N,N’,N’-tris(trimethylsilyl)hydrazine(dichloro)phosphane | 111437-98-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: N,N’,N’-tris(trimethylsilyl)hydrazine(dichloro)phosphane
• 英文别名: N,N',N'-[tris(trimethylsilyl)]hydrazino(dichloro)phosphane；dichloro-N,N',N'-[tris(trimethylsilyl)]hydrazinophosphane；dichloro[N,N',N'-tris-(trimethylsilyl)hydrazino]phosphane；N,N',N'-[tris(trimethylsilyl)hydrazino]dichlorophosphane；dichloro[N,N',N'-tris(trimethylsilyl)hydrazino]phosphane；N,N',N'-tris(trimethylsilyl)hydrazinodichlorophosphane；1-Dichlorophosphanyl-1,2,2-tris(trimethylsilyl)hydrazine
• CAS: 111437-98-0
• 化学式: C₉H₂₇Cl₂N₂PSi₃
• 分子量: 349.463
• InChiKey: FSMUJBCLXJVXRL-UHFFFAOYSA-N

物化性质

• 沸点：
  291.0±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.71
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N’,N’-tris(trimethylsilyl)hydrazine(dichloro)phosphane 以 乙醚 、 正己烷 、 苯 为溶剂， 反应 150.0h， 生成 六甲基二硅氮烷
  参考文献：
  名称：

  Vasisht, S. K.; Kaur, Tripat P.; Usha, K., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 107, # 1-4, p. 189 - 196

  摘要：

  DOI：
• 作为产物：
  描述：

  Lithium-tris(trimethylsilyl)hydrazid 在 三氯化磷 作用下， 以 乙醚 为溶剂， 反应 12.0h， 以94%的产率得到N,N’,N’-tris(trimethylsilyl)hydrazine(dichloro)phosphane
  参考文献：
  名称：

  Niecke, Edgar; Altmeyer, Oliver; Nieger, Martin, Angewandte Chemie, 1991, vol. 103, # 9, p. 1158 - 1159

  摘要：

  DOI：

文献信息

• Titanocene-Mediated Formation of Phosphorus−Phosphorus Bonds
  作者：Markus Schaffrath、Alexander Villinger、Dirk Michalik、Uwe Rosenthal、Axel Schulz

  DOI：10.1021/om701038p

  日期：2008.4.1

  Furthermore, the known diphosphene Mes*P═PMes* (4) (Mes* = 2,4,6-tri-tert-butylphenyl) and the dichlorodiphosphine Mes*(Cl)PP(Cl)Mes* (5) were prepared by reaction of Cp2Ti(btmsa) with Mes*PCl2. The reaction of Cp2Ti(btmsa) with the sterically less demanding PhPCl2 resulted in the isolation of a triphosphinato complex. The diphosphine Ph2P−PPh2 (6) was synthesized by reaction of Ph2PCl with Cp2Ti(btmsa)

  Cp的反应2的Ti（btmsa）[btmsa =双（三甲基甲硅烷基）乙炔（ME 3 SiC≡CSiMe 3）]用笨重的二氯膦导致取决于所使用的化学计量diphosphenes或dichlorodiphosphines的形成。将（Me 3 Si）2 NN（SiMe 3）PCl 2（1）转化为双[三（三甲基甲硅烷基）肼基]二氯二膦（2）或双[三（三甲基甲硅烷基）肼基]二膦（3），具体取决于过量使用1或Cp 2的Ti（btmsa）。根据原料比例，Cp 2 TiCl 2除了1或3之外，还获得了作为副产物的（Cp 2 TiCl）2或（Cp 2 TiCl）2。化合物2和3通过X射线衍射在结构上表征。此外，已知的diphosphene的MES *P═PMa href=https://www.molaid.com/MS_310095 target="_blank">MES*（4）（MES * = 2,4,6-三-叔丁基苯基）和dichlorodiphosphine的MES *（Cl）的PP（CL）的MES *（5）通过制备Cp
• Staudinger Reaction as a Way Out To Avoid Cyclization in the Reaction of Silylated Dichloro(hydrazino)phosphane with Trimethylsilyl Azide
  作者：Axel Schulz、Alexander Villinger

  DOI：10.1002/ejic.200800446

  日期：2008.9

  Reaction of dichloro-N,N′,N′-[tris(trimethylsilyl)]hydrazinophosphane (1) with Me3SiN3 leads after an initial chlorine/azide exchange in a Staudinger reaction to a new phosphorus azide. The in situ formed phosphoranimine reacts with GaCl3 by Me3SiCl elimination, resulting in a phosphoranimino–dichlorogallane, which dimerizes to a Ga2N2-four-membered ring. The overall reaction at ambient temperature

  二氯-N,N',N'-[三(三甲基甲硅烷基)]肼基膦 (1) 与 Me3SiN3 的反应在施陶丁格反应中初始氯/叠氮化物交换后生成新的叠氮化磷。原位形成的磷胺通过 Me3SiCl 消除与 GaCl3 反应，产生磷氨基-二氯没食子烷，其二聚化为 Ga2N2 四元环。环境温度下的整体反应代表快速且干净的高产率反应（反应时间为 2 小时）。形成的叠氮基-磷氨基-二氯没食子烷的二聚体得到了充分表征，并显示在 103 °C 以上的温度下稳定。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• GaCl3-assisted [3+2] cycloaddition: A route to new binary PN-heterocycles
  作者：Peter Mayer、Axel Schulz、Alexander Villinger

  DOI：10.1016/j.jorganchem.2006.10.024

  日期：2007.6

  dipolarophile Mes∗–NP–Cl (Mes∗ = 2,4,6-tri-tert-butylphenyl) was reacted with the 1,3-dipole (TMS)2N–N(TMS)–PCl2 (TMS = trimethylsilyl) yielding the kinetically stabilized [3+2] cycloaddition product triazadiphosphole, Mes∗N3P2, stabilized as GaCl3 adduct. Synthesis, structure and bonding are discussed.

  从[3 + 2]合成工具套件开始，可以根据称为GaCl 3辅助[3 + 2]环加成的新合成方法，分离出新的PN-杂环。根据这一概念的亲偶极的MES * -NP-CL（MES *  = 2,4,6-三-叔丁基苯基）与1,3-偶极（TMS）反应2 N-N（TMS）-PCl 2（TMS =三甲基甲硅烷基）产生动力学稳定的[3 + 2]环加成产物三氮杂二磷腈MES * N 3 P 2，稳定为GaCl 3加合物。讨论了合成，结构和键合。
• Transition‐Metal‐Free Boron–Carbon Bond Activation: Insertion of an NNP Fragment into a Boron–Carbon Bond
  作者：Markus Kowalewski、Burkhard Krumm、Peter Mayer、Axel Schulz、Alexander Villinger

  DOI：10.1002/ejic.200700895

  日期：2007.12

  reaction with B(C6F5)3 resulted in the formation of a novel diazadiphosphetidine with a phosphorus(III) atom attached to a pentafluorophenyl group, which can be regarded as a formal NNP fragment insertion into a B–C bond.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  研究了含氟路易斯酸如纯 BF3、 ·OEt2 和 B(C6F5)3 对 (Me3Si)2N-N(SiMe3)-PCl2 中 Me3SiCl 消除的影响和反应性。与 B( )3 的反应导致形成一种新的二氮杂二膦酸，其中磷 (III) 原子连接到五氟苯基，这可以看作是一个正式的 NNP 片段插入到 B-C 键中。 (© Wiley- VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Synthesis of 1,3-Dichloro-<i>cyclo</i>-1,3-diphosphadiazanes from Silylated Amino(dichloro)phosphanes
  作者：Axel Schulz、Alexander Villinger、Andrea Westenkirchner

  DOI：10.1021/ic4017728

  日期：2013.10.7

  The synthesis of 1,3-dichloro-cyclo-1,3-diphosphadiazanes [ClP(mu-NR)](2) via elimination of Me3SiCl from silylated amino(dichloro)phosphanes, R-N(SiMe3)PCl2, was studied by different synthetic protocols starting from R-N(H)SiMe3 (R = Si(SiMe3)(3) = Hyp, N(SiMe3)(2), Mes* = 2,4,6-tri-tert-butylphenyl, Ter = 2,4-bis(2,4,6-trimethylphenyl)phenyl, Dipp = 2,6-diisopro-pylphenyl, Dmp = 2,6-dimethylphenyl, Ad = Adamantyl, Trityl = Ph3C, Tos = tosyl = CH3C6H4SO2, n-Oct = n-octyl, and Me3Si).A new synthetic route using trimethylsilyl-substituted amino(dichloro)phosphanes, R-N(SiMe3)PCl2, was developed to form cyclo-diphosph(III)-azanes simply by adding a mixture of RfOH/base (RfOH = hexafluoroisopropanole). By this method electron-rich/-poor aryl-, silyl-, and bissilylamino-substituted cyclo-diphosph(III)-azanes are accessible such as the unprecedented (Me3Si)(2)N-substituted species [ClP(mu-NN(SiMe3)(2))](2) starting from tris(trimethylsilyl)hydrazine and PCl3. Additionally, the difficulties with the preparation of cyclo-diphosphadiazanes depending on the starting materials, solvents, and bases due to the competition of different reaction channels are studied.