(E)-[1-(phenyl)-2-(1,1,3,3,3-pentamethyldisiloxane)]ethene

• 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: (E)-[1-(phenyl)-2-(1,1,3,3,3-pentamethyldisiloxane)]ethene
• 英文别名: 1,1,1,3,3-pentamethyl-3-[(1E)-2-phenylethenyl]-disiloxane；dimethyl-[(E)-2-phenylethenyl]-trimethylsilyloxysilane
• 化学式: C₁₃H₂₂OSi₂
• 分子量: 250.488
• InChiKey: ZLLVQELIBCDLLZ-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  溴苯 、 (E)-[1-(phenyl)-2-(1,1,3,3,3-pentamethyldisiloxane)]ethene 在 [PdCl₂P(OCH₂CMe₂NH)OCH₂CMe₂NH₂] 、 四丁基氟化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 以95%的产率得到反式-1,2-二苯乙烯
  参考文献：
  名称：

  An efficient synthesis of functional stilbenes in Hiyama coupling reaction catalysed by H-spirophosphorane palladium complex

  摘要：

  An efficient Hiyama cross-coupling reaction of functionalised styrylsilanes with iodo- and bromobenzene has been performed using complex [PdCl2P(OCH2CMe2NH) OCH2CMe2NH2] as precatalyst. The styrylsilanes underwent cross-coupling reactions with excellent selectivity and yield, up to 99%, of the corresponding E-stilbenes. When (E)-[1-(4-bromophenyl)-2-(1,1,3,3,3-pentamethyldisiloxy)]ethene was used as a source of the silane, a homocoupling reaction took place and polymeric compound containing 0.77% of palladium in the form of Pd(0) nanoparticles was obtained. This material used as a catalyst made it possible to obtain 40% and 38% of the Hiyama cross-coupling product in two subsequent runs. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2011.09.025
• 作为产物：
  描述：

  (Z)-1,1,1,3,3-pentamethyl-3-styryldisiloxane 在 五甲基二硅氧烷 、 RhI(PPh₃)3 作用下， 反应 1.0h， 以100%的产率得到(E)-[1-(phenyl)-2-(1,1,3,3,3-pentamethyldisiloxane)]ethene
  参考文献：
  名称：

  Isomerization of (Z)-alkenylsilanes to (E)-isomers with hydrosilane and RhI(PPh₃)₃

  摘要：

  (E)-2-苯乙烯基硅烷的异构化反应在60°C下，使用20-100 mol％的硅氢化合物和0.1 mol％的RhI（PPh3）3催化剂，1小时内易于发生转化为（Z）异构体，其机理是通过烯基硅烷插入到氢化铑中，然后进行β-氢化物消除。关键词：硅氢化，异构化，RhI（PPh3）3，烯基硅烷，硅氢化合物。

  DOI：

  10.1139/v01-129

文献信息

• Mononuclear ruthenium complex and organic synthesis reaction using same
  申请人：KYUSHU UNIVERSITY, NATIONAL UNIVERSITY CORPORATION

  公开号：US09884316B2

  公开（公告）日：2018-02-06

  A neutral or cationic mononuclear ruthenium divalent complex represented by formula (1) can actualize exceptional catalytic activity in at least one reaction among a hydrosilylation reaction, hydrogenation reaction, and carbonyl compound reduction reaction. (In the formula, R1-R6 each independently represent a hydrogen atom or an alkyl group, aryl group, aralkyl group, organooxy group, monoorganoamino group, diorganoamino group, monoorganophosphino group, diorganophosphino group, monoorganosilyl group, diorganosilyl group, triorganosilyl group, or organothio group optionally substituted by X; at least one pair comprising any of R1-R3 and any of R4-R6 together represents a crosslinkable substituent; X represents a halogen atom, organooxy group, monoorganoamino group, diorganoamino group, or organothio group; L each independently represent a two-electron ligand other than CO and thiourea ligands; two L may bond to each other; and m represents an integer of 3 or 4.)

  根据公式（1）表示的中性或阳离子单核钌二价配合物，可以在至少一个反应中实现卓越的催化活性，包括氢硅化反应、氢化反应和羰基化合物还原反应。 （在公式中，R1-R6每个独立地代表一个氢原子或一个烷基、芳基、芳烷基、有机氧基、单有机胺基、双有机胺基、单有机膦基、双有机膦基、单有机硅基、双有机硅基、三有机硅基或有机硫基，可由X取代；R1-R3和R4-R6中的至少一对共同代表一个可交联的取代基；X代表一个卤素原子、有机氧基、单有机胺基、双有机胺基或有机硫基；L各自独立地代表一个除CO和硫脲配体以外的双电子配体；两个L可以相互结合；m代表一个3或4的整数。）
• Mononuclear iron complex and organic synthesis reaction using same
  申请人：KYUSHU UNIVERSITY, NATIONAL UNIVERSITY CORPORATION

  公开号：US10363551B2

  公开（公告）日：2019-07-30

  A mononuclear iron bivalent complex having iron-silicon bonds, which is represented by formula (1), can exhibit an excellent catalytic activity in at least one reaction selected from three reactions, i.e., a hydrosilylation reaction, a hydrogenation reaction and a reaction for reducing a carbonyl compound. (In the formula, R1 to R6 independently represent a hydrogen atom, an alkyl group which may be substituted by X, or the like; X represents a halogen atom, or the like; L1 represents at least one two-electron ligand selected from an isonitrile ligand, an amine ligand, an imine ligand, a nitrogenated heterocyclic ring, a phosphine ligand, a phosphite ligand and a sulfide ligand, wherein, when multiple L1's are present, two L1's may be bonded to each other; L2 represents a two-electron ligand that is different from a CO ligand or the above-mentioned L1, wherein, when multiple L2's are present, two L2's may be bonded to each other; and m1 represents an integer of 1 to 4 and m2 represents an integer of 0 to 3, wherein the sum total of m1 and m2 (i.e., m1+m2) satisfies 3 or 4.)

  具有铁-硅键的单核二价铁络合物，其由公式（1）表示，可以在三个反应中选择至少一个反应表现出优异的催化活性，即硅氢化反应、氢化反应和还原羰基化合物的反应。 （在公式中，R1至R6独立代表氢原子、可能被X取代的烷基团等；X代表卤素原子等；L1代表至少一种从异腈配体、胺配体、亚胺配体、氮杂环、膦配体、亚磷酸盐配体和硫化物配体中选择的两电子配体，其中，当存在多个L1时，两个L1可以相互连接；L2代表与CO配体或上述L1不同的两电子配体，其中，当存在多个L2时，两个L2可以相互连接；m1代表1至4的整数，m2代表0至3的整数，其中m1和m2的总和（即m1+m2）满足3或4。）
• Catalyst design for iron-promoted reductions: an iron disilyl-dicarbonyl complex bearing weakly coordinating η2-(H–Si) moieties
  作者：Yusuke Sunada、Hironori Tsutsumi、Keisuke Shigeta、Ryota Yoshida、Toru Hashimoto、Hideo Nagashima

  DOI：10.1039/c3dt52598h

  日期：——

  Iron disilyl dicarbonyl complex 1, in which two H–Si moieties of the 1,2-bis(dimethylsilyl)benzene ligand were coordinated to the iron center in an η2-(H–Si) fashion, was synthesized by the reaction of (η4-C6H8)Fe(CO)3 with 2 equiv. of 1,2-bis(dimethylsilyl)benzene under photo-irradiation. Complex 1 demonstrated high catalytic activity toward the hydrogenation of alkenes, the hydrosilylation of alkenes and the reduction of carbonyl compounds.

  铁二硅基二羰基配合物1通过(η⁴-C6H8)Fe(CO)3与2当量1,2-双(二甲基硅基)苯在光照射下反应合成，其中1,2-双(二甲基硅基)苯配体的两个H-Si部分以η²-(H-Si)方式与铁中心配位。配合物1对烯烃的氢化、烯烃的氢硅化以及羰基化合物的还原表现出高效的催化活性。
• RhCl(PPh₃)₃/NaI Catalyst System for Hydrosilylation of 1-Alkynes: Stereodivergent Syntheses of E- and Z-Alkenylsilanes with Heteroatom Substituents on Silicon
  作者：Atsunori Mori、Eisuke Takahisa、Hiroshi Kajiro、Kazunori Hirabayashi、Yasushi Nishihara、Tamejiro Hiyama

  DOI：10.1246/cl.1998.443

  日期：1998.5

  Both (E)- and (Z)-alkenylsilanes are synthesized by the reaction of hydrosilanes and 1-alkynes catalyzed by RhCl(PPh3)3/NaI or RhI(PPh3)3 highly selectively.

  (E)-和(Z)-烯基硅烷均可通过在RhCl(PPh3)3/NaI或RhI(PPh3)3催化下，高度选择性地由氢硅烷与1-炔烃反应合成。
• Dehydrogenative silylation of terminal alkynes by iridium catalyst
  作者：Rie Shimizu、Takamasa Fuchikami

  DOI：10.1016/s0040-4039(99)02174-7

  日期：2000.2

  Dehydrogenative silylation of terminal alkynes with hydrosilanes proceeds in the presence of iridium catalyst to afford the corresponding silylacetylenes. When phenylacetylene and triethylsilane were heated in dry DME in the presence of Ir4(CO)12–PPh3, (2-phenylethynyl)triethylsilane was obtained in 96% yield with little of hydrosilylated products. The present method is applicable for a variety of

  末端炔烃与氢硅烷的脱氢甲硅烷基化反应在铱催化剂的存在下进行，得到相应的甲硅烷基乙炔。在Ir 4（CO）12 -PPh 3的存在下，在干燥的DME中加热苯基乙炔和三乙基硅烷时，得到的（2-苯基乙炔基）三乙基硅烷收率为96％，几乎没有氢化硅烷化产物。本方法适用于各种末端炔烃和氢硅烷，以高收率和高选择性得到相应的甲硅烷基乙炔。