PhSi(OCy)₃ | 13340-45-9

• 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: PhSi(OCy)₃
• 英文别名: Phenyl-tricylohexyloxy-silan；tris-cyclohexyloxy-phenyl-silane；Tris-cyclohexyloxy-phenyl-silan；Tricyclohexyloxy(phenyl)silane
• CAS: 13340-45-9
• 化学式: C₂₄H₃₈O₃Si
• 分子量: 402.649
• InChiKey: MIXFLJSOOJGFAL-UHFFFAOYSA-N

物化性质

• 沸点：
  196 °C(Press: 1 Torr)
• 密度：
  1.039 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  5.88
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  苯硅烷 、 环己酮 在 Wilkinson's catalyst 作用下， 生成 PhSi(OCy)₃
  参考文献：
  名称：

  通过氢化硅烷化还原羰基化合物：I.三（三苯基膦）氯铑催化羰基化合物的氢化硅烷化

  摘要：

  使用三（三苯基膦）氯铑作为催化剂，对各种羰基化合物（例如简单的醛，简单的酮，α，β-不饱和羰基化合物，α-二酮，酰基氰化物和在α-碳上具有吸电子基团的酮）进行氢化硅烷化描述。这些甲硅烷基醚和甲硅烷基烯醇醚的溶剂分解得到相应的还原产物。发现α，β-不饱和羰基化合物的氢化硅烷化通过1，4-加成进行。获得三乙基硅烷与铑-（I）配合物的氧化加合物作为反应中间体。根据加合物的红外光谱和远红外光谱对加合物的结构进行了讨论。

  DOI：

  10.1016/s0022-328x(00)86954-5

文献信息

• Reduction of carbonyl compounds via hydrosilylation
  作者：Iwao Ojima、Mitsuru Nihonyanagi、Tetsuo Kogure、Miyoko Kumagai、Shuji Horiuchi、Kimiyo Nakatsugawa、Yoichiro Nagai

  DOI：10.1016/s0022-328x(00)86954-5

  日期：1975.8

  electron-withdrawing group on the α-carbon using tris(triphenylphosphine)chlororhodium as a catalyst is described. Solvolysis of these silyl ethers and silyl enol ethers afforded the corresponding reduced products. The hydrosilylation of α,β-unsaturated carbonyl compounds was found to proceed by 1,4-addition. An oxidative adduct of triethylsilane to the rhodium-(I) complex was obtained as a reaction intermediate

  使用三（三苯基膦）氯铑作为催化剂，对各种羰基化合物（例如简单的醛，简单的酮，α，β-不饱和羰基化合物，α-二酮，酰基氰化物和在α-碳上具有吸电子基团的酮）进行氢化硅烷化描述。这些甲硅烷基醚和甲硅烷基烯醇醚的溶剂分解得到相应的还原产物。发现α，β-不饱和羰基化合物的氢化硅烷化通过1，4-加成进行。获得三乙基硅烷与铑-（I）配合物的氧化加合物作为反应中间体。根据加合物的红外光谱和远红外光谱对加合物的结构进行了讨论。
• [EN] FIRST-ROW TRANSITION METAL HYDROGENATION AND HYDROSILYLATION CATALYSTS<br/>[FR] CATALYSEURS D'HYDROGÉNATION ET D'HYDROSILYLATION À BASE DE MÉTAUX DE TRANSITION DE LA PREMIÈRE COLONNE
  申请人：UNIV ARIZONA STATE

  公开号：WO2014201082A1

  公开（公告）日：2014-12-18

  Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  过渡金属化合物，特别是具有四齿和/或五齿支撑配体的过渡金属化合物被描述，以及其制备方法和将这些化合物用作加氢和/或加硅催化剂的用途。
• An Efficient Catalyst Based on Manganese Salen for Hydrosilylation of Carbonyl Compounds
  作者：Vamshi K. Chidara、Guodong Du

  DOI：10.1021/om400805v

  日期：2013.9.23

  A manganese salen complex is shown to be an effective (pre)catalyst in the hydrosilylation of aldehydes and ketones. The present system features an earth-abundant and inexpensive base metal, low catalyst loading, and functional group tolerance. Mechanistic studies suggest that the reaction likely proceeds through a reduced manganese(III) hydride species that undergoes electrophilic attack by the carbonyl substrates.
• Woronkow; Schabarowa, Zhurnal Obshchei Khimii, 1959, vol. 29, p. 1528,1530;engl.Ausg.S.1501,1503
  作者：Woronkow、Schabarowa

  DOI：——

  日期：——
• 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.