• 英文别名: tricarbonyl(1,2-bis(diphenylphosphino)ethane)ruthenium(0)；Ru(1,2-bis(diphenylphosphino)ethane)(CO)3；Ru(CO)3(Ph2PCH2CH2PPh2)；Ru(CO)3(dppe)
• CAS: 58201-22-2
• 化学式: C₂₉H₂₄O₃P₂Ru
• 分子量: 583.525
• InChiKey: HJRFGQFVVILJDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [1,2-双(二苯基膦基)乙烷]三羰基钌 、 厄多司坦 以 甲苯 为溶剂， 以93%的产率得到Ru(CO)2{C(O)N(O-MeC6H4)O}(1,2-bis(diphenylphosphino)ethane)
  参考文献：
  名称：

  Gargulak, Jerry D.; Berry, Amanda J.; Noirot, Mark D., Journal of the American Chemical Society, 1992, vol. 114, # 23, p. 8933 - 8945

  摘要：

  DOI：
• 作为产物：
  描述：

  Ru(CO)4(η(1)-1,2-bis(diphenylphosphino)ethane) 以 正庚烷 为溶剂， 生成 [1,2-双(二苯基膦基)乙烷]三羰基钌
  参考文献：
  名称：

  五配位钌羰基配合物上二齿膦配体的螯合动力学。

  摘要：

  配合物的Ru（CO）的螯合动力学4（η 1 - （P-P））已经在庚烷中的研究，其中，P-P =苯基2 P（CH 2）Ñ PPH 2（Ñ = 1，2，3，或4，即dppm，dppe，dppp或dppb），Ph 2 P（NMe）PPh 2（dppma），Ph 2 P（o -C 6 H 4）PPh 2（dpp-苯）或R 2 P （CH 2）2 PR 2（R = Me或Cy，即dmpe或dcpe）。通过二齿配体与Ru（CO）4反应原位制备复合物（C 2 H 4），其本身是通过在C 2 H 4下将Ru 3（CO）12光解而原位制备的。最初形成的Ru（CO）4（η 1 - （P-P））络合物干净地反应，以形成轴向赤道的Ru（CO）3（η 2 - （P-P）），如图的晶体结构P-p = dppe，dmpe和dpp-苯时，它们的FTIR光谱与其他产品的相似度非常接近。螯合的产物在溶液或固态下进一步反应，当P-P

  DOI：

  10.1021/om000289t

文献信息

• Structure and reactivity of the zero-valent ruthenium complex Ru(1,2-bis(diphenylphosphino)ethane)(CO)3 and the dicationic ruthenium dimer [Ru2(1,2-bis(diphenylphosphino)ethane)2(CO)6]2+
  作者：Steven J. Skoog、Amy L. Jorgenson、John P. Campbell、Michelle L. Douskey、Eric Munson、Wayne L. Gladfelter

  DOI：10.1016/s0022-328x(97)00731-6

  日期：1998.4

  The dicationic complex was fully characterized by solution spectroscopic methods and by single crystal X-ray diffraction [trigonal crystal system, space group P3121, a=20.566(2) Å, c=13.871(2) Å, V=5080.7(8) Å3, Z=3] and found to have a dimeric structure with two octahedral units sharing a common apex via a Ru(I)–Ru(I) single bond. One octahedral unit is rotated approximately 45° relative to the other

  Ru（DPPE）（CO）3的结构通过单晶X射线衍射[单斜晶体系统，空间群P 2 1 / n，a = 12.2353（2）Å，b = 16.0803（3）Å，c表征。= 14.2451（3）A，β = 111.109（1）°，V = 2614.62（9）埃3，ž = 4]，结果为间三角双锥和四方锥中间。茹（DPPE）（CO）的单电子氧化3使用[（η 5 -C 5 H ^ 5）2的Fe] [PF 6 ]产生的[Ru 2（DPPE）2（CO）6 ] [PF 6 ] 2。通过溶液光谱法和单晶X射线衍射[三角晶系统，空间群P3 1 21，a = 20.566（2）Å，c = 13.871（2）Å，V = 5080.7（8 ）完全表征了该双效复合物。 ）3，Z= 3]，发现具有二聚体结构，其中两个八面体单元通过Ru（I）-Ru（I）单键共享一个共同的顶点。一个八面体单元相对于另一个八面体旋转大约45°
• The reaction of M(CO)₃(Ph₂PCH₂CH₂PPh₂) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products
  作者：Danièle Schott、Philip Callaghan、John Dunne、Simon B. Duckett、Cyril Godard、José M. Goicoechea、Jeremy N. Harvey、John. P. Lowe、Roger J. Mawby、Georg Müller、Robin N. Perutz、Rinaldo Poli、Michael K. Whittlesey

  DOI：10.1039/b407457b

  日期：——

  reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO)(2)(dppe)(H)(2) and Fe(CO)(2)(dppe)(H)(2) has been examined by NMR spectroscopy and rationalised by theoretical methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centres interchange positions while the two hydride ligands are unaffected. A second pathway involving

  研究了Ru（CO）（3）（dppe）和Fe（CO）（3）（dppe）（dppe = Ph（2）PCH（2）CH（2）PPh（2））与对氢的光化学反应通过原位光化学分析得到Ru（CO）（2）（dppe）（H）（2）的NMR谱图，显示出氢化物共振显着增强，而在Fe（CO）（2）（dppe）中可见到正常信号（H）（2）。此效应与关键中间体Ru（CO）（2）（dppe）的单重态电子状态相关，而Fe（CO）（2）（dppe）为三重态。DFT计算显示出与此图一致的电子基态。Ru（CO）（2）（dppe）（H）（2）和Fe（CO）（2）（dppe）（H）（2）的通量已通过NMR光谱进行了检查并通过理论方法进行了合理化，表明存在两种用于配体交换的途径。首先，磷和羰基中心互换位置，而两个氢化物配体不受影响。发现涉及所有三个配体组互换的第二种途径的能量略高。过渡态的HH距离与金属键合的二氢配体一致。但是，沿重排途径未发现局部最低值（中间值）。
• Homogeneous Catalytic Carbonylation of Nitroaromatics. 8. Kinetic and Mechanistic Studies of the Carbon-Nitrogen Bond and Product Forming Steps from Ru(Ph2PCH2CH2PPh2)(CO)2[C(O)OCH3]2: The Turnover Limiting Reactions in the Catalytic Cycle
  作者：Jerry D. Gargulak、Wayne L. Gladfelter

  DOI：10.1021/ja00088a015

  日期：1994.5

  Mechanistic studies of the reaction of (OC-6-32)-dicarbonylbis(methoxycarbonyl)[1,2-bis(diphenylphosphino)ethane] ruthenium(II) with p-toluidine to form N,N'-di-p-tolylurea are presented. The overall reaction was studied from 22 to 103 degrees C and was found to be first order with respect to each reactant. Spectroscopic and kinetic studies between 22 and 52 degrees C showed that the reaction proceeds through a species, Ru(dppe)(CO)(2)[C(O)OCH3][C(O)-NH(p-tolyl)], which is in equilibrium with Ru(dppe)(CO)(2)[C(O)OCH3](2). The mechanism of the C-N bond forming step is proposed to involve nucleophilic attack on a coordinated Ru-CO moiety with subsequent cleavage of the C(O)-OMe bond. The methoxycarbonyl-carbamoyl complex decomposes in a unimolecular fashion to liberate CH3OH, the starting catalyst Ru(dppe)(CO)(3), and p-tolyl isocyanate, which is immediately scavenged by excess amine to form N,N'-di-p-tolylurea. Studies of the analogous bis(isopropylcarbamoyl) complex provided supporting evidence for isocyanate elimination. Thermolysis of (OC-6-32)-dicarbonylbis(isopropylcarbamoyl)[1,2-bis(diphenylphosphino)ethane] ruthenium(II) yields isopropylamine, the starting catalyst Ru(dppe)(CO)(3), and isopropyl isocyanate, which reacts with isopropylamine over time to form diisopropylurea. The kinetics obtained from all of the stoichiometric reactions were combined into a suitable expression and found to lie on the same Arrhenius activation energy plot as the overall rate of the catalytic reaction.
• Homogeneous Catalytic Carbonylation of Nitroaromatics. 7. Transesterification and an Intramolecular Ligand-Hopping Mechanism for Isomerization in the Bis(methoxycarbonyl) Complex Ru(Ph2PCH2CH2PPh2)(CO)2[C(O)OCH3]2
  作者：Jerry D. Gargulak、Wayne L. Gladfelter

  DOI：10.1021/om00014a048

  日期：1994.2

  The bis(methoxycarbonyl) complex (OC-6-32)-dicarbonylbis(methoxycarbonyl)[1,2-bis(di-phenylphosphino)ethane[ruthenium(II) (3) isomerizes to (OC-6-2'2)-dicarbonylbis(methoxycarbonyl)[1,2-bis(diphenylphosphino)ethane]ruthenium(II) (3') via an intramolecular methoxide migration to an adjacent metal carbonyl. Isolation of pure 3, followed by dissolution in benzene-d6 at ambient temperature, results in the formation of an equilibrium mixture of the two species within 3 h. The assignment of methoxide migration as the mechanism of isomerization is based on kinetic analysis of the isomerization via NMR spectroscopic methods, (CO)-C-13 ligand exchange with 3, and attempted isotopic crossover experiments. Reacting 3 with Ru(dppe)(CO)2[C(O)-OCD3]2 in a 1.15:1 ratio under ambient conditions over 2 days did not result in observable scrambling of the isotopic labels. Transesterification of the two methoxycarbonyl groups occurs rapidly in the presence of excess alcohol. The rates of exchange with CD3OD for the two methoxycarbonyl ligands on 3 were found to be independent of each other and were quantified by NMR spectroscopic methods.