1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane | 57322-00-6

• 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: 1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane
• 英文别名: prP4；1,1,4,8,11,11-Hexaphenyl-1,4,8,11-tetraphosphaundecane；2-diphenylphosphanylethyl-[3-[2-diphenylphosphanylethyl(phenyl)phosphanyl]propyl]-phenylphosphane
• CAS: 57322-00-6
• 化学式: C₄₃H₄₄P₄
• 分子量: 684.717
• InChiKey: FBQMUPJLBLHPOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  47
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.16
• 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：

  、 1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane 以 丙酮 为溶剂， 以12%的产率得到[Mo(O)Cl(κ4-(1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane))](B(C6H5)4)
  参考文献：
  名称：

  Exchange of isonitrile ligands in the complex [Mo(O)Cl(CNMe)4]+ by the tetraphos ligand prP4: Stereochemical influences on the reaction course

  摘要：

  Reaction of [Mo(O)Cl(CNMe)(4)](+) with the linear tetraphos ligand meso and rac prP(4) leads to a mixture of [Mo(O)Cl(kappa(4)-meso-prP(4))](+) and [Mo(O) Cl(CNMe)(kappa(3)-rac-prP(4))](+) which are identified by X-ray structural analysis and/or P-31 NMR spectroscopy. In the meso kappa(4)-product both of the phenyl groups of the central phosphorus atoms are oriented towards the oxo ligand whereas in the rac kappa(3)-product one of these phenyl groups is oriented to the oxo and the other to the chloro ligand. The origin of the different coordination modes lies in the different steric demands of the oxo and chloro ligands. The influences of the steric interactions are enhanced by the fact that exchange of the fourth isonitrile is difficult. This hypothesis is supported by the preparation of the complex [Mo(O)Cl(CNMe)(dpepp)]PF6 whose isonitrile ligand is inert towards exchange by monophosphines, even under drastic conditions. (C) 2011 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.02.044
• 作为产物：
  描述：

  2-氯乙基(二苯基)膦 、 1,3-双(二苯基膦)丙烷 在 lithium 作用下， 以 四氢呋喃 为溶剂， 生成 1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane
  参考文献：
  名称：

  具有四磷烷配体的第一个 Chatt 型双（二氮）-钼（0）配合物的立体选择性合成

  摘要：

  第一个具有四磷烷配体的 Chatt 型 MoO 二氮配合物已被制备，并通过 NMR 以及红外和拉曼光谱进行表征。重要的是，所采用的反应路线允许该复合物的立体定向合成为反式-[Mo(N2)2(meso-prP4)]（prP4 = 具有中心丙烯桥的四磷配体）。反应过程中的立体选择性是由氧化碘化钼 (IV) 前体 [Mo(O)I(prP4)]+ 诱导的，该前体将 prP4 的桥连 P 原子的两个苯基团引导成内消旋构型。该论文建立了一种合成单核 MoO 二氮和相关钼配合物与多齿磷烷配体的一般策略，这是迄今为止不可能的。而且，由于两个二膦单元通过烷基桥连接，所得四磷 N2 配合物在合成固氮的 Chatt 循环反应中比传统的双（二磷）配合物表现出更高的热力学稳定性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  DOI：

  10.1002/ejic.200800417

文献信息

• One-step synthesis of Mo(0) and W(0) bis(dinitrogen) complexes with the linear tetraphosphine ligand prP4: stereoselective formation of cis-[M(N2)2(rac-prP4)] and trans-[M(N2)2(meso-prP4)]; M = Mo, W
  作者：René Römer、Christian Gradert、Alexander Bannwarth、Gerhard Peters、Christian Näther、Felix Tuczek

  DOI：10.1039/c0dt01646b

  日期：——

  ethylene bridges and a central propylene bridge). The synthesis starts from MoCl5 and WCl6, respectively, employing Mg as reductant. Whereas the electrochemical reduction of the oxido–iodido–molybdenum(IV) complex [Mo(O)I(meso-prP4]+ (1) only gave trans-[Mo(N2)2(meso-prP4)] (2a; Römer et al., Eur. J. Inorg. Chem.2008, 3258), the direct synthesis under normal conditions affords both trans and cis complexes

  新型Chatt型合成途径 钼（0） 和 W（0）双（二氮）提出了与配体prP 4形成的配合物（prP 4是具有两个乙烯 桥梁和中央 丙烯桥）。综合从氯化钼5 和 WCl 6分别雇用 镁作为还原剂。鉴于电化学还原的氧化物–碘–钼（IV）复合物[Mo（O）I（meso -prP 4 ] +（1）仅给出反式-[Mo（N 2）2（meso -prP 4）]（图2a ;罗梅尔。等人，。。。欧洲药典J.无机化学2008，3258），在正常条件下直接合成，得到两者的反式与顺式络合物图2a和2b中。反应产物通过振动和NMR光谱表征。此外，单晶X射线结构的确定顺式- α - [沫（N 2）2（外消旋-prP 4）]（2b）被执行。与反式相反 双（二氮）钼（0）由内消旋的prP 4配体支持的复合物2a，相应的顺式复合物仅由prP 4的rac异构体协调。还研究了2与酸的反应性，导致NNH 2 复杂的 [ MoF
• Mono- and di-nuclear rhodium complexes of meso- and dl-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane. Stereochemical control of reactivity and complexation geometry
  作者：John M. Brown、Lewis R. Canning

  DOI：10.1016/0022-328x(84)80173-4

  日期：1984.5

  4-pentanedionatorhodium and HBF4 to give the dinuclear rhodium complex (3). This underwent hydrogenation slowly in methanol solution with deposition of rhodium metal and formation of a mononuclear complex (5) with four coordinated phosphorus nuclei, also obtained by independent synthesis. This proved to be highly susceptible to oxidation, forming a dioxygen complex (6) with P(1) and P(3) mutually trans. The lower

  将内消旋-和dl -1,1,4,7,10,10-六苯基-1,4,7,10-四磷烷（200°C，10分钟）热解，然后从乙醇/二氯甲烷中分馏结晶得到两个尖锐的熔融的非对映异构体。在此显示为内消旋异构体的较高熔点的化合物与1，5-环辛二烯-2，4-戊二酮基铑和HBF 4反应，得到双核铑配合物（3）。使其在甲醇溶液中缓慢氢化，并沉积铑金属并形成具有四个配位磷核的单核络合物（5），这也是通过独立合成获得的。事实证明，它极易氧化，形成双氧配合物（6），并且P（1）和P（3）相互trans。较低熔点的dl-异构体在与1，5-环辛二烯-2，4-戊二去离子铑和HBF 4反应时同样形成了双核铑配合物（4）。它与络合物3相比，与氢的反应更快，形成单核二氢化物（7）和金属铑。在环己烯的存在下，形成四配位的次膦酸酯铑配合物（9）。尽管此处P（1）和P（4）是相互反式的，但它与氧反应生成二氧配合物（10），而与一氧化碳反应生成五配位的单羰基（11）。
• The Linear Tetraphos Ligand prP₄ (1,1,4,8,11,11-Hexaphenyl-1,4,8,11-tetraphosphaundecane, Ph₂PCH₂CH₂P(Ph)CH₂CH₂CH₂P(Ph)CH₂CH₂PPh₂):  Synthesis and Characterization of <i>cis</i>- and <i>trans</i>-[Fe(NCS)₂(prP₄)]^†
  作者：Carsten M. Habeck、Christian Hoberg、Gerhard Peters、Christian Näther、Felix Tuczek

  DOI：10.1021/om030579k

  日期：2004.6.1

  The stereochemistry of prP(4) (1,1,4,8, 11, 1 1-hexaphenyl- 1,4,8, 1 1-tetraphosphaundecane) and its coordination properties in mononuclear complexes are explored. The free ligand is obtained as a mixture of meso and rac diastereomers from the reaction of dilithium 1,3-bis(phenylphosphido)propane-tetrakis(tetrahydrofuran) ("Lippp") with 2 equiv of 1-chloro-2(diphenylphosphino)ethane. Reaction of prP(4) with FeCl2 and KSCN leads to cis- and trans[Fe(NCS)(2)(prP(4))] complexes of the meso and the rac ligands; the composition of this mixture has been fully analyzed. The iron isothiocyanato complexes cis-alpha- and trans-[Fe(NCS)(2)(racprP(4))] have been characterized by X-ray structure determinations. The UP NMR spectrum of the free tetraphos ligand shows an AA'XX' coupling scheme with three groups of signals centered at -20.6 and -20.7 ppm and at -12.4 ppm, which belong to the rac and meso isomers, respectively. P-31 NMR spectra of the cis and trans iron isothiocyanato complexes of rac-prP(4) exhibit AA'XX' patterns as well, which can be reproduced by simulation. trans[Fe(NCS)(2)(meso-prP(4))] is identified by its P-31 NMR spectrum, which is similar to that of its rac counterpart. On the basis of NMR spectroscopy it is found that the cis-alpha complex of the rac ligand converts into the trans-rac complex with a half-life of approximately 2 days. Infrared and Raman spectra of the cis-alpha and trans isomers of [Fe(NCS)2(rac-prP4)] reveal characteristic differences in the region of the C-N stretching vibrations.
• Exchange of isonitrile ligands in the complex [Mo(O)Cl(CNMe)4]+ by the tetraphos ligand prP4: Stereochemical influences on the reaction course
  作者：Ludger Söncksen、René Römer、Christian Näther、Gerhard Peters、Felix Tuczek

  DOI：10.1016/j.ica.2011.02.044

  日期：2011.8

  Reaction of [Mo(O)Cl(CNMe)(4)](+) with the linear tetraphos ligand meso and rac prP(4) leads to a mixture of [Mo(O)Cl(kappa(4)-meso-prP(4))](+) and [Mo(O) Cl(CNMe)(kappa(3)-rac-prP(4))](+) which are identified by X-ray structural analysis and/or P-31 NMR spectroscopy. In the meso kappa(4)-product both of the phenyl groups of the central phosphorus atoms are oriented towards the oxo ligand whereas in the rac kappa(3)-product one of these phenyl groups is oriented to the oxo and the other to the chloro ligand. The origin of the different coordination modes lies in the different steric demands of the oxo and chloro ligands. The influences of the steric interactions are enhanced by the fact that exchange of the fourth isonitrile is difficult. This hypothesis is supported by the preparation of the complex [Mo(O)Cl(CNMe)(dpepp)]PF6 whose isonitrile ligand is inert towards exchange by monophosphines, even under drastic conditions. (C) 2011 Elsevier B. V. All rights reserved.
• Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand
  作者：René Römer、Gerald Stephan、Carsten Habeck、Christian Hoberg、Gerhard Peters、Christian Näther、Felix Tuczek

  DOI：10.1002/ejic.200800417

  日期：2008.7

  The first Chatt-type Mo0 dinitrogen complex with a tetraphosphane ligand has been prepared and characterized by NMR as well as infrared and Raman spectroscopy. Importantly, the employed reaction route allows the stereospecific synthesis of this complex as trans-[Mo(N2)2(meso-prP4)] (prP4 = a tetraphos ligand with a central propylene bridge). The stereoselectivity in the reaction course is induced by

  第一个具有四磷烷配体的 Chatt 型 MoO 二氮配合物已被制备，并通过 NMR 以及红外和拉曼光谱进行表征。重要的是，所采用的反应路线允许该复合物的立体定向合成为反式-[Mo(N2)2(meso-prP4)]（prP4 = 具有中心丙烯桥的四磷配体）。反应过程中的立体选择性是由氧化碘化钼 (IV) 前体 [Mo(O)I(prP4)]+ 诱导的，该前体将 prP4 的桥连 P 原子的两个苯基团引导成内消旋构型。该论文建立了一种合成单核 MoO 二氮和相关钼配合物与多齿磷烷配体的一般策略，这是迄今为止不可能的。而且，由于两个二膦单元通过烷基桥连接，所得四磷 N2 配合物在合成固氮的 Chatt 循环反应中比传统的双（二磷）配合物表现出更高的热力学稳定性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)