bis(tolyl-3)silane | 70111-01-2

• 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: bis(tolyl-3)silane
• 英文别名: Bis(3-methylphenyl)silane；bis(3-methylphenyl)silane
• CAS: 70111-01-2
• 化学式: C₁₄H₁₆Si
• 分子量: 212.367
• InChiKey: FPBAHVJHTGZVOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.42
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  [Rh(SC6H4OMe-p)(PMe3)3] 、 bis(tolyl-3)silane 以53%的产率得到RhH(SiH(C6H4-m-Me)2)(SC6H4-p-OMe)(PMe3)3
  参考文献：
  名称：

  Preparation and structures of hydrido (organosilyl) arenethiolatorhodium(III) complexes with PMe3 ligands. Irreversible and reversible oxidative addition of an SiH bond to thiolatorhodium (I) complexes

  摘要：

  Thiolatorhodium(I) complexes, Rh(SAr)L-3 (Ar=Ph (1), C6H4-p-Me (2), C6H4-p-OMe (3); L = PMe3), react with HSi(OMe)(3) and with HSiCl3 to give hydrido(silyl)arenethiolatorhodium(III) complexes, RhH(SiX3)(SAr)L-3 (X=OMe, Cl). Crystallographic results of RhH[Si(OMe)(3)](SPh)L-3 as well as NMR spectra of the complexes show octahedral coordination around the Rh center with thiolato and silyl ligands at mutually trans positions and three PMe3 ligands at meridional coordination sites. Hydride(triphenylsilyl)arenethiolatorhodium(III) complexes, RhH(SiPh3)(SAr)L-3 (Ar=Ph, C6H4-p-Me), are obtained from reaction of Rh(SAr)L-3 with excess HSiPh3. The complexes undergo reductive elimination of HSiPh3 in benzene solution at room temperature to regenerate thiolatorhodium(I) complexes and HSiPh3. Thermodynamic parameters of the reaction, Rh(SC6H4-p-Me)L-3 + HSiPh3 = RhH(SiPh3)(SC6H4-p-Me)L-3, are determined as Delta H degrees=-61.7+/-0.7 kJ mol(-1), Delta S degrees=-227+/-15 J mol(-1) deg(-1) and Delta G degrees=5.9 kJ mol(-1) at 298 K. Crystallographic results of RhH(SiPh3)(SAr)L-3 show that the Rh-Si bonds are significantly longer than those of RhH[Si(OMe)(3)](SPh)L-3. Reaction of HSiEt3 with 1-3 does not give oxidative addition products at all. Diarylsilanes, H2SiPh2, H2Si(C6H4-p-Me)(2), H2Si(C6H4-m-Me)(2) and H2Si(C6H4-p-F)(2), react readily with Rh(SAr)L-3 to give the corresponding oxidative addition products, RhH(SiHAr'(2))(SAr)L-3, that do not undergo reductive elimination of diarylsilane in the solutions.

  DOI：

  10.1016/s0020-1693(97)05449-2
• 作为产物：
  描述：

  Di-(m-tolyl)-dichlor-silan 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以76%的产率得到bis(tolyl-3)silane
  参考文献：
  名称：

  新型芳基取代硅烷第二部分：二芳基硅二氢化物的合成和表征

  摘要：

  图形摘要 摘要 一系列新的和以前发表的二氢化硅，R2SiH2（R = 苄基、芴基、对甲苯基、对正丁基、对联苯、间甲苯基、邻甲苯基、2,4-二甲苯基、2,6 -二甲苯基、对联苯、1-萘基、9-蒽基），使用 1H、13C 和 29Si NMR 光谱合成和表征。在本文报道的二氢化硅物质和新型二氢化物之间比较了取代基体积对 29Si NMR 位移的影响。此外，采用单晶X射线衍射来阐明所有固体二氢化硅和室温下液体对甲苯基2SiH2的分子结构。这些化合物以边对面、π-π堆积和CH3…π相互作用的形式表现出非共价的分子间相互作用。

  DOI：

  10.1080/10426507.2015.1094657

文献信息

• Highly selective redistribution of primary arylsilanes to secondary arylsilanes catalyzed by Ln(CH₂C₆H₄NMe₂-<i>o</i>)₃@SBA-15
  作者：Chenjun Guo、Min Li、Jue Chen、Yunjie Luo

  DOI：10.1039/c9cc07493g

  日期：——

  Rare-earth metal tris(aminobenzyl) complexes Ln(CH2C6H4NMe2-o)3 (Ln = La, Y) were grafted onto the dehydroxylated periodic mesoporous silica support SBA-15 to generate the organometallic–inorganic hybrid materials Ln(CH2C6H4NMe2-o)3@SBA-15 (Ln = La (2a), Y (2b)), which demonstrated extremely high selectivity (>99%) in catalyzing the redistribution of primary arylsilanes to secondary arylsilanes without

  将稀土金属三（氨基苄基）配合物Ln（CH 2 C 6 H 4 NMe 2 - o）3（Ln = La，Y）接枝到脱羟基的周期性介孔二氧化硅载体SBA-15上，以生成有机金属-无机杂化材料Ln（CH 2 C 6 H 4 NMe 2 - o）3 @ SBA-15（Ln = La（2a），Y（2b）））在催化伯芳基硅烷向仲芳基硅烷的再分布方面表现出极高的选择性（> 99％），而无需严格控制反应条件。在三个催化循环后，杂化材料仍显示出完美的选择性和活性。
• Synthesis of Stereodefined Trisubstituted Alkenyl Silanes Enabled by Borane Catalysis and Nickel Catalysis
  作者：Yunxiao Zhang、Yanran Chen、Zeguo Zhang、Shanshan Liu、Xiao Shen

  DOI：10.1021/acs.orglett.9b04505

  日期：2020.2.7

  Regioselective and stereoselective synthesis of trisubstituted alkenyl silanes via hydrosilylation is challenging. Herein, we report the first β-anti-selective addition of silanes to thioalkynes with B(C6F5)3 as the catalyst. The reaction shows broad substrate scope. The products were proven to be useful intermediates to other trisubstituted alkenyl silanes by Ni-catalyzed stereoretentive cross-coupling reactions

  通过氢化硅烷化的三取代烯基硅烷的区域选择性和立体选择性合成是具有挑战性的。本文中，我们报道了以B（C6F5）3为催化剂向硫代炔烃中的硅烷的第一个β-抗选择性加成反应。反应显示出广泛的底物范围。通过CS键的Ni催化的立体保持性交叉偶联反应，证明该产物是其他三取代的烯基硅烷的有用中间体。一项机理研究表明，硫代炔对活化的甲硅烷基中间体的亲核攻击可能是决定速率的步骤。
• Highly Regio‐ and Enantioselective Hydrosilylation of <i>gem</i> ‐Difluoroalkenes by Nickel Catalysis
  作者：Dachang Bai、Fen Wu、Lingna Chang、Manman Wang、Hao Wu、Junbiao Chang

  DOI：10.1002/anie.202114918

  日期：2022.3

  Highly efficient enantioselective nickel-catalyzed hydrosilylation of gem-difluoroalkenes has been realized. This system integrates direct generation of difluoromethylated stereocenters and enantioselective carbon(sp3)−silicon bond formation.

  已经实现了偕二氟烯烃的高效对映选择性镍催化氢化硅烷化。该系统集成了二氟甲基化立体中心的直接生成和对映选择性碳（sp 3）-硅键的形成。
• Selective homo- and cross-desilacoupling of aryl and benzyl primary silanes catalyzed by a barium complex
  作者：Zhizhou Liu、Xianghui Shi、Jianhua Cheng

  DOI：10.1039/d0dt01158d

  日期：——

  Under mild conditions (25 °C, 5 mol% cat.), highly selective homo- and cross-desilacoupling of aryl and benzyl primary silanes to secondary silanes was achieved by the use of the heteroleptic barium aminobenzyl complex [(TpAd,iPr)Ba(CH2C6H4NMe2-o)] (TpAd,iPr = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) (1) as a catalyst. Dihydrosilanes originating from catalytic redistribution and cross-desilacoupling

  在温和的条件下（25°C，5 mol％催化），通过使用杂芳基钡氨基苄基络合物[（Tp Ad，iPr），实现了芳基和苄基伯硅烷与仲硅烷的高选择性均-和交叉-脱硅偶联。Ba（CH 2 C 6 H 4 NMe 2 - o）]（Tp Ad，iPr =氢三（3-金刚烷基-5-异丙基-吡唑基）硼酸酯）（1）。分离出了源自催化重分布和交叉脱硅偶联反应的二氢硅烷，收率很高，这表明钡络合物在仲芳基和苄基硅烷合成中的可行性应用。
• Divalent Ytterbium Complex-Catalyzed Homo- and Cross-Coupling of Primary Arylsilanes
  作者：Xiaojuan Liu、Li Xiang、Elisa Louyriac、Laurent Maron、Xuebing Leng、Yaofeng Chen

  DOI：10.1021/jacs.8b12138

  日期：2019.1.9

  Redistribution of primary silanes through C-Si and Si-H bond cleavage and reformation provides a straightforward synthesis of secondary silanes, but the poor selectivity and low efficiency severely hinders the application of this synthetic protocol. Here, we show that a newly synthesized divalent ytterbium alkyl complex exhibits unprecedentedly high catalytic activity toward the selective redistribution

  通过 C-Si 和 Si-H 键裂解和重组重新分配初级硅烷提供了二级硅烷的直接合成，但选择性差和效率低严重阻碍了该合成协议的应用。在这里，我们展示了一种新合成的二价镱烷基配合物对伯芳基硅烷选择性重新分布为仲芳基硅烷表现出前所未有的高催化活性。更重要的是，这种配合物还有效地催化了吸电子取代伯芳基硅烷和给电子取代伯芳基硅烷之间的交叉偶联，生成含有两种不同芳基的仲芳基硅烷。DFT 计算表明，该反应总是涉及在将 PhSiH3 轻松添加到 Yb-E (E = C, H) 键时放热形成高价硅。这种高价化合物可以很容易地直接生成 Yb-Ph 络合物，或者通过形成 Yb-H 间接生成，这是形成 Ph2SiH2 的关键络合物。