N-trimethylsilyl [tris(pyrrolidino)]phosphazene | 648419-38-9

• 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-trimethylsilyl [tris(pyrrolidino)]phosphazene
• 英文别名: Tripyrrolidin-1-yl(trimethylsilylimino)-lambda5-phosphane；tripyrrolidin-1-yl(trimethylsilylimino)-λ5-phosphane
• CAS: 648419-38-9
• 化学式: C₁₅H₃₃N₄PSi
• 分子量: 328.513
• InChiKey: JHQGHZHVZOVICK-UHFFFAOYSA-N

物化性质

• 沸点：
  398.0±25.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  22.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-trimethylsilyl [tris(pyrrolidino)]phosphazene 在 溴 、 benzyl potassium 、 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 、 甲苯 、 苯 为溶剂， 反应 90.5h， 生成 1-[tris(pyrrolidino)phosphazenyl bis(pyrrolidino)phosphazenyl]naphthalene
  参考文献：
  名称：

  A New Synthetic Pathway to the Second and Third Generation of Superbasic Bisphosphazene Proton Sponges: The Run for the Best Chelating Ligand for a Proton

  摘要：

  We present the up to now strongest chelating neutral pincer ligand for the simplest electrophile of chemistry, the proton. Two novel bisphosphazene proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) and its higher homologue P-2-TPPN, were obtained via a Staudinger reaction and investigated concerning their structural features and basic properties by experimental and computational means. They exhibit experimental pK(BH)(+) values in acetonitrile of 32.3 and 42.1, respectively, exceeding the existing basicitiy record for proton sponges by more than 10 orders of magnitude. We show that Schwesinger's concept of homologization of phosphazene bases and Alder's concept of proton chelation in a constrained geometry regime of basic centers can be combined in the design of highly basic nonionic superbases of pincer type.

  DOI：

  10.1021/ja409760z
• 作为产物：
  描述：

  (三氯甲基)三甲基硅烷 、 Iminotri-1-pyrrolidinylphosphorane 生成 N-trimethylsilyl [tris(pyrrolidino)]phosphazene
  参考文献：
  名称：

  胍基磷腈：THF 和气相中的设计、合成和碱度

  摘要：

  提出了创建新一代非离子超强碱的原理。它基于使用四甲基胍或容易获得的 1,3-二甲基咪唑烷-2-亚胺将四烷基胍基、1,3-二甲基咪唑烷-2-亚氨基或双（四烷基胍基）carbimino 基团连接到亚氨基正膦基团的磷原子上。已经合成了七种新的非离子超碱性磷腈碱，四甲基胍基取代了 P 原子。它们的碱强度是通过分光光度法滴定在四氢呋喃 (THF) 溶液中确定的，并与专为本研究设计的八种参考超碱 P2- 和 P4-亚氨基正膦进行比较。几种胍基和N',N',N'',N''的气相碱度 计算了-四甲基胍基(tmg)-取代的磷腈及其环状类似物，并确定了(tmg)3P=Nt-Bu和(tmg)3P=Nt-Bu x HBF4的晶体结构。对于 THF 介质中的四甲基胍基，该原理的巨大碱度增加效果得到了实验验证：当从 (dma)3P=Nt-Bu (pKalpha = 18.9) 移动到 (tmg)3P=Nt-Bu 时，碱度增加（

  DOI：

  10.1021/ja053543n

文献信息

• Constrained-Geometry Bisphosphazides Derived from 1,8-Diazidonaphthalene: Synthesis, Spectroscopic Characteristics, Structural Features, and Theoretical Investigations
  作者：Julius F. Kögel、Nuri C. Abacılar、Felicia Weber、Benjamin Oelkers、Klaus Harms、Borislav Kovačević、Jörg Sundermeyer

  DOI：10.1002/chem.201304498

  日期：2014.5.12

  Attempts to protonate the obtained bisphosphazides and to prove the computationally predicted pKBH+ values through NMR titration reactions resulted in their decay, which again was rationalized by theoretical calculations. Altogether we present the so far most extensive spectroscopic, structural and theoretical investigation of constrained geometry bisphosphazides and their Brønsted and Lewis basic properties

  对1,8-二叠氮萘与磷（III）结构单元之间的Staudinger反应进行的研究是合成超碱性双磷腈质子海绵的关键步骤，得到了一组具有受限几何1,8-二取代萘骨架的双磷叠氮化物。该化合物类别不仅因为其出乎意料的高稳定性而引起了我们的兴趣，而且还特别是由于其在理论上预测的双磷腈类似物范围内的碱性，可以将其称为两个高度碱性氮原子的受限几何相互作用。11个带有简单P-氨基以及P-胍基取代基，氮杂磷杂环戊烷部分，P 2结构单元或衍生自L的手性P-氨基取代基的新双磷叠氮化物出现脯氨酸。对它们的光谱性质以及部分发色和结构特征进行了研究。在吡咯烷基取代的TPPN（2N 2）（TPPN = 1,8-双（三spyrrolidinophosphazenyl）萘）的情况下，从理论上和实验上逐步研究了氮的去除，这导致了TPPN（1N 2）的分离和结构表征）在一个分子中带有磷叠氮化物和磷腈官能团。尝试质子化获得的双磷叠氮化物并证明计算预测的p
• Mono‐Phosphazenyl Phosphines (R ₂ N) ₃ P=N–P(NR ₂ ) ₂ – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates
  作者：Julius F. Kögel、Sebastian Ullrich、Borislav Kovačević、Sebastian Wagner、Jörg Sundermeyer

  DOI：10.1002/zaac.202000108

  日期：2020.7.15

  We present a convenient three‐step synthesis of amino substituted phosphazenyl phosphines of the general formula (R2N)3P=N–P(NR2)2 [NR2 = N(CH2)4, N(CH2)5, N(CH2)6]. These easily accessible mixed valent compounds display a surprisingly high proton affinity and basicity in the same range as the corresponding Schwesinger diphosphazene (Me2N)3P=N–P=NEt(NMe2)2 (Et‐P2) and Verkade's proazaphosphatrane superbases

  我们提出了通式（R 2 N）3 P = N–P（NR 2）2 [NR 2 = N（CH 2）4，N（CH 2）5的氨基取代的磷腈基膦的便捷三步合成方法，N（CH 2）6 ]。这些容易获得的混合价化合物在与相应的Schwesinger二磷腈（Me 2 N）3 P = N–P = NEt（NMe 2）2（Et-P 2）和Verkade的proazaphosphatrane超级碱基。在中心的[P III –N = P V ]支架中，膦P III而不是磷腈N III原子是质子亲和性，碱度和供体强度最高的中心。作为P-碱，标题化合物的计算出的质子亲和力在265.8（NR 2 = NMe 2）和274.7 kcal · mol –1 [NR 2 = N（CH 2）4 ]之间，p K BH +值在26.4（NR 2 = NMe 2）和31.5 [NR 2 = N（CH 2）4 ]在乙腈刻度上。作为P-亲
• Acid−Base Equilibria in Nonpolar Media. 4. Extension of the Self-Consistent Basicity Scale in THF Medium. Gas-Phase Basicities of Phosphazenes
  作者：Ivari Kaljurand、Toomas Rodima、Aino Pihl、Vahur Mäemets、Ivo Leito、Ilmar A. Koppel、Masaaki Mishima

  DOI：10.1021/jo034537h

  日期：2003.12.1

  Eleven new phenyl-substituted phosphazenes (P-1-, P-3-, and P-4-bases) have been synthesized by the Staudinger or the Kirsanov reactions. The UV-vis spectrophotometric titration method was used to establish the relative basicity of them, and to extend the ion-pair basicity scale for THF medium. These measurements together with our previous work give a continuous basicity scale in THF ranging from 2.6 (2-MeO-pyridine) to 26.6 (2-Cl-C6H4P4(pyrr) phosphazene) in pK(alpha) units: that is for 24 orders of magnitude and containing 58 compounds (pyridines, anilines, amines, guanidines, amidines, phosphazenes). Ion-pair formation was taken into account by using the Fuoss equation. DeltapK(ip) values of some phosphazene indicators estimated earlier by the C-13 NMR method were revised. For some of the phosphazenes gas-phase basicities were measured.