Tribenzhydryloxy(phenyl)silane | 1536256-47-9

• 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: Tribenzhydryloxy(phenyl)silane
• CAS: 1536256-47-9
• 化学式: C₄₅H₃₈O₃Si
• 分子量: 654.88
• InChiKey: FFAOJGDYXBQTIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.25
• 重原子数：
  49
• 可旋转键数：
  13
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  二苯甲酮 、 苯硅烷 在 [[(tris[2(dimethylamino)ethyl]-amine)ZnH][B{C₆H₃(CF₃)₂}₄]] 作用下， 以 氘代乙腈 为溶剂， 反应 6.0h， 生成 Tribenzhydryloxy(phenyl)silane
  参考文献：
  名称：

  末端氢氧化锌†

  摘要：

  现已分离出热稳定的末端氢氧化锌阳离子。通过将二氧化碳，碳二亚胺和二苯甲酮以便捷的方式插入Zn–H键中，可以证明氢化物配体的亲核性。使用PhSiH 3进行的催化氢化硅烷化的初步研究表明，在BPh 3存在下，氢化锌阳离子可以选择性地将CO 2还原为PhSi（OCHO）3。

  DOI：

  10.1039/c8cc09839e

文献信息

• A Pentacoordinate Mn(II) Precatalyst That Exhibits Notable Aldehyde and Ketone Hydrosilylation Turnover Frequencies
  作者：Chandrani Ghosh、Tufan K. Mukhopadhyay、Marco Flores、Thomas L. Groy、Ryan J. Trovitch

  DOI：10.1021/acs.inorgchem.5b01825

  日期：2015.11.2

  found to possess an intermediate-spin (S = 3/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ5-N,N,N,N,N-PyEtPDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min–1 when employed under solvent-free conditions. This optimization allowed for isolation

  在吡啶取代的双（亚氨基）吡啶配体PyEt PDI存在下加热（THF）2 MnCl 2，制备相应的二卤化物配合物（PyEt PDI）MnCl 2。使用过量的Na / Hg的这种前体的还原导致螯合物甲基基团的脱质子化，得到双（烯酰胺）三（吡啶） -支持的产品，（κ 5 - Ñ，Ñ，Ñ，Ñ，ñ - PyEt PDEA）的Mn 。该配合物通过单晶X射线衍射表征，发现具有中间自旋（S = 3 /2）通过Evans方法和电子顺磁共振波谱法测定Mn（II）中心。此外，（κ 5 - Ñ，Ñ，Ñ，Ñ，ñ - PyEt PDEA）Mn为确定为醛和酮的氢化硅烷化的有效预催化剂，表现出向上的周转频率2475分钟-1时溶剂下使用免费条件。这种优化可以分离出相应的醇，在两种情况下，还可以分离出部分反应的甲硅烷基醚PhSiH（OR）2 [R = Cy和CH（Me）（n Bu）]。对于（κ观察到的醛氢化硅烷化活性5 - ñ，N，N，N，N
• Robust Two-Coordinate Zn(II) Organocations Supported by Bulky-Yet-Flexible IPr* Carbene: Synthesis, Structure, and Distinct Reactivity in Hydrosilylation Catalysis
  作者：Xuejuan Xu、Christophe Gourlaouen、Béatrice Jacques、Samuel Dagorne

  DOI：10.1021/acs.organomet.3c00282

  日期：2023.10.9

  [IPr*-ZnR]+ series are less Lewis acidic than their [IPr-ZnR]+, yet they display a distinct reactivity in hydrosilylation catalysis. Thus, cation [6]+ catalyzes at room-temperature styrene and alkyne hydrosilylation with HSiEt3 as the silane source. Remarkably, it is also a highly effective ketone/aldehyde hydrosilylation catalysis for a rather broad silane and ketone scope and performs much better than

  本研究详细介绍了 [IPr*-Zn-R] + (IPr* = 1,3-双[2,6-双(二苯基甲基)-4-]类型的新型 Zn(II) 基有机阳离子的合成和表征[甲基苯基]-1,3-二氢-2H-咪唑-2-亚基；R=烷基、芳基）及其在苯乙烯、炔烃和羰基硅氢加成催化中的应用。通过IPr*与等摩尔量的ZnR 2反应制备中性IPr*加合物[IPr*-ZnR 2 ] ( 1 , R = Me; 2 , R = Et; 3 , R = Ph)并在良好的条件下分离。产量。尽管 IPr* 存在严重的空间位阻，但化合物1 – 3在溶液中具有鲁棒性，反映了卡宾 IPr* 体积大但灵活的性质。加合物1和2可以很容易地被 [Ph 3 C][B(C 6 F 5 ) 4 ] 电离，产生双配位 Zn(II) 阳离子 [IPr*-ZnMe] + ([ 4 ] + ) 和 [IPr *-ZnEt] + ([ 5 ] + )，两者均以
• A Highly Active Manganese Precatalyst for the Hydrosilylation of Ketones and Esters
  作者：Tufan K. Mukhopadhyay、Marco Flores、Thomas L. Groy、Ryan J. Trovitch

  DOI：10.1021/ja4116346

  日期：2014.1.22

  The reduction of ((PDI)-P-Ph2PPr)MnCl2 allowed the preparation of the formally zerovalent complex, ((PDI)-P-Ph2PPr)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h(-1) in the absence of solvent. Loadings as low as 0.01 mol % were employed, and ((PDI)-P-Ph2PPr)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. ((PDI)-P-Ph2PPr)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of ((PDI)-P-Ph2PPr)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.
• Hydrosilylation of Aldehydes and Ketones Catalyzed by a Terminal Zinc Hydride Complex, [κ³-Tptm]ZnH
  作者：Wesley Sattler、Serge Ruccolo、Mahnaz Rostami Chaijan、Tawfiq Nasr Allah、Gerard Parkin

  DOI：10.1021/acs.organomet.5b00506

  日期：2015.10.12

  Tris(2-pyridylthio)methyl zinc hydride, [kappa(3)-Tptm]ZnH, is an effective catalyst for multiple insertions of carbonyl groups into the Si-H bonds of PhxSiH4-x (x = 1, 2). Specifically, [kappa(3)-Tptm]ZnH catalyzes the insertion of a variety of aldehydes and ketones into the Si-H bonds of PhSiH3 and Ph2SiH2 to afford PhSi[OCH(R)R'](3) and Ph,Si[OCH(R)R'](2), respectively. The mechanism for hydrosilylation is proposed to involve insertion of the carbonyl group into the Zn-H bond to afford an alkoxy species, followed by metathesis with the silane to release the alkoxysilane and regenerate the zinc hydride catalyst. Multiple insertion of prochiral ketones results in the formation of diastereomeric mixtures of alkoxysilanes that can be identified by NMR spectroscopy.