[ClP(μ-N-di(2,6-isopropylphenyl))]₂ | 511548-93-9

• 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: [ClP(μ-N-di(2,6-isopropylphenyl))]₂
• 英文别名: [ClP(μ-NDipp)]₂；1,3-dichloro-2,4-bis(2,6-di-isopropylphenyl)-cyclo-1,3-diphospha-2,4-diazane；[DippNPCl]2；2,4-Dichloro-1,3-bis[2,6-di(propan-2-yl)phenyl]-1,3,2,4-diazadiphosphetidine
• CAS: 511548-93-9
• 化学式: C₂₄H₃₄Cl₂N₂P₂
• 分子量: 483.401
• InChiKey: OKPXCPWOURTEBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  [ClP(μ-N-di(2,6-isopropylphenyl))]₂ 在 碘代三甲硅烷 、 sodium iodide 作用下， 以 二氯甲烷 为溶剂， 反应 72.5h， 以87%的产率得到1,3-diiodo-2,4-bis(2,6-di-isopropylphenyl)-cyclo-1,3-diphospha-2,4-diazane
  参考文献：
  名称：

  Synthesis of Blue Imino(pentafluorophenyl)phosphane

  摘要：

  The reaction of AgC6F5 with monomeric iminophosphanes of Mes*-N=P-X (X = Cl, I) in CH2Cl2 at ambient temperature gives imino(pentafluorophenyl)phosphane, Mes*N=P(C6F5) (1), in almost quantitative yield (96%), which could be isolated as a highly viscous blue oil. The same reaction with LiC6F5 results in the formation of imino(amino)phosphane (C6F5)(2)P-N(Mes*)-P=NMes* (2) (yield 93%). In the second series of experiments the analogous reaction of MC6F5 (M = Ag, Li) with dimeric [Cl-P(mu-N -Dipp)](2) was studied, leading to the formation of [R-P(mu-N-Dipp)](2) (R = C6F5) (3) for M = Ag, while only decomposition products such as P(C6F5)(3) were observed in the reaction with the Li salt. Highly labile Mes*-N=P-C6F5 (1) decomposes at ambient temperatures, forming among other products the diphosphane (C6F5)(2)P-F(C6F5)(2) (4). Reaction of 1 with Fe-2(CO)(9) yields the iron carbonyl complexes Mes*-N=P(C6F5)center dot Fe(CO)(4) (5) and [Mes*-N=P(C6F5)](2)center dot Fe(CO)(3) (6). The structure, bonding, and potential energy surface are discussed on the basis of B3LYP/6-31G(d, p) computations. According to time-dependent B3LYP calculations, the blue color of 1 arises from an n -> pi* electronic transition.

  DOI：

  10.1021/ic200623x
• 作为产物：
  描述：

  2,6-二异丙基苯胺 在 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 以23%的产率得到[ClP(μ-N-di(2,6-isopropylphenyl))]₂
  参考文献：
  名称：

  Sequential dehydrochloride coupling of trichlorophosphine with 2,6-di-isopropylaniline: aminophosphine precursors to phosphetidines

  摘要：

  使用³¹P NMR光谱法研究了PCl₃与DippNH₂（Dipp = 2,6-二异丙基苯基）的多种化学计量比例。去氢氯化偶联反应由于Dipp取代基的中等立体障碍而得到介导。报告了氨基二氯膦（1）、氨基四氯二膦（4）和二氯膦烯（7）的分离和表征数据。观察结果提供了新的关于卤代膦与主要胺类的去氢氯化偶联产物的认识。关键词：磷、氮、磷氮杂环、磷膦烯、亚胺膦。

  DOI：

  10.1139/v02-161

文献信息

• Preparation of the [(DippNP)₂(P₄)₂]²⁺-Dication by the Reaction of [DippNPCl]₂ and a Lewis Acid with P₄
  作者：Michael H. Holthausen、Jan J. Weigand

  DOI：10.1021/ja906878q

  日期：2009.10.14

  a disguised bifunctional Lewis acid [DippNP](2)(2+) obtained from the cyclo-1,3-diphospha-2,4-diazane [DippNPCl](2) for P(4) functionalization. This has enabled the targeted preparation of novel mono- and dicationic phosphorus-rich clusters [(DippNP)(2)(P(4))Cl](+) and [(DippNP)(2)(P(4))(2)](+). The utilization of such a bifunctional phosphenium cation represents a rational and potentially versatile

  白磷 P(4) 的受控活化为磷化学的许多方面提供了一个关键的切入点。N-杂环卡宾和卡宾样主族元素片段对 P(4) 的激活和功能化具有相当大的当前兴趣。在这篇通讯中，我们报告了首次使用从环-1,3-二磷酸-2,4-二氮烷 [DippNPCl](2) 中获得的伪装双功能路易斯酸 [DippNP](2)(2+) 用于 P (4)功能化。这使得能够靶向制备新型单和双阳离子富磷簇 [(DippNP)(2)(P(4))Cl](+) 和 [(DippNP)(2)(P(4))(2 )](+)。这种双功能鏻阳离子的利用代表了一种合理且具有潜在通用性的合成方法，用于使用 P(4) 作为构建块组装大型集群。
• Chiral Ditopic Cyclophosphazane (CycloP) Ligands: Synthesis, Coordination Chemistry, and Application in Asymmetric Catalysis
  作者：Torsten Roth、Hubert Wadepohl、Dominic S. Wright、Lutz H. Gade

  DOI：10.1002/chem.201302327

  日期：2013.10.4

  dichlorocyclophosphazanes [ClP(μ‐NR)}2] containing chiral and achiral R groups was obtained from simple commercially available amines and PCl3. Their condensation reactions with axially chiral biaryl diols yielded ansa‐bridged chiral cyclophosphazane (CycloP) ligands. This highly modular methodology allows extensive elaboration of the ligand set, in which the chirality can be introduced at the diol bridge

  从简单的市售胺和PCl 3获得了一系列含有手性和非手性R基团的二氯环磷氮烷[ClP（μ‐NR）} 2 ] 。它们与轴向手性联芳基二醇的缩合反应产生了ansa桥联的手性环磷氮烷（CycloP）配体。这种高度模块化的方法学允许对配体集进行详尽的阐述，其中可以在二醇桥和/或酰胺基R基团上引入手性。这提供了观察催化中的匹配和不匹配效应的可能性。合成了一系列二十个CycloP配体，并通过多核NMR光谱，HRMS，元素分析以及在某些情况下的单晶X射线衍射进行了表征。这些研究表明，所有对位的CycloP配体都是C 2对称，使它们的金属配位点对称。使用晚期过渡金属CycloP配合物作为催化剂，探索了两个公认的对映选择性反应。γ-烯基磺酰胺的金催化加氢胺化反应以及二烯和醛的不对称镍催化的三组分偶联反应。CycloP配体的空间需求对在两个反应中观察到的反应性和选择性都有微妙的影响。在金催化的反应中，对映体的
• Synthesis and structures of [S(H)P(μ-NR)]₂, potential building blocks for inorganic phosphorus–sulfur macrocycles
  作者：Callum G. M. Benson、Vladislav Vasilenko、Raúl García-Rodríguez、Andrew D. Bond、Silvia González Calera、Lutz H. Gade、Dominic S. Wright

  DOI：10.1039/c5dt02069g

  日期：——

  potential new building blocks for inorganic macrocycles of the type [P(μ-NR)}2(μ-S)]n. NMR spectroscopic studies and DFT calculations show that the preference for the cis or trans isomers of III is largely influenced by the steric demands of the R-group, with cis isomers being preferred for bulky substituents. This is an important factor in regard to applications in macrocycle synthesis since the cis

  氯-磷（III）氮杂二聚体[ClP（μ-NR）] 2与LiSH的反应产生了二聚体[S （H）P（μ-NR）] 2（III），这是潜在的新构建基类型[P（μ-NR）} 2（μ-S）] n的无机大环。NMR光谱研究和DFT计算表明，III的顺式或反式异构体的偏好在很大程度上受R-基团的空间需求的影响，顺式异构体是大体积取代基的首选。自从顺式 安排已预先安排好要进行环化。
• Activation of Small Molecules by Phosphorus Biradicaloids
  作者：Alexander Hinz、Rene Kuzora、Uwe Rosenthal、Axel Schulz、Alexander Villinger

  DOI：10.1002/chem.201403964

  日期：2014.11.3

  molecules bearing single, double, and triple bonds. Addition of chalcogens (O2, S8, Sex and Tex) led to the formation of dichalcogen‐bridged P2N2 heterocycles, except from the reaction with molecular oxygen, which gave a P2N2 ring featuring a dicoordinated PIII and a four‐coordinated PV center. In formal [2πe+2πe] addition reactions, small unsaturated compounds such as ethylene, acetylene, acetone,

  双自由基[P（μ-NTer）] 2的反应活性被用来激活带有单键，双键和三键的小分子。硫族元素（O 2，S 8，Se x和Te x）的添加导致了二氢桥联的P 2 N 2杂环的形成，除了与分子氧的反应外，它还形成了一个P 2 N 2配位的P 2 N 2环。III和四坐标P V中央。在正式[2πe+2πe]加成反应，如乙烯，乙炔，丙酮，乙腈，二苯乙炔，苯基碳二和双（三甲基硅烷基）sulfurdiimide小的不饱和化合物被容易地添加到P 2 Ñ 2的biradicaloid的杂环[P（μ ‐NTer）] 2，产生新的杂原子笼状化合物。详细研究了双自由基[P（μ-NTer）] 2的合成，反应和键合，以及所有加成产物的合成，性质和结构特征。
• 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.