(1,3,5,7,9,11,14-Heptacyclopentyl-7,14-dihydroxy-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.3.3.15,11]hexadecan-3-yl)oxy-methyl-diphenylsilane | 634203-31-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1,3,5,7,9,11,14-Heptacyclopentyl-7,14-dihydroxy-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.3.3.15,11]hexadecan-3-yl)oxy-methyl-diphenylsilane
• CAS: 634203-31-9
• 化学式: C₄₈H₇₈O₁₂Si₈
• 分子量: 1071.82
• InChiKey: JIQOZGYBHJUNLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.75
• 重原子数：
  68
• 可旋转键数：
  11
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  133
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (1,3,5,7,9,11,14-Heptacyclopentyl-7,14-dihydroxy-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.3.3.15,11]hexadecan-3-yl)oxy-methyl-diphenylsilane 在 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (7-Chloro-1,3,5,9,11,13,15-heptacyclopentyl-2,4,6,8,10,12,14,16,17,18,19-undecaoxa-7-phospha-1,3,5,9,11,13,15-heptasilatetracyclo[9.5.1.13,9.15,15]nonadecan-13-yl)oxy-methyl-diphenylsilane
  参考文献：
  名称：

  POSSphites—monophosphites derived from incompletely condensed silsesquioxanes

  摘要：

  A straightforward three-step synthetic route is followed to obtain nanostructured silsesquioxane based monophosphite compounds 1-3. which we named POSSphites. These compounds. derived from (c-C5H9)(7)Si7O9(OH)(3) and commercially available phenol derivatives. differ mainly in the steric bulk around the phosphorus atom. Preliminary results in the rhodium-catalyzed hydroformylation of 1-octene exemplify the use of these ligands for homogeneous catalysis. High activities, with a turnover frequency of up to 5000 h(-1) were obtained. Ligands 1-3 are the first silsesquioxane derived monophosphite ligands to be successfully applied in homogeneous catalysis. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.09.064
• 作为产物：
  描述：

  甲基二苯基氯硅烷 、 1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane-endo-3,7,14-triol 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (1,3,5,7,9,11,14-Heptacyclopentyl-7,14-dihydroxy-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.3.3.15,11]hexadecan-3-yl)oxy-methyl-diphenylsilane
  参考文献：
  名称：

  POSSphites—monophosphites derived from incompletely condensed silsesquioxanes

  摘要：

  A straightforward three-step synthetic route is followed to obtain nanostructured silsesquioxane based monophosphite compounds 1-3. which we named POSSphites. These compounds. derived from (c-C5H9)(7)Si7O9(OH)(3) and commercially available phenol derivatives. differ mainly in the steric bulk around the phosphorus atom. Preliminary results in the rhodium-catalyzed hydroformylation of 1-octene exemplify the use of these ligands for homogeneous catalysis. High activities, with a turnover frequency of up to 5000 h(-1) were obtained. Ligands 1-3 are the first silsesquioxane derived monophosphite ligands to be successfully applied in homogeneous catalysis. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.09.064

文献信息

• Versatile Phosphite Ligands Based on Silsesquioxane Backbones
  作者：Jarl Ivar van der Vlugt、Jens Ackerstaff、Tessa W. Dijkstra、Allison M. Mills、Huub Kooijman、Anthony L. Spek、Auke Meetsma、Hendrikus C. L. Abbenhuis、Dieter Vogt

  DOI：10.1002/adsc.200303186

  日期：2004.3

  molecular structures for the complexes trans-[PdCl2(3)] (5), cis-[Mo(CO)4(3)] (6) and the dinuclear complex [Rh(μ-Cl)(CO)}2(κ2-3)] (7) have been determined. In the rhodium-catalyzed hydroformylation of 1-octene high activities, with turnover frequencies of up to 6800 h−1, are obtained with these new nanosized phosphorus ligands.

  倍半硅氧烷用作配体骨架，用于合成具有3,3'-5,5'-四（叔丁基）-2,2'-dioxa-1,1'-联苯取代基的新型亚磷酸酯化合物。亚磷酸酯和二齿亚磷酸酯均以高收率制备。两种倍半硅氧烷被用作起始原料。单亚膦酸酯1和单亚磷酸酯2由衍生自完全缩合的倍半硅氧烷骨架（c -C 5 H 9）7 Si 7 O 12 SiOT1的倍半氧化oxide制得。二亚磷酸酯3合成与不完全冷凝的单甲硅烷二硅烷醇开始（c -C 5 H 9）7 Si 7 O 9（OSiMePh 2）（OH）2。对于单亚磷酸酯2，相应的反式-[PtCl 2（2）]络合物4通过NMR光谱以及X射线晶体学进行表征，这是完全缩合的羰基官能化倍半硅氧烷骨架的第一个实例。二齿配体3的配位通过NMR光谱以及X射线晶体学研究了Pd，Mo和Rh的含量。各种协调模式都被证明是可能的。用于复合物中的分子结构的反式- [的PdCl 2（3）]（5），顺式-
• Methyl Aluminosilsesquioxanes, Models for Lewis Acidic Silica-Grafted Methyl Aluminum Species
  作者：Maria D. Skowronska-Ptasinska、Robbert Duchateau、Rutger A. van Santen、Glenn P. A. Yap

  DOI：10.1021/om0102596

  日期：2001.8.1

  conversion of 3a into 3c was not observed. Complex 4 slowly isomerizes into 3c, which consecutively isomerizes into the thermodynamic most stable isomeric mixture (1000 h at 76 °C, Ea = 117 kJ·mol-1). Treating Cp2ZrMe2 with the Brønsted acid III gave clean transfer of a silsesquioxane ligand to zirconium, yielding [(c-C5H9)7Si7O11(OSiMePh2)]ZrCp2 (5). The methyl aluminosilsesquioxanes 1a and 2−4 are not

  研究了羟基倍半硅氧烷（c -C 5 H 9）7 Si 8 O 12（OH）（I）和（c -C 5 H 9）7 Si 7 O 9（OH）2 OSiMePh 2（II）用于二氧化硅接枝的烷基铝。用I处理AlMe 3得到聚合的[（c -C 5 H 9）7 Si 8 O 13] AlMe 2 } n（1a），它很容易转变成相应的单体吡啶加合物[（c -C 5 H 9）7 Si 8 O 13 ] AlMe 2 ·Py（1b）。当AlMe 3与II反应时，显着量的2：1产物[（c -C 5 H 9）7 Si 7 O 11（OSiMePh 2）]（AlMe 2）2 } 2（2）和布朗斯台德酸性的1：2产物[（ç -C 5 ħ 9）7的Si 7 ø 11（OSiMePh 2）] 2的Al - } H + }（III获得）除了反应的主要产物，[（c -C 5 H 9）7 Si 7 O 11（OSiMePh
• Silsesquioxane Models for Geminal Silica Surface Silanol Sites. A Spectroscopic Investigation of Different Types of Silanols
  作者：Tessa W. Dijkstra、Robbert Duchateau、Rutger A. van Santen、Auke Meetsma、Glenn P. A. Yap

  DOI：10.1021/ja0122243

  日期：2002.8.1

  and FT-IR studies show that the two silanols of the geminal silsesquioxanes 4-6 are different from each other with respect to hydrogen bonding, both in solution and in the solid state. Hydrogen bonding of the geminal silanol-containing silsesquioxanes was examined and compared to hydrogen bonding in silsesquioxanes possessing vicinal or isolated silanol groups. The relative Brønsted acidity of the geminal

  不完全缩合的单硅烷化倍半硅氧烷 (c-C5H9)7Si7O9(OSiRR'2)(OH)2 (SiRR'2 = SiMe3, SiMe2C(H)CH2, SiMePh2) 在胺存在下与 SiCl(4) 反应，得到二氯化合物 (c-C5H9)7Si7O9(OSiRR'2)O2SiCl2 (1-3)。这些化合物可以水解成相应的含有孪生硅烷醇的倍半硅氧烷，(c-C5H9)7Si7O9(OSiRR'2)O2Si(OH)2 (4-6)。在升高的温度下，孪生倍半硅氧烷 4 和 5 发生缩合反应并形成封闭笼型倍半硅氧烷单硅烷醇 (c-C5H9)7Si8O12(OH)。空间位阻更大的孪生倍半硅氧烷 6 在溶液中发生分子间脱羟基，产生热力学稳定的二聚二硅烷醇，[(c-C5H9)7Si7O9(OSiMePh2)(O2Si(OH)-)]2-(mu-O) (7)。NMR 和 FT-IR 研究表明，在溶液和固态中，孪生倍半硅氧烷
• Steric Factors Affecting the Brønsted Acidity of Aluminosilsesquioxanes
  作者：Maria D. Skowronska-Ptasinska、Robbert Duchateau、Rutger A. van Santen、Glenn P. A. Yap

  DOI：10.1002/1099-0682(20011)2001:1<133::aid-ejic133>3.0.co;2-u

  日期：2001.1

  Hydrogen bonding between the acidic SiO(H)-->Al proton and the pendant silyl ether function is effectively reduced by increasing the steric bulk of the silyl ether substituents, resulting in a higher acidity for 1b compared to that of 1a. With the silsesquioxane ligand (c-C5H9)(8)Si8O11 (OH)(2), which lacks pendant silyl ether functions, the acidic proton cannot satisfactorily be stabilized and this renders

  通过使 AlMe3 与两当量的 (c-C5H9)(7)Si7O9(OH)(2)OSiR3 反应，相应的布朗斯台德酸性铝硅倍半氧烷 [(c-C5H9)(7)Si7O11(OSiR3)]Al[(c-C5H9) (7)Si7O10(OH)OSiR3] [SiR3 = SiMe3 (1a), SiMePh2 (1b)]。这些配合物很容易与三乙胺反应生成相应的铵盐 [(c-C5H9)(7)Si7O11(OSiR3)](2)Al}(-)(HNEt3)(+) (2a,b)。通过增加甲硅烷基醚取代基的空间体积，酸性 SiO(H)-->Al 质子和侧基甲硅烷基醚官能团之间的氢键有效地减少，导致 1b 与 1a 相比具有更高的酸度。使用缺乏侧基甲硅烷基醚功能的倍半硅氧烷配体 (c-C5H9)(8)Si8O11 (OH)(2)，酸质子不能令人满意地稳定，这使得假定的布朗斯台德酸 [(c-C5H9)(8)Si8
• Gerritsen, Gijsbert; Duchateau, Robbert; Santen, Rutger A. van, Organometallics, 2003, vol. 22, p. 100 - 110
  作者：Gerritsen, Gijsbert、Duchateau, Robbert、Santen, Rutger A. van、Yap, Glenn P. A.

  DOI：——

  日期：——