lithium 2,4,6-tris(tert-butyl)phenylphosphide | 83115-13-3

• 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: lithium 2,4,6-tris(tert-butyl)phenylphosphide
• 英文别名: lithium 2,4,6-tri-tert-butylphenylphosphide；lithium (2,4,6-tri-t-butylphenyl)phosphide；(2,4,6-tri-t-butylphenyl)lithiophosphide；lithium 2,4,6-tri-t-butylphenylphosphide；lithium;(2,4,6-tritert-butylphenyl)phosphanide
• CAS: 83115-13-3
• 化学式: C₁₈H₃₀LiP
• 分子量: 284.351
• InChiKey: YXLMDALBFKINQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.35
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium 2,4,6-tris(tert-butyl)phenylphosphide 以 四氢呋喃 为溶剂， 生成 P-(2,4,6-tri-tert-butylphenyl)-Si,Si-bis(2,4,6-trimethylphenyl)phosphasilene
  参考文献：
  名称：

  Smit, C. N.; Bickelhaupt, F., Phosphorus and Sulfur and the Related Elements, 1987, vol. 30, p. 357 - 360

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4,6-tri-t-butylphenylphosphonous dichloride 在 lithium aluminium tetrahydride 、 正丁基锂 作用下， 以 乙醚 为溶剂， 生成 lithium 2,4,6-tris(tert-butyl)phenylphosphide
  参考文献：
  名称：

  Diphosphenes (RP:PR). Synthesis and NMR characterization

  摘要：

  DOI：

  10.1021/ja00385a060

文献信息

• Reactions of (THF) W(CO)5 with some diphosphenes carrying bulky aryl and phenoxy groups
  作者：De-Lie An、Kozo Toyota、Masafumi Yasunami、Masaaki Yoshifuji

  DOI：10.1016/0022-328x(95)05843-e

  日期：1996.2

  The reaction of (THF)W(CO)5 (THF = tetrahydrofuran) with asymmetrical diphosphenes carrying bulky aryl and phenoxy groups gave end-on-type complexes on either phosphorus atom. One of the complexes was analyzed by X-ray crystallography indicating that the major complex suffers less from the steric bulk.

  （THF）W（CO）5（THF =四氢呋喃）与带有庞大芳基和苯氧基的不对称二膦的反应在任一磷原子上均产生端基型配合物。通过X射线晶体学分析了一种配合物，表明主要配合物受空间体积的影响较小。
• Synthese, Koordinationschemie und Ligandeneigenschaften sekundärer Phosphane R(Ar*)PH mit sperrigen aromatischen Resten - Molekülstruktur von Ph(2,4,6-iPr₃C₆H₂)PH, (2,4,6-iPr₃C₆H₂)₂PH und ClAu[PhP(2,4,6-Bu₃C₆H₂)H] / Synthesis, Coordination Chemistry and Ligand Properties of Secondary Phosphines R(Ar*)PH with Bulky Aromatic Substituents - Molecular Structure of Ph(2,4,6-iPr₃C₆H₂)PH, (2,4,6-iPr₃C₆H₂)₂PH and ClAu[PhP(2,4,6-tBu₃C₆H₂)H]
  作者：David J. Brauer、Frank Bitterer、Frank Dörrenbach、Gisbert Heßler、Othmar Stelzer、Carl Krüger、Frank Lutz

  DOI：10.1515/znb-1996-0819

  日期：1996.8.1

  The secondary phosphines R(Ar*)PH(R = Me, iPr, Ph, Mes, Ar*) (2a-2h) with bulky aromatic substituents Ar* (Ar* = 2,3,6-R′ ₃C₆H₂, R′ = iPr, tBu) are obtained in good yields by reaction of RPCl₂, PCl₃, PBr₃ or Ar*P(Cl, Br)₂ with 2,4,6-tBu₃C₆H₂Li or 2,4,6- iPr₃C₆H₂MgBr and subsequent reduction of the intermediate halophosphines R(Ar*)PX(X = Cl, Br) with LiAlH₄. The X-ray structural analysis of Ph(2,4,6-iPr₃C₆H₂)PH (2g), space group P₁, shows P-C-distances of 1.824(1) and 1.838(1)Å. The lithium derivatives of 2a-2c are monomeric in solution as indicated by the 1 :1 :1 : 1-quartet ⁷L i - ³¹P fine structure of the ³¹P 1H} NMR signals at low temperatures. 2a-2c and 2f-2h form Ni(0) and Fe(0) complexes (CO)₃NiL (6a-6f) and Fe(CO)₄L (7a-7d), respectively. The Tolman electronic parameters of the bulky ligands are almost identical. Within the series 2a-2h the spatial shielding of the P atoms has been estimated using advanced molecular modeling techniques. The bulky ligand 2c forms coinage metal complexes [C u(CH₃CN)₂(2c)₂] [PF₆] (8), Cu₂Cl₂(2c)₂ (9) and Cl-Au(2c) (10). While 10 is monomeric in solution, in the solid state it forms pairs of head to tail oriented monomers with almost linear Cl - Au - P skeletons (Cl - Au - P 175.47(9)°) as shown by an X-ray structural analysis.

  次磷膦R（Ar*）PH（R = Me, iPr, Ph, Mes, Ar*）（2a-2h），其中Ar*为大体积芳香基团（Ar* = 2,3,6-R′3C6H2，R′ = iPr，tBu），通过RPCl2、PCl3、PBr3或Ar*P（Cl，Br）2与2,4,6-tBu3C6H2Li或2,4,6-iPr3C6H2MgBr的反应，并通过还原中间卤代磷膦R（Ar*）PX（X = Cl，Br）与LiAlH4得到高产率。苯基（2,4,6-iPr3C6H2）PH（2g）的X射线结构分析，空间群P1，显示P-C距离为1.824(1)和1.838(1)Å。2a-2c的锂衍生物在溶液中是单体的，如低温下1:1:1:1四重态7Li-31P精细结构的31P 1H} NMR信号所示。2a-2c和2f-2h形成Ni(0)和Fe(0)配合物（CO）3NiL（6a-6f）和Fe（CO）4L（7a-7d），差不多具有相同的Tolman电子参数。在系列2a-2h中，利用先进的分子建模技术估计了P原子的空间屏蔽效应。大体积配体2c形成了铜配合物[Cu(CH3CN)2(2c)2][PF6]（8）、Cu2Cl2(2c)2（9）和Cl-Au(2c)（10）。虽然10在溶液中是单体的，但在固态中形成了头对尾定向单体的成对结构，具有几乎线性的Cl - Au - P骨架（Cl - Au - P 175.47(9)°），如X射线结构分析所示。
• Development of a new sterically protecting auxiliary of the metacyclophane type and application to unsymmetrical diphosphene, 1,3-diphosphaallene, and 1,4-diphosphabutatrieneElectronic supplementary information (ESI) available: Physical data. See http://www.rsc.org/suppdata/cc/b2/b209666h/
  作者：Kozo Toyota、Akitake Nakamura、Masaaki Yoshifuji

  DOI：10.1039/b209666h

  日期：2002.11.29

  A new bulky bromobenzene of the metacyclophane type was converted to an unsymmetrically substituted 1,4-diphos-phabutatriene whose spin-spin coupling constant (3Jpp) turned out to be larger, for the first time, than the 2Jpp value of the corresponding 1,3-diphosphaallene.

  一种新的间环烷型大体积溴苯被转化为不对称取代的1,4-二磷-苯丁三烯，其自旋-自旋耦合常数（3Jpp）首次大于相应的1的2Jpp值， 3-二磷杂戊烯。
• Synthesis, structure, and reactivity of platinum compounds featuring terminal amido and phosphido ligands
  作者：Rory Waterman、Daniel J. Mindiola、Christopher R. Clough、Gregory L. Hillhouse

  DOI：10.1016/j.ica.2014.07.038

  日期：2014.10

  dmp = 2,6-dimesitylphenyl, Mes∗ = 2,4,6-tri-tert-butylphenyl). Both families of compounds resist attempts to deprotonate the amido or phosphido ligand with either external bases or through alkane or arene elimination. Compound 11 reacts with various acids to afford salts having the cation [(dtbpe)PtMe(PH2Mes∗)]+ [12]+. Compounds 6, 9·0.5Et2O, 10·Et2O, 11·Et2O, and the salt [12][BArf4] were structurally

  摘要使用空间受限的1,2-双（二叔丁基膦基）乙烷（dtbpe）配体，形成了一般形式（dtbpe）PtX（NHAr）的末端苯胺基化合物家族（X = Cl，2; Me，6 ;（Ph，7; Ar = 2,6-二异丙基苯基）以及（dtbpe）Pt（NHPh）2（8）是通过使用（dtbpe）PtCl2进行盐复分解以高分离产率制备的。同样，制备了新的立体式末端磷酸酯化合物，其通式为（dtbpe）PtX（PHAr）（X / Ar = Cl / dmp，9; Cl / Mes ∗，10; Me / Mes ∗，11;其中dmp = 2 ，6-二甲苯基苯基，Mes ＝ 2,4,6-三叔丁基苯基）。这两类化合物都可以抵抗用外部碱基或通过烷烃或芳烃消除使酰胺或磷配体去质子化的尝试。化合物11与各种酸反应，得到具有阳离子[（dtbpe）PtMe（PH2Mes ∗）] + [12] +的盐。化合物6、9·0.5Et2O，10·Et2O，
• Preparations and Sulfurization Reactions of (2,4-Di-<i>t</i>-butyl-6-methoxyphenyl)phosphine and 1-(2,4-Di-<i>t</i>-butyl-6-methoxyphenyl)-2-(2,4,6-tri-<i>t</i>-butylphenyl)diphosphene
  作者：Masaaki Yoshifuji、De-Lie An、Kozo Toyota、Masafumi Yasunami

  DOI：10.1246/cl.1993.2069

  日期：1993.12

  A phosphonous dichloride carrying 2,4-di-t-butyl-6-methoxyphenyl as a novel sterically protecting group was prepared and converted to an unsymmetrical diphosphene, which reacted with sulfur to give the corresponding diphosphene sulfide and thiadiphosphirane. The phosphonous dichloride was reduced to the corresponding primary phosphine, which was sulfurized to a dithioxophosphorane. The dithioxophosphorane reacted with benzophenone to give thiobenzophenone.

  制备了一种含有 2,4-二叔丁基-6-甲氧基苯基作为新型立体保护基团的二氯化膦，并将其转化为非对称的二磷蒽，该二磷蒽与硫反应生成相应的硫化二磷蒽和硫代二膦环。二氯化膦被还原成相应的伯膦，伯膦又被硫化成二硫代磷烷。二硫代磷烷与二苯甲酮反应生成硫代二苯甲酮。