5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinomethoxy)calix<4>arene | 178152-74-4

• 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: 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinomethoxy)calix<4>arene
• 英文别名: 5,11,17,23-tetra-tert-butyl-25,27-bis(ethoxycarbonylmethoxy)-26,28-bis(diphenylphosphinomethoxy)calix[4]arene；5,11,17,23-tetra-tert-butyl-25,27-bis(diphenylphosphinomethoxy)-26,28-diethoxycarbonylmethoxycalix[4]arene；5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinomethoxy)calix[4]arene；ethyl 2-[[5,11,17,23-tetratert-butyl-26,28-bis(diphenylphosphanylmethoxy)-27-(2-ethoxy-2-oxoethoxy)-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaenyl]oxy]acetate
• CAS: 178152-74-4；158780-09-7
• 化学式: C₇₈H₉₀O₈P₂
• 分子量: 1217.52
• InChiKey: RGUAYKKXURFQSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.38
• 重原子数：
  88.0
• 可旋转键数：
  18.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  89.52
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  trans-chlorohydridobis(triphenylphosphine)platinum(II) 、 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinomethoxy)calix<4>arene 以 二氯甲烷 为溶剂， 以71%的产率得到trans-P,P'-chlorohydrido[5,11,17,23-tetra-tert-butyl-25,27-bis(ethoxycarbonylmethoxy)-26,28-bis(diphenylphosphinomethoxy)calix[4]arene]platinum(II)
  参考文献：
  名称：

  Capping calixarenes with metallodiphosphine fragments: towards intracavity reactions

  摘要：

  四种二取代的5,11,17,23-四-tert-丁基-25,27-二-RCH₂ O-26,28-双(二苯基膦甲氧基)卡立克[4]芳烃的配位性质进行了研究。[R = C(O)NEt₂ L₁, C(O)OEt L₂, (R)-C(O)NHCH(Me)Ph L₃ 或 CH₂ OMe L₄]化合物L₁与[Au(thf)(SC₄H₈)]BF₄（thf = 四氢呋喃，SC₄H₈ = 四氢硫代烯）和AgBF₄反应，分别生成螯合物[AuL₁]BF₄ ₁和[AgL₁]BF₄ ₂。L₁与trans-[PtH(Cl)(PPh₃)₂]反应成功生成trans-[PtH(Cl)L₁] ₃，其中铂氢键部分被包裹在卡立克芳烃腔内。结构相关的阳离子络合物[PtH(PPh₃)Lᵢ]BF₄（Lᵢ = L₁₄, L₃₅ 或 L₄₆）通过将trans-[PtH(thf)(PPh₃)₂]BF₄与二膦Lᵢ处理，以高产率得到，PPh₃配体与氢负离子配体呈反式排列。用AgBF₄从3中引出氯离子，得到复合物[PtH(L₁)]BF₄ ₇，其中卡立克芳烃作为三齿P₂O酰胺配体，而金属平面位于卡立克芳烃隧道的一端。与PPh₃反应导致配位酰胺的替换生成4，而与4,4'-联吡啶反应则得到了双核络合物[(L₁)HPt(4,4'-bipy)PtH(L₁)][BF₄]₂₈。trans-[PtH(Cl)(PPh₃)₂]与Lᵢ反应生成通式为[PtH(PPh₃)Lᵢ]Cl（类型A）和[PtH(Cl)Lᵢ]（类型B）的复合物混合物。A:B的比例取决于R基团的配位能力，因为这些基团作为内溶剂分子促进了PPh₃的替代。对于含有强供体的R基团，例如L₁和L₂，型B的络合物被优先生成；而与L₄反应则选择性地导致[PtH(PPh₃)L₄]Cl型络合物的生成，不形成B型络合物。在至少一种情况下（L₃），显示出类型A的络合物可以转化为B型络合物。与二甲基乙炔二羧酸酯的反应产生了插入产物trans-P,P′-[Pt(MeO₂CCCHCO₂Me)L₁]BF₄，其中两个酰胺争夺配位。复合物7与四氰乙烯（tcne）瞬时反应生成铂(0)络合物[Pt(tcne)L₁]，其NMR光谱表明酰胺之间的配位平面快速翻转。与[Pt(MeO₂CCCHCO₂Me)L₁]BF₄相比，铜羰基络合物[Rh(CO)Lᵢ]BF₄（Lᵢ = L₁ 或 L₃）中强三齿P₂O配位普遍存在，其是由[Rh(CO)₂(thf)₂]BF₄与相应的二膦反应所得。

  DOI：

  10.1039/a701954h
• 作为产物：
  描述：

  5,11,17,23-tetra-tert-butyl-25,27-di(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene 在 苯硅烷 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 109.0h， 生成 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinomethoxy)calix<4>arene
  参考文献：
  名称：

  Multifunctional phosphane and phosphane oxide ligands derived from p-tert-butylcalix[4]arene. Synthesis of a large diphosphane with C2 symmetry and behaving as a cis or trans binding ligand

  摘要：

  The calix[4]arene derived di(phosphane oxide) 2 (cone conformation) was obtained in 78% yield by treatment of 1 with 2 equiv NaO(t)Bu followed by reaction with 2 equiv Ph2P(O)CH2OTs. When KO(t)Bu was used instead of NaO(t)Bu, the partial cone isomer 2' was formed. Reaction of 2 with PhSiH3 in refluxing toluene afforded quantitatively the mixed di(ester)-di(phosphane) ligand 3; crystal data of 3: monoclinic, C21c; a = 24.091(7), b = 14.416(4), c = 25.270(8) angstrom, beta = 128.07(2)-degrees, V = 6909.1(5) angstrom3, Z = 4 and R(F) = 5.8%. The molecule which lies on a C2 axis adopts a distorted cone conformation; the angle formed between the ester substituted phenolic rings is 10.5(2)-degrees and that between the phosphane substituted rings is 95.0(1)-degrees. The phosphorus lone pairs point towards the exterior of the space defined by the four calixarene substituents, whereas the two ester groups are directed to the interior of this cavity. Ligand 3 reacts with [PtCl2(PhCN)2] in THF to yield cis-PtCl2 . 3 (4) in 91% yield. The sequential reaction of [RhCl(1,5-cyclooctadiene)]2 with 2 equiv AgBF4 and 2 equiv 3 gave the cationic complex cis-[Rh(1,5-cyclooctadiene) . 3](BF4) (5). Reaction of carbon monoxide with commercial RuCl3 in boiling 2-ethoxyethanol and subsequent addition of 3 gave cis-cis-trans-P,P-[RuCl2(CO)2 . 3] (6). Complexes 4-6 display fluxional behaviour in solution. All compounds were characterized by elemental analysis and IR and H-1, P-31, and C-13 NMR spectroscopy.

  DOI：

  10.1016/0022-328x(94)84035-0

文献信息

• Preparation, luminescence and interactions with Li+, Na+ and U022+ of two new metallocalix[4]arene complexes of iridium(I)
  作者：Jonathan Gagnon、Cyrille Loeber、Dominique Matt、Pierre D. Harvey

  DOI：10.1016/0020-1693(95)04858-8

  日期：1996.2

  Abstract Two new complexes of Ir(I) using diphosphine and diphosphinite calix[4]arene ligands have been prepared and characterized. The luminescent lowest energy excited MLCT state (metal-to-ligand charge transfer) has been addressed theoretically by extended Huckel molecular orbital calculations (EHMO), and a Franck-Condon analysis on the absorption spectra using the time dependent Heller's theory

  摘要制备并表征了使用二膦和二亚膦酸杯杯[4]芳烃配体制备的Ir（I）的两种新型配合物。理论上已经通过扩展的Huckel分子轨道计算（EHMO）解决了发光最低能量激发的MLCT状态（金属到配体的电荷转移），并使用时变的Heller理论对吸收光谱进行了Franck-Condon分析。 。通过添加底物（U0 2 2+，Li +，Na +），研究了两种络合物在77 K乙醇中对re的扰动。随添加底物而变化的幅度随U0 2 2+> Li +> Na +的变化而变化。