[Ru(dinitrogen)(tris[2-(diphenylphosphino)ethyl]phosphine)] | 195048-77-2

• 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: [Ru(dinitrogen)(tris[2-(diphenylphosphino)ethyl]phosphine)]
• CAS: 195048-77-2
• 化学式: C₄₂H₄₂N₂P₄Ru
• 分子量: 799.774
• InChiKey: WNFJFJLDMYZEOV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [Ru(dinitrogen)(tris[2-(diphenylphosphino)ethyl]phosphine)] 、 氢气 以 四氢呋喃 为溶剂， 生成 [RuH₂(tris[2-(diphenylphosphino)ethyl]phosphine)]
  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：

  [(P(CH2CH2PPh2)3)Ru(H)(η(1)-N2)][BPh4] 在 苯基锂 作用下， 以80%的产率得到[Ru(dinitrogen)(tris[2-(diphenylphosphino)ethyl]phosphine)]
  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

文献信息

• Base-Induced Dehydrogenation of Ruthenium Hydrazine Complexes
  作者：Leslie D. Field、Hsiu L. Li、Scott J. Dalgarno、Ruaraidh D. McIntosh

  DOI：10.1021/ic302449n

  日期：2013.2.4

  (PP3iPr = P(CH2CH2PiPr2)3) with hydrazine, phenylhydrazine, and methylhydrazine afforded side-on bound hydrazine complexes [RuCl(η2-H2N-NH2)(η3-PP3iPr)]+, [RuCl(η2-H2N-NHPh)(η3-PP3iPr)]+, and [RuCl(η2-H2N-NHMe)(η3-PP3iPr)]+. The analogous reactions of [RuCl2(PP3Ph)] (PP3Ph = P(CH2CH2PPh2)3) with hydrazine, phenylhydrazine, and methylhydrazine afforded end-on bound hydrazine complexes [RuCl(η1-H2N-NH2)(PP3Ph)]+

  将[RuCl（PP的治疗3我镨）] +氯-（PP 3我镨= P（CH 2 CH 2 P我镨2）3）与肼，苯肼和甲基肼，得到侧面上结合的肼复合物将[RuCl（ η 2 -H 2 N-NH 2）（η 3 -PP 3我镨）] +，将[RuCl（η 2 -H 2 N-二NHPh基）（η 3 -PP 3我镨）] +和将[RuCl（η 2 -H 2 N-二NHMe）（η 3 -PP 3我镨）] +。的类似反应将[RuCl 2（PP 3博士）]（PP 3博士= P（CH 2 CH 2 PPH 2）3）与肼，苯肼，甲基肼和提供端上结合的肼复合物将[RuCl（η 1 -H 2 N-NH 2）（PP 3博士）] +，将[RuCl（η 1 -H 2的N- NHPh基）（PP 3博士）] +，和将[RuCl（η 1 -H 2的N- NHMe）（PP 3博士）] +。用强碱处理母体肼配合物[RuCl（N 2 H 4）（PP
• C−H Bond Cleavage in Thiophenes by [P(CH₂CH₂PPh₂)₃Ru]. UV Flash Kinetic Spectroscopy Discloses the Ruthenium−Thiophene Adduct Which Precedes C−H Insertion
  作者：Claudio Bianchini、Juan A. Casares、Robert Osman、David I. Pattison、Maurizio Peruzzini、Robin N. Perutz、Fabrizio Zanobini

  DOI：10.1021/om9703898

  日期：1997.10.1

  reaction of isolated 4 with 2,5-Me2T. The Ru(0) transient, [(PP3)Ru], generated by laser flash photolysis in either cyclohexane or THF solution, has been detected and characterized by UV−vis spectroscopy. [(PP3)Ru] reacts with T (k2 = (1.4 ± 0.2) × 106 dm3 mol-1 s-1), yielding an adduct [(PP3)Ru(T)]. In cyclohexane, [(PP3)Ru(T)] decays to the C−H insertion product 5 with first-order kinetics (k = 20 ±

  [（PP 3）RuH 2 ]（PP 3 = P（CH 2 CH 2 PPh 2）3）（1）在THF中，在惰性气氛（N 2，Ar或He）存在下于23°C进行光解噻吩（T）或2-噻吩甲酸乙酯（2-CO 2 Et T）的合成得到（氢化物）2-噻吩配合物[（PP 3）Ru（H）（2-Tyl）]（5）（Tyl = C 4 H 3 S）和[（PP 3）Ru（H）（2-CO 2 EtTyl）]（7）（CO 2 EtTyl = C 4H 2（CO 2 Et）S）。CH插入产物5和7也可以通过Ru（0）二氮配合物[（PP 3）Ru（N 2）]（4）在THF中与T或2-CO 2 Et T的热反应选择性地获得。配合物5和7是光化学和热稳定的。在相当的条件下，在存在T的情况下，Os衍生物[（PP 3）OsH 2 ]在THF中的光解仅产生CH插入产物[（PP 3）Os（H）（2-Tyl）]。的光解1在氮气下在23℃和在2
• Reduction of Dinitrogen to Ammonia and Hydrazine on Low-Valent Ruthenium Complexes
  作者：Leslie D. Field、Hsiu L. Li、P. Manohari Abeysinghe、Mohan Bhadbhade、Scott J. Dalgarno、Ruaraidh D. McIntosh

  DOI：10.1021/acs.inorgchem.8b02850

  日期：2019.2.4

  The ruthenium(0) dinitrogen complexes [Ru(N2)(PP3R)] [PP3R = P(CH2CH2PR2)3; R = iPr or Cy] react with triflic acid and other strong acids to afford mixtures of ammonia and hydrazine. In this reaction, Ru(0) is oxidized to Ru(II), and depending on the solvent, Ru(II) benzene or triflate complexes are isolated and characterized from the reactions with triflic acid as the final metal-containing products

  钌（0）二氮配合物[Ru（N 2）（PP 3 R）] [PP 3 R = P（CH 2 CH 2 PR 2）3；R =我镨或赛扬]与三氟甲磺酸和其它强酸反应，得到氨和肼的混合物。在该反应中，Ru（0）被氧化为Ru（II），根据溶剂的不同，分离出Ru（II）苯或三氟甲磺酸盐配合物，并从与三氟甲磺酸的反应中进行表征，以三氟甲磺酸作为反应的最终含金属产物。分离出Ru（II）产物，并还原成Ru（0）二氮配合物，从而提供了一个减少配位二氮的循环。