| 195048-79-4

• CAS: 195048-79-4
• 化学式: C₄₄H₄₆P₄Ru
• 分子量: 799.814
• InChiKey: MKPYLIBDUAIEHC-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：

  以 四氢呋喃 、 N,N-二甲基乙酰胺 为溶剂， 60.0~80.0 ℃ 、101.33 kPa 条件下， 生成
  参考文献：
  名称：

  钌催化乙烯和CO 2合成丙烯酸盐的机理研究

  摘要：

  在这里，我们描述了钌催化乙烯和CO 2合成丙烯酸盐的详细机理分析。催化循环的所有主要步骤，即（i）乙烯和CO 2的氧化环化生成钌内酯，（ii）通过热β-H消除钌内酯成氢化丙烯酰基络合物，以及（iii）由氢化丙烯酰基络合物通过碱介导的乙烯配位的零价钌络合物的生成，随着电子的增多而加快丰富的情结。这些结果表明，最后两个过程是通过羧酸根阴离子离解生成的阳离子钌络合物进行的。作为丙烯酸酯催化合成的另一种可能途径，还研究了钌促进的内酯向乙烯配位的零价钌配合物的碱促进裂解，并且发现反应进行顺利，其中反应速率取决于碱性。基地。与化学计量反应性相比，

  DOI：

  10.1021/acs.organomet.9b00659
• 作为产物：
  描述：

  在 potassium tert-butylate 作用下， 以 四氢呋喃 、 N,N-二甲基乙酰胺 为溶剂， 50.0~80.0 ℃ 、101.33 kPa 条件下， 生成
  参考文献：
  名称：

  钌催化乙烯和CO 2合成丙烯酸盐的机理研究

  摘要：

  在这里，我们描述了钌催化乙烯和CO 2合成丙烯酸盐的详细机理分析。催化循环的所有主要步骤，即（i）乙烯和CO 2的氧化环化生成钌内酯，（ii）通过热β-H消除钌内酯成氢化丙烯酰基络合物，以及（iii）由氢化丙烯酰基络合物通过碱介导的乙烯配位的零价钌络合物的生成，随着电子的增多而加快丰富的情结。这些结果表明，最后两个过程是通过羧酸根阴离子离解生成的阳离子钌络合物进行的。作为丙烯酸酯催化合成的另一种可能途径，还研究了钌促进的内酯向乙烯配位的零价钌配合物的碱促进裂解，并且发现反应进行顺利，其中反应速率取决于碱性。基地。与化学计量反应性相比，

  DOI：

  10.1021/acs.organomet.9b00659
• 作为试剂：
  描述：

  乙烯 、 二氧化碳 在 、 potassium tert-butylate 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 140.0 ℃ 、3.0 MPa 条件下， 反应 12.0h， 生成 丙烯酸钾
  参考文献：
  名称：

  带有四齿膦配体的钌（0）配合物的反应性：在乙烯和CO 2催化合成丙烯酸酯盐中的应用

  摘要：

  通过使用带有四齿膦配体的零价富电子钌配合物，通过乙烯和CO 2的氧化环化反应生成了五元钌内酯。对该钌内酯进行热的，可逆的β-H消除反应，得到丙烯酸基（氢化）钌（II）配合物，在用碱处理后会释放出丙烯酸盐。该反应成功地用于从乙烯和CO 2的钌催化的丙烯酸酯盐的首次合成中。这项研究证明了富电子的钌（0）配合物在CO 2固定化学中作为催化剂的可行性。

  DOI：

  10.1021/acs.organomet.8b00789

文献信息

• Photochemistry of M(PP₃)H₂ (M = Ru, Os; PP₃ = P(CH₂CH₂PPh₂)₃):  Preparative, NMR, and Time-Resolved Studies
  作者：Robert Osman、David I. Pattison、Robin N. Perutz、Claudio Bianchini、Juan A. Casares、Maurizio Peruzzini

  DOI：10.1021/ja963797w

  日期：1997.9.1

  Photochemical reaction of Ru(PP3)H-2 (PP3 = P(CH2CH2PPh2)(3)) in THF under a rigorously inert atmosphere yields the cyclometalated complex Ru[(Ph2PCH2CH2)(2)P(CH2CH2PPhC6H4)]H. The latter is converted back to Ru(PP3)H-2 under H-2 and reacts even with traces of N-2 to yield Ru(PP3)(N-2). The dinitrogen complex may be synthesized directly by a number of methods. NMR spectroscopy shows that photolysis of Ru(PP3)H-2 under C2H4 and CO yields Ru(PP3)(C2H4) and Ru(PP3)(CO), respectively. Photolysis of Ru(PP3)H-2 with HSiEt3 in THF yields Ru(PP3)(SiEt3)H, while photolysis in mixtures of THF and benzene at low temperature yields Ru(PP3)(Ph)H. The latter is also generated by reduction of Ru(PP3)Cl-2 in the presence of benzene. Os(PP3)(Ph)H is formed either by photolysis of Os(PP3)H-2 or by reduction of Os(PP3)Cl-2 in the presence of benzene. Irradiation of Os(PP3)H-2 in THF or THF/hexane mixtures initially yields the THF C-H activation product, Os(PP3)(2-C4H7O)H. This complex is also generated by reduction of Os(PP3)Cl-2 with sodium naphthalenide under N-2 in the presence of THF. Os(PP3)(2-C4H7O)H is converted to the cyclometalated complex, Os[(Ph2PCH2CH2)(2)P(CH2CH2PPhC6H4)]H, on irradiation in THF and to Os(PP3)(Ph)H on irradiation in benzene. Reaction of Os(PP3)H-2 with CH3OTf (Tf = triflate) yields Os(PP3)(OTf)H, which is converted to the labile Os(PP3)(CH3)H on reaction with methyllithium. Laser flash photolysis of Ru(PP3)H-2 in cyclohexane (laser wavelength 308 nm) yields transient Ru(PP3) with an absorption maximum at 395 nm. The transient reacts with H-2, C6H6, HSiEt3, CO, N-2, C2H4, and THF with little discrimination; the second-order rate constants for these reactions lie in the range 5 x 10(5)-2x 10(6) dm(3) mol(-1) s(-1) at 295 K. Kinetic isotope effects have been determined for the reaction with benzene and THF, as 1.5 (0.2) and 1.1 (0.2), respectively. Activation parameters for reaction of Ru(PP3) are as follows: with HSiEt3 Delta H-double dagger = 35 (2) kJ mol(-1), Delta S-double dagger = -18 (6) J K-1 mol(-1); with C6H6 Delta H-double dagger = 39 (4) kJ mol(-1), Delta S-double dagger approximate to 0 J K-1 mol(-1). The reaction with THF yields a short-lived adduct, probably bound through oxygen, which is rapidly converted to the cyclometalated product. Laser flash photolysis of Os(PP3)H-2 generates transient Os(PP3) (lambda(max) = 390 nm). The transient kinetics of Os(PP3) are substantially different from its ruthenium analogue. It reacts with alkanes and shows different behavior toward THF but is unaffected by addition of H-2.Rate constants in the range 6 x 10(4)-6 x 10(5) dm(3) mol(-1) s(-1) (295 K) are presented for reaction with C6H6, THF, HSiEt3, CO, C2H4, N-2, and several alkanes. Kinetic isotope effects have been determined for the reactions with methylcyclohexane and benzene as 5.6 (1.5) and 0.6 (0.1), respectively. The rate constants for reaction with alkanes rise in the order, methylcyclohexane < pentane < heptane < methane. The rate constants for reaction with methane and benzene are insignificantly different. Following reaction of Os(PP3) with THF to form Os(PB)(THF), C-H insertion occurs with a first-order rate constant of 4.2 (8) x 10(3) s(-1) with k(H)/k(D) = 2.6 (0.4). The activation parameters for reaction of Os(PP3) with substrates are as follows: with pentane Delta H-double dagger = 27 (1) kJ mol(-1), Delta S-double dagger = -59 (4) J K-1 mol(-1); with HsiEt(3), Delta H-double dagger = 31 (5) kJ mol(-1), Delta S-double dagger = -27 (12) J K-1 mol(-1); with C6H6 Delta H-double dagger = 38 (3) kJ mol(-1), Delta S-double dagger = -7 (9) J K-1 mol(-1).