N-phenyl-P-(2,4,6-tri-t-butylphenyl)iminomethylenephosphine | 91508-77-9

• 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: N-phenyl-P-(2,4,6-tri-t-butylphenyl)iminomethylenephosphine
• 英文别名: 1-phenyl-3-(2,4,6-tri-t-butylphenyl)-1-aza-3-phosphaallene；N-phenyl-P-(2,4,6-tri-tert-butylphenyl)iminomethylenephosphine；2,4,6-(t-Bu)3C6H2PCNPh
• CAS: 91508-77-9
• 化学式: C₂₅H₃₄NP
• 分子量: 379.525
• InChiKey: LBOKFXKUFKGIJH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-phenyl-P-(2,4,6-tri-t-butylphenyl)iminomethylenephosphine 在 水 作用下， 以 氘代氯仿 为溶剂， 反应 48.0h， 生成 2,4,6-tri-tert-butylphenylphosphine oxide
  参考文献：
  名称：

  某些非常稳定的1-磷-丙二烯的分离和表征：空间保护的亚氨基亚甲基和亚乙烯基膦

  摘要：

  通过用2,4,6-三叔丁基苯基进行空间保护，获得了非常稳定的亚氨基亚甲基膦（3）和亚乙烯基膦（4），并描述了一些光谱数据。

  DOI：

  10.1016/s0040-4039(01)90047-4
• 作为产物：
  描述：

  (2,4,6-三-叔-丁基苯基)膦 在 正丁基锂 作用下， 生成 N-phenyl-P-(2,4,6-tri-t-butylphenyl)iminomethylenephosphine
  参考文献：
  名称：

  某些非常稳定的1-磷-丙二烯的分离和表征：空间保护的亚氨基亚甲基和亚乙烯基膦

  摘要：

  通过用2,4,6-三叔丁基苯基进行空间保护，获得了非常稳定的亚氨基亚甲基膦（3）和亚乙烯基膦（4），并描述了一些光谱数据。

  DOI：

  10.1016/s0040-4039(01)90047-4

文献信息

• Phosphaazaallene Dimerization and Phosphaallene Isomerization:  Catalysis by Zerovalent Palladium and Platinum Complexes
  作者：Marie-Anne David、John B. Alexander、David S. Glueck、Glenn P. A. Yap、Louise M. Liable-Sands、Arnold L. Rheingold

  DOI：10.1021/om960782y

  日期：1997.2.1

  Several Pd(0) complexes catalyze the dimerization of Mes*PCNPh [2, Mes* = 2,4,6-(t-Bu)3C6H2] to the unsymmetrical heterocycle Mes*P(μ-CNPh)NPh(μ-CPMes*) (5). The symmetrical dimer [Mes*P(μ-CNPh)]2 (7), which forms slowly by uncatalyzed dimerization of 2, does not interconvert with 5; both 5 and 7 were structurally characterized by X-ray crystallography. The Pt complexes PtL2[η2-(P,C)-Mes*PCNPh] [8

  几种Pd（0）配合物催化Mes * PCNPh [ 2，Mes * = 2,4,6-（t -Bu）3 C 6 H 2 ]的二聚为不对称杂环Mes * P（μ-CNPh）NPh（ μ-CPMes*）（5）。对称二聚体[Mes * P（μ-CNPh）] 2（7）由2的未催化二聚作用缓慢形成，但不与5互变。两个5和7进行了结构表征通过X射线晶体学。的Pt配合物PTL 2 [η 2 - （P，C ^）* -Mes PCNPh] [ 8，L = 1 / 2 DPPE（PH 2 PCH 2 CH 2 PPH 2）; 9，L = PPh 3 ; 参照图10，L ＝ PCy 3（Cy ＝ cC 6 H 11）]，制备了催化中间体的模型。将Mes * PCCPh 2（3）异构化为phosphaindan [2,4-（t -Bu ）2 C 6 H 2（6-CMe 2 CH 2 PCH CPh 2）]（6），这
• A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis, Structure, Reactivity, and Computational Studies
  作者：Congcong Zhang、Guohua Hou、Guofu Zi、Wanjian Ding、Marc D. Walter

  DOI：10.1021/jacs.8b09746

  日期：2018.10.31

  The synthesis, structure, and reactivity of a base-free terminal actinide phosphinidene metallocene have been comprehensively studied. The salt metathesis reaction of the thorium methyl iodide complex Cp‴2Th(I)Me (2; Cp‴ = η5-1,2,4-(Me3C)3C5H2) with Mes*PHK (Mes* = 2,4,6-(Me3C)3C6H2) in THF furnishes the first stable base-free terminal phosphinidene actinide metallocene, Cp‴2Th═PMes* (3). Density functional

  已经全面研究了无碱末端锕系膦亚茂金属茂的合成、结构和反应性。甲基碘化钍配合物 Cp‴2Th(I)Me (2; Cp‴ = η5-1,2,4-(Me3C)3C5H2) 与 Mes*PHK (Mes* = 2,4,6-) 的盐复分解反应(Me3C)3C6H2) 在 THF 中提供了第一个稳定的无碱末端膦亚锕系茂金属，Cp‴2Th=PMes* (3)。密度泛函理论 (DFT) 表明，Cp‴2Th2+ 和 [PMes*]2- 片段之间的键比相关的亚钍复合物中的键更共价。虽然膦化物配合物 3 对炔烃没有反应性，但它​​与各种杂不饱和分子如 CS2、异硫氰酸酯、腈、异腈和有机叠氮化物反应，形成二硫代碳化物、酰亚胺配合物、金属氮丙啶和叠氮化合物。
• Preparation and Hydrolysis of Some Sterically Protected 1-Aza-3-phosphaallenes
  作者：Takashi Niitsu、Naoki Inamoto、Kozo Toyota、Masaaki Yoshifuji

  DOI：10.1246/bcsj.63.2736

  日期：1990.9

  Some sterically protected 1-aza-3-phosphaallenes carrying 2,4,6-tri-t-butylphenyl group were prepared and the hydrolysis reactions of these azaphosphaallenes were studied.

  制备了一些带有2,4,6-三叔丁基苯基的空间保护的1-氮杂-3-磷烯并研究了这些氮杂磷烯的水解反应。
• Rhodium-Mediated Stoichiometric P:C Bond Cleavage and Catalytic Isomerization in Phosphacumulenes
  作者：Marie-Anne David、Sara N. Paisner、David S. Glueck

  DOI：10.1021/om00001a007

  日期：1995.1

  Reaction of Rh(PCy(3))(2)Cl (4a, Cy = cyclo-C6H11 with the phosphacumulenes Mes*P=C=X (X = O (1) X = NPh (2); Mes* = 2,4,6-(t-Bu)(3)C6H2) results in P=C bond cleavage to form [2,4-(t-Bu)(2)C6H2(6-CMe(2)CH(2)PH)](5) and trans-Rh(PCy(3))(2)Cl(CX) (6, X = O; 7,X = NPh), respectively. In contrast, 4a and related Rh(I) PPh(3) complexes are catalyst precursors for the rearrangement of Mes*P=C=CPh(2) 13) to its isomer [2,4-(t-Bu)(2)C6H2(6-CMe(2)CH(2)PCH=CPh(2))] (8); the intermediate [Rh(PCy(3))[eta(2)(P,C)-Mes*P=C=CPh(2)]Cl](n) (9a), which is itself an active catalyst for the isomerization, was isolated and characterized spectroscopically.
• Phosphinidene Transfer Reactions of the Terminal Phosphinidene Complex Cp2Zr(:PC6H2-2,4,6-t-Bu3)(PMe3)
  作者：Tricia L. Breen、Douglas W. Stephan

  DOI：10.1021/ja00153a013

  日期：1995.12

  The terminal zirconium phosphinidene complex Cp(2)Zr(PR*)(PMe(3)) (R* = C6H2-2,4,6-t-Bu(3)) 2 has been synthesized in high yield, and its reactivity has been investigated. The compound Cp(2)ZrMe(PHR*) 1 is unstable with respect to the loss of methane; in the presence of PMe(3) this reaction yielded 2. Reactions of 2 with benzophenone, benzaldehyde, or isophthalaldehyde produced phosphaalkenes PhCH=PR* 3, Ph(2)C=PR* 4, and 1,3-C6H2(CH=PR*)(2) 5, respectively. PhN=C=PR* 6 resulted from the reaction of 2 with phenyl isothiocyanate while the use of cyclohexanone afforded the enolate Cp(2)Zr(PHR*)(OC6H9) 7. Phosphinidene group transfer also took place in reactions of 2 with the appropriate organic dihalide or epoxide. In this way phosphaalkenes CH2=PR* 8 and CHCl=PR* 9, phosphirane (CH(2)CH(2)PR*) 10, phospholane 1,2-C6H4(CH(2)PR*)(2) 11 and substituted phosphiranes (CH2CH)(CHCH2-PR*) 12, CH2C(CCH(2)PR*) 13, (PhCHCH(Ph)PR*) 15, and trans-(PhCHCH(2)PR*) 16 were synthesized. The use of propylene oxide yielded the enolate Cp(2)Zr(PHR*)(OCH2CH=CH2) 17. Similar reactions of 2 with heavier group 14 dihalides and sulfides furnished Cp(2)Zr(PR*(SiMe(2)Cl))Cl 18, PR*(SiMe(2)Cl)(2) 19, (Me(2)GeCl)(2) PR* 20, (Me(2)GePR*)(2) 21, (t-Bu(2)SnPR*)(2) 22, and (Me(2)SnPR*)(2) 23. Intramolecular phosphinidene transfer occurred in reactions of 2 with benzonitrile and dicyclohexylcarbodiimide, giving Cp(2)Zr(PMe(3))(NC(Ph)(PR*)) 25 and Cp(2)Zr(N(Cy))(2)C=PR* 26, respectively. Crystallographic data are reported for compounds 22, 25b, and 26.