tris(2-(dicyclohexylphosphanyl)ethyl)phosphane | 146337-60-2

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: tris(2-(dicyclohexylphosphanyl)ethyl)phosphane
• 英文别名: tris[2-(dicyclohexylphosphino)ethyl]phosphine；tris(dicyclohexyl-phosphinoethyl)phosphine；tris(2-dicyclohexylphosphanylethyl)phosphane
• CAS: 146337-60-2
• 化学式: C₄₂H₇₈P₄
• 分子量: 706.976
• InChiKey: LWMGCLLMJCACDU-UHFFFAOYSA-N

物化性质

• 沸点：
  754.8±59.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tris(triphenylphosphine)ruthenium(II) chloride 、 tris(2-(dicyclohexylphosphanyl)ethyl)phosphane 以 二氯甲烷 为溶剂， 以88%的产率得到[RuCl(tris(2-dicyclohexylphosphinoethyl)phosphine)]Cl
  参考文献：
  名称：

  Use of the new ligand P(CH2CH2PCy2)3 in the synthesis of dihydrogen complexes of iron(II) and ruthenium(II)

  摘要：

  The novel bulky and basic tetradentate ligand P(CH2CH2PCy2)3 (PP3Cy) is synthesized by the LiN(i-Pr)2-Catalyzed addition reaction of dicyclohexylphosphine (HPCy2) to P(CH=CH2)3. Treatment of RuCl2(PPh3)3 with PP3Cy produces the five-coordinate square-pyramidal complex [RuCl(PP3CY)]Cl, Which is converted into [RuCl(PP3Cy)]BPh4 when treated with NaBPh4. Similarly, FeCl2 reacts with PP3CY to give [FeCl(PP3CY)]Cl. The structure of the tetraphenylborate salt [FeCI(PP3CY)] BPh4 is trigonal bipyramidal around Fe(II); crystals are monoclinic, space group P2(1)/c, with a = 12.699(4) angstrom, b = 29.046(16) angstrom, c = 17.026(7) angstrom, beta = 103.14(3)-degrees, and V = 6116(5) angstrom3 for Z = 4; R = 0.065. Reaction of [RuCl(PP3Cy)]Cl with excess NaBH4 in THF yields mer-RuH(eta2-BH4)(eta3-PP3Cy.BH3), where the tetraphosphine is bound via three P atoms to ruthenium and the BH3 is bound to a dangling terminal PCY2 group of the tetraphosphine. The monohydride complex RuHCl(PP3Cy) is obtained from the reaction of [RuCl(PP3CY)]Cl with excess NaOMe in refluxing THF. The eta2-dihydrogen complex[RuH(eta2-H2)(PP3CY)]BPh4 is synthesized by treating [RuCl(PP3CY)]BPh4 with 1 equiv of NaBH4 under an atmosphere of dihydrogen. The analogous iron complex is also described. The nonclassical structures of [MH(eta2-H2)(PP3CY)]BPh4 (M = Fe, Ru) are established by H-1, P-31, and T1 NMR measurements and the observation of a 1J(HD) coupling constant of 28 Hz in the isotopomer [RuD(HD)(PP3-Cy)]+. Despite the steric bulk of the ligand, the complexes adopt an octahedral geometry, [MH(H2)(PP3CY)]+, instead of a trigonal-bipyramidal ligand geometry with an H3 ligand.

  DOI：

  10.1021/om00027a046
• 作为产物：
  描述：

  乙烯基溴化镁 、 二环己基膦 在 三氯化磷 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以81%的产率得到tris(2-(dicyclohexylphosphanyl)ethyl)phosphane
  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：

  2-氨基苯甲腈 在 cobalt(III) acetylacetonate 、 tris(2-(dicyclohexylphosphanyl)ethyl)phosphane 、 potassium tert-butylate 、 氢气 作用下， 以 叔丁醇 为溶剂， 120.0 ℃ 、3.0 MPa 条件下， 反应 18.0h， 以86%的产率得到2-氨基苄胺
  参考文献：
  名称：

  通过使用钴膦催化剂将腈选择性加氢成伯胺

  摘要：

  提出了使用非贵金属基体系将腈催化加氢成伯胺的一般程序。Co（acac）3与三[2-（二环己基膦基）乙基]膦结合可有效催化多种（杂）芳族和脂肪族腈的选择性加氢反应，生成相应的胺。

  DOI：

  10.1002/cssc.201601843

文献信息

• Ammonia and Hydrazine from Coordinated Dinitrogen by Complexes of Iron(0)
  作者：Leslie D. Field、Hsiu L. Li、Scott J. Dalgarno、Ruaraidh D. McIntosh

  DOI：10.1002/ejic.201900058

  日期：2019.4.16

  The iron(0) dinitrogen complexes [Fe(N2)(PP3)] (PP3 = P(CH2CH2PR2)3, R = Ph, iPr, Cy) were synthesized by reduction of the precursor chloro complexes with potassium graphite. On reaction with triflic acid, [Fe(N2)(PP3)] complexes afforded ammonia and hydrazine in yields of up to 23 and 16% respectively. The complex [Fe(N2)(PP3)] which has only been previously synthesized in situ, has now been isolated

  铁 (0) 二氮配合物 [Fe(N2)(PP3)] (PP3 = P(CH2CH2PR2)3, R = Ph, iPr, Cy) 是通过用钾石墨还原前体氯配合物来合成的。在与三氟甲磺酸反应时，[Fe(N2)(PP3)] 络合物以分别高达 23% 和 16% 的产率提供氨和肼。以前仅在原位合成的复合物 [Fe(N2)(PP3)] 现在已被分离出来，并通过 15N NMR 光谱和 X 射线晶体学进行了充分表征。
• Catalytic Dinitrogen Reduction at the Molybdenum Center Promoted by a Bulky Tetradentate Phosphine Ligand
  作者：Qian Liao、Nathalie Saffon-Merceron、Nicolas Mézailles

  DOI：10.1002/anie.201408664

  日期：2014.12.15

  Stoichiometric reduction of N2 at a Mo center stabilized by a bulky tetradentate phosphine ligand () allowed isolation of Mo–imidoamine and Mo–imido complexes. Both complexes as well as the MoII precursor are equally suitable catalysts for the synthesis of NTMS3 (TMS=trimethylsilyl) from N2, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the

  通过笨重的四齿膦配体（）稳定的Mo中心的N 2的化学计量还原使得可以分离Mo-亚氨基胺和Mo-亚氨基复合物。络合物以及Mo II前体均是同样合适的催化剂，用于由N 2，TMSC1和电子源合成NTMS 3（TMS =三甲基甲硅烷基）。机理研究证明，TMS自由基至少参与其中一个催化步骤。
• COMPOSITION AND POLYMER
  申请人：Asahi Kasei Kabushiki Kaisha

  公开号：EP2735581B1

  公开（公告）日：2021-07-14
• Composition and Polymer
  申请人：Nakamura Akitake

  公开号：US20140121293A1

  公开（公告）日：2014-05-01

  Disclosed is a composition comprising (A) at least one compound selected from the group consisting of an ether compound having two or more ether groups, a trivalent phosphorus compound, and a ketone compound, (B) a boron trihalide, and (C) an episulfide compound.
• US9334371B2
  申请人：——

  公开号：US9334371B2

  公开（公告）日：2016-05-10