[PPN][RuCl₃(CO)₃] | 102532-53-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [PPN][RuCl₃(CO)₃]
• 英文别名: Bis(triphenyl-lambda5-phosphanylidene)azanium;carbon monoxide;trichlororuthenium(1-)；bis(triphenyl-λ5-phosphanylidene)azanium;carbon monoxide;trichlororuthenium(1-)
• CAS: 102532-53-6；81436-51-3
• 化学式: C₃Cl₃O₃Ru*C₃₆H₃₀NP₂
• 分子量: 830.049
• InChiKey: BSPLVUXVNXTDPY-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  8.36
• 重原子数：
  49
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [PPN][RuCl₃(CO)₃] 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  二氧化碳与甲醇催化由阴离子钌配合的Hydrocondensation：隔离，结构表征，和双核阴离子的[Ru催化启示2（CO）4（μ 2 -η 2 -CO 2 CH 3）2（μ 2 -OCH 3）Cl 2 ] -

  摘要：

  发现阴离子钌络合物[Ru（CO）3 Cl 3 ] -（1）在强碱存在下催化由CO 2，H 2和CH 3 OH形成甲酸甲酯。从基本甲醇溶液中，双核阴离子的[Ru 2（CO）4（μ 2 -η 2 -CO 2 CH 3）2（μ 2 -OCH 3）氯2 ] - （2）已分离为双（三苯基膦亚基）铵盐，并通过单晶X射线衍射分析进行了表征。在阴离子2中，两个的Ru（CO）2 C1单位由μ保持在一起2 -OCH 3配体和由两个μ 2 -η 2 -OCOCH 3桥; 除了三个桥接配体之外，没有直接的Ru-Ru相互作用（距离3.380Å）。发现络合物2与2当量的[OCH 3 ]反应-得到两个反应性中间体3和4，后者被认为是加氢缩合反应中的催化活性物质。对光谱数据的基础和芳族类似物从反应的隔离2与各种酚，的构成的[Ru 2（CO）6（OCH 3）4（μ 2 -OCH 3）] - ，提出了活性种4。消除水作为CO

  DOI：

  10.1021/om960062r
• 作为产物：
  描述：

  水合三氯化钌 、 一氧化碳 、 双(三苯基正膦基)氯化铵 以 甲醇 为溶剂， 以81%的产率得到[PPN][RuCl₃(CO)₃]
  参考文献：
  名称：

  二氧化碳与甲醇催化由阴离子钌配合的Hydrocondensation：隔离，结构表征，和双核阴离子的[Ru催化启示2（CO）4（μ 2 -η 2 -CO 2 CH 3）2（μ 2 -OCH 3）Cl 2 ] -

  摘要：

  发现阴离子钌络合物[Ru（CO）3 Cl 3 ] -（1）在强碱存在下催化由CO 2，H 2和CH 3 OH形成甲酸甲酯。从基本甲醇溶液中，双核阴离子的[Ru 2（CO）4（μ 2 -η 2 -CO 2 CH 3）2（μ 2 -OCH 3）氯2 ] - （2）已分离为双（三苯基膦亚基）铵盐，并通过单晶X射线衍射分析进行了表征。在阴离子2中，两个的Ru（CO）2 C1单位由μ保持在一起2 -OCH 3配体和由两个μ 2 -η 2 -OCOCH 3桥; 除了三个桥接配体之外，没有直接的Ru-Ru相互作用（距离3.380Å）。发现络合物2与2当量的[OCH 3 ]反应-得到两个反应性中间体3和4，后者被认为是加氢缩合反应中的催化活性物质。对光谱数据的基础和芳族类似物从反应的隔离2与各种酚，的构成的[Ru 2（CO）6（OCH 3）4（μ 2 -OCH 3）] - ，提出了活性种4。消除水作为CO

  DOI：

  10.1021/om960062r
• 作为试剂：
  描述：

  二氧化碳 、 氢气 在 [PPN][RuCl₃(CO)₃] 、 bis(triphenylphosphoranylidene)ammonium iodide 作用下， 以 N-甲基吡咯烷酮 为溶剂， 160.0 ℃ 、8.0 MPa 条件下， 反应 5.0h， 生成 水
  参考文献：
  名称：

  Reverse Water-Gas Shift Reaction Catalyzed by Mononuclear Ru Complexes

  摘要：

  A series of mononuclear Ru halogen carbonyl complexes, [PPN][Ru X-3 (CO)(3)] (X = Cl, Br, and I), were found to catalyze the reverse water-gas shift reaction (RWGSR: H-2 + CO2 -> CO + H2O). The Ru species in the reaction solution were investigated in situ using a high-pressure IR spectroscopy apparatus, which showed that [RuCl3(CO)(3)](-) was the exclusive Ru species when [PPN][RuCl3(CO)(3)] was used as a catalyst. On the basis of the IR spectra of stepwise reaction experiments, a plausible reaction mechanism for the mononuclear species is proposed.

  DOI：

  10.1021/cs400809k

文献信息

• Promoter Effect of Chloride Ions on the Ruthenium-Catalyzed Hydroesterification of Ethylene with Methyl Formate. Design and Evaluation of New Poly- and Mononuclear Catalyst Precursors
  作者：Noel Lugan、Guy Lavigne、Jean Marc Soulie、Sylvie Fabre、Philippe Kalck、Jean Yves Saillard、Jean Francois Halet

  DOI：10.1021/om00004a027

  日期：1995.4

  The catalytic hydroesterification of ethylene with methyl formate to produce methyl propionate is shown to take place in the presence of trinuclear ruthenium carbonyl complexes modified by anionic nucleophiles such as amido (anilinopyridyl), alkoxy (pyridonate), or halide ligands, regarded as potential promoters. The best results (100% conversion, 99% selectivity) are obtained with the mixture Ru-3(CO)(12) + [PPN]Cl(1/1) under the following experimental conditions: [HCOOMe]/[cat.] = 345, DMF solvent, P(C2H4) = 20 atm (at 25 degrees C), T = 160 degrees C, time 12 h. The complex [PPN][Ru-3(mu(3)-Cl)(CO)(9)] (3) resulting from the addition of [PPN]Cl to Ru-3(CO)(12) reacts cleanly with an excess of [PPN]Cl in refluxing THF under a stream of inert gas to produce the unique dianionic species [PPN](2)[Ru-4(mu-Cl)(2)(CO)(11)] (4) (70% yield). The X-ray structure analysis of 4 is reported (triclinic P1, No. 2, a 18.209(2) Angstrom, b = 18.877(3) Angstrom, c = 13.895(2) Angstrom, a = 110.70(1)degrees, beta = 108.43(1)degrees, gamma = 87.43(1)degrees, V = 4226(1) Angstrom(3), Z = 2, R = 0.053, R(w) = 0.069). The dianionic tetranuclear unit of 4 consists of a basic triangular metal framework ''Ru-3(CO)(9)'' one face of which is supported by a spiked ''Ru(CO)(2)Cl-2'' fragment involving a 16e metal center exhibiting a square pyramidal geometry. Extended Huckel MO calculations indicate a large HOMO/LUMO gap (1.45 eV). Facile loss of Cl- from the above dianion is induced by capture of CO, leading to the known butterfly complex [PPN][Ru-4(mu-Cl)(CO)(13)] (5). Complex 4 also reacts with O-2 at 25 degrees C to provide the new oxo derivative [PPN](2)[RU(4)(mu(4)-O)(mu-Cl)(4)(CO)(10)] (6) The structure of 6 has been determined by X-ray diffraction (triclinic P1, No. 2, a = 13.226(5) Angstrom, b = 25.533(2) Angstrom, c = 12.771(3) Angstrom, a = 92.39(1)degrees, beta 114.77(3)degrees, gamma = 85.92(2)degrees, V = 3906(2) Angstrom(3), Z = 2, R = 0.038, R(w) = 0.045). Its dianionic unit consists of a distorted quadratic antiprism based on two rectangular faces RU(mu-Cl)(2)RU and containing an encapsulated oxygen atom linked to the four ruthenium centers. The anionic complexes 4-6 also act as catalyst precursors for the hydroesterification reaction. Analysis of the solutions recovered at the end of all catalytic runs indicate the presence of [PPN](2)[Ru-6(C)(CO)(16)] as the principal metal-containing derivative. The probable mononuclear nature of the active species is suggested. A detailed investigation of the catalytic system based on [PPN][Ru(CO)(3)Cl-3] (7) (prepared here in 81% yield by a new one-pot procedure) is reported. The results show that catalysis in the presence of the latter complex takes place readily without an induction period. Furthermore, a comparative evaluation of the four salts 7, [PPN][Ru(CO)(3)I-3] (8), [PPN][Ru(CO)(3)Cl2I] (9), and [PPN][Ru(CO)(3-)CII2] (10) as catalyst precursors reveals that chloride is a better promoter than iodide under the experimental conditions defined above, using DMF (or related amides) as solvent. Catalysis in the presence of 7 (and 3 equiv of NEt(3) as cocatalyst) is complete within 2 h (100% conversion and 99% selectivity; overall turnover frequency 170 h(-1), corresponding to an initial activity of the order of 700 h(-1)).Complex 7 is seen to react readily with DMF at 160 degrees C within 30 min to produce the new complex [PPN][Ru(CO)(2)Cl-3(eta(1)-DMF)] (11), isolated in 60% yield. The X-ray structure of 11 is reported (monoclinic P2(1)/c, a = 9.000(2) Angstrom, b = 21.176(2) Angstrom, c = 21.080(1) Angstrom, beta = 93.89(8)degrees, V = 4008.3(9) Angstrom(3), Z = 4, R = 0.028, R(w) = 0.030). The three chloride ligands adopt a meridional arrangement, whereas the DMF ligand, bound via its oxygen atom, occupies one of the two apical sites.
• Generation of Alkyl(dicarbonyl)(chloro)-ruthenium Dimers in the Ruthenium-Catalyzed Addition of Alkyl Formates to Ethylene
  作者：Sylvie Fabre、Philippe Kalck、Guy Lavigne

  DOI：10.1002/anie.199710921

  日期：1997.5.15
• Hydrocondensation of Carbon Dioxide with Methanol Catalyzed by Anionic Ruthenium Complexes:  Isolation, Structural Characterization, and Catalytic Implications of the Dinuclear Anion [Ru₂(CO)₄(μ₂-η²-CO₂CH₃)₂(μ₂-OCH₃)Cl₂]^-
  作者：Georg Süss-Fink、Jean-Marc Soulié,、Gerd Rheinwald、Helen Stoeckli-Evans、Yoshiyuki Sasaki

  DOI：10.1021/om960062r

  日期：1996.7.23

  The anionic ruthenium complex [Ru(CO)3Cl3]- (1) was found to catalyze the formation of methyl formate from CO2, H2, and CH3OH in the presence of a strong base. From the basic methanol solution, the dinuclear anion [Ru2(CO)4(μ2-η2-CO2CH3)2(μ2-OCH3)Cl2]- (2) has been isolated as the bis(triphenylphosphoranylidene)ammonium salt and characterized by a single-crystal X-ray diffraction analysis. In anion

  发现阴离子钌络合物[Ru（CO）3 Cl 3 ] -（1）在强碱存在下催化由CO 2，H 2和CH 3 OH形成甲酸甲酯。从基本甲醇溶液中，双核阴离子的[Ru 2（CO）4（μ 2 -η 2 -CO 2 CH 3）2（μ 2 -OCH 3）氯2 ] - （2）已分离为双（三苯基膦亚基）铵盐，并通过单晶X射线衍射分析进行了表征。在阴离子2中，两个的Ru（CO）2 C1单位由μ保持在一起2 -OCH 3配体和由两个μ 2 -η 2 -OCOCH 3桥; 除了三个桥接配体之外，没有直接的Ru-Ru相互作用（距离3.380Å）。发现络合物2与2当量的[OCH 3 ]反应-得到两个反应性中间体3和4，后者被认为是加氢缩合反应中的催化活性物质。对光谱数据的基础和芳族类似物从反应的隔离2与各种酚，的构成的[Ru 2（CO）6（OCH 3）4（μ 2 -OCH 3）] - ，提出了活性种4。消除水作为CO