| 195048-87-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 195048-87-4
• 化学式: C₄₂H₄₂N₂OsP₄
• 分子量: 888.904
• InChiKey: SNZZQEUFVVAMMG-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：

  四氢呋喃 、 以 四氢呋喃 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  Photochemistry of M(PP₃)H₂ (M = Ru, Os; PP₃ = P(CH₂CH₂PPh₂)₃):  Preparative, NMR, and Time-Resolved Studies

  摘要：

  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).

  DOI：

  10.1021/ja963797w
• 作为产物：
  描述：

  、 氮 在 sodium naphthalenide 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Photochemistry of M(PP₃)H₂ (M = Ru, Os; PP₃ = P(CH₂CH₂PPh₂)₃):  Preparative, NMR, and Time-Resolved Studies

  摘要：

  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).

  DOI：

  10.1021/ja963797w