2,4,6-tris[bis(trimethylsilyl)methyl]phenyl(mesityl)SiCN(2,4,6-tri-tert-butylphenyl)

• 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: 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl(mesityl)SiCN(2,4,6-tri-tert-butylphenyl)
• 英文别名: Tbt(Mes)SiCN(Mes*)；(mesityl)(2,4,6-tris[bis(trimethylsilyl)methyl]phenyl)Si(CNC6H2-2,4,6-(t-Bu)3
• 化学式: C₅₅H₉₉NSi₇
• 分子量: 970.996
• InChiKey: FYJGWIZWQLROJI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.45
• 重原子数：
  63
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,4,6-tris[bis(trimethylsilyl)methyl]phenyl(mesityl)SiCN(2,4,6-tri-tert-butylphenyl) 在 n-BuLi 、 Na*K 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 生成 ((4-(mesitylsilyl)-5-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)bis(trimethylsilyl)methyl)-1,3-phenylene)bis(methanetriyl))tetrakis(trimethylsilane)
  参考文献：
  名称：

  Synthesis of Alkali Metal Salts of Borylsilyl Anions Utilizing Highly Crowded Silylboranes and Their Properties

  摘要：

  The lithium salt of a borylsilyl anion, [Tbt(Mes)SiBpin](-)Li(+) (11: Tbt = 2,4,6-tris[bis(trimethylsilyl)-methyl]phenyl, Mes = mesityl, pin = pinacolato), was synthesized by the boron-metal exchange reaction of a diborylsilane, Tbt(Mes)Si(Bpin)(2) (8), which was synthesized by the insertion of a highly crowded diarylsilylene, Tbt(Mes)Si: (1), into the B-B bond of a diborane(4) compound, B(2)pin(2). Although a salt of the borylsilyl anion 11 could not be isolated due to its thermal instability, the investigation of the reactivity of the anion revealed that 11 is a possible precursor for Si-functionalized silylboranes as well as Si,Si-difunctionalized silanes. Furthermore, the borylsilyl anion [Tbt(Mes)SiB Scat](-) (27: Scat = dithiocatecholato), which was synthesized by a procedure similar to that used for 11, showed a reactivity different from that of 11. Theoretical calculations for the borylsilyl anions revealed that the anion 27 has a boratasilene character; namely, the Si-B bond has a double-bond character due to the donation of an electron pair of the negatively charged silicon atom into the vacant p-orbital of the adjacent boron atom.

  DOI：

  10.1021/om7008974

文献信息

• Insertion of an Overcrowded Silylene into Hydro- and Haloboranes:  A Novel Synthesis of Silylborane Derivatives and Their Properties
  作者：Takashi Kajiwara、Nobuhiro Takeda、Takahiro Sasamori、Norihiro Tokitoh

  DOI：10.1021/om049558w

  日期：2004.9.1

  Silylene complex 3a reacted with BH3·PPh3 as well to give the corresponding silylborane-phosphine complex Tbt(Mes)SiHBH2·PPh3 (12). In addition, silylene 2 thermally generated from the corresponding disilene, Tbt(Mes)SiSi(Mes)Tbt (1), gave 12 when reacted with BH3·PPh3. These results strongly suggested that the reactions of 3 with BH3·THF and BH3·PPh3 proceeded via insertion of a silylene, Tbt(Mes)Si: 

  稳定的甲硅烷基-异氰化物配合物TBT（MES）SiCNAr（3a，Ar = MES *; 3b，Ar = TBT; 3c，Ar = Tip; TBT = 2,4,6-tris [双（三（三甲基甲硅烷基）甲基]苯基， MES =三甲苯基，MES * = 2,4,6-三-叔丁基苯基，提示= 2,4,6-三异丙基）与硼化合物进行了研究。的反应图3a，b与BH 3 ·THF，得到第一稳定silylborane-胩络合物，TBT（MES）SiHBH 2 ·CNAR（图4a，b）。亚甲硅烷基络合物3a与BH 3 ·PPh 3反应还得到相应的甲硅烷基硼烷-膦配合物TBT（MES）SiHBH 2 ·PPh 3（12）。此外，当与BH 3 ·PPh 3反应时，由相应的二甲苯TBT（MES）Si Si（MES）TBT（1）热生成的亚甲硅2生成12。这些结果有力地表明3与BH 3 ·THF和BH 3 ·PPh
• Reaction of a Stable Silylene–Isocyanide Complex with Nitrile Oxides: A New Approach to the Generation of a Silanone
  作者：Nobuhiro Takeda、Norihiro Tokitoh、Renji Okazaki

  DOI：10.1246/cl.2000.244

  日期：2000.3

  silanone [Tbt(Mes)Si=O; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes = mesityl] (8) was generated via intermediary 1,2,4-oxazasiletes by the reaction of a stable silylene–isocyanide complex with nitrile oxides. In a THF solution, silanone 8 underwent intramolecular cyclization with migration of a trimethylsilyl group in Tbt group to the oxygen atom of the Si=O double bond.

  过度拥挤的硅烷酮 [Tbt(Mes)Si=O; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes = mesityl] (8) 是通过中间体 1,2,4-oxazasilites 通过稳定的亚甲硅烷 - 异氰化物配合物与腈氧化物的反应生成的。在THF溶液中，硅烷酮8发生分子内环化，Tbt基团中的三甲基甲硅烷基迁移到Si=O双键的氧原子上。
• A Novel Reaction Mode in the Cycloaddition of Thermally Generated Silylenes with Conjugated Dienes
  作者：Nobuhiro Takeda、Norihiro Tokitoh、Renji Okazaki

  DOI：10.1246/cl.2000.622

  日期：2000.6

  A thermally generated silylene bearing bulky substituents, Tbt(Mes)Si: (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Mes = 2,4,6-trimethylphenyl), reacted with isoprene at room temperature to give the corresponding 2-vinylsilirane, which thermally isomerized to the corresponding 3-silolene, while silylene underwent competitive [1+2] and [1+4] cycloadditions with 2,4-dimethyl-1,3-butadiene.

  热生成的带有庞大取代基的亚甲硅烷，Tbt(Mes)Si：（Tbt = 2,4,6-三[双（三甲基甲硅烷基）甲基]苯基；Mes = 2,4,6-三甲基苯基），在室温下与异戊二烯反应得到相应的 2-乙烯基硅烷，其热异构化为相应的 3-硅油烯，而硅烯与 2,4-二甲基-1,3-丁二烯进行竞争性 [1+2] 和 [1+4] 环加成。
• Unprecedented insertion reaction of a silylene into a B–B bond and generation of a novel borylsilyl anion by boron–metal exchange reaction of the resultant diborylsilane
  作者：Takashi Kajiwara、Nobuhiro Takeda、Takahiro Sasamori、Norihiro Tokitoh

  DOI：10.1039/b409575h

  日期：——

  diarylsilylene, Tbt(Mes)Si: (1, Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes = mesityl), thermally generated from overcrowded disilene Tbt(Mes)Si=Si(Mes)Tbt (2) or stable silylene-isocyanide complex (3a), was found to insert into a B-B bond of bis(pinacolato)diboron, B2(pin)2 (4), and the boron-lithium exchange reaction of the resulting diborylsilane gave the first borylsilyl anion.

  动力学稳定的二芳基亚甲硅烷基Tbt（Mes）Si：（1，Tbt = 2,4,6-三[双（三（三甲基甲硅烷基）甲基]苯基，Mes =异丁烯基]），是由拥挤的二甲苯Tbt（Mes）Si = Si（发现Mes）Tbt（2）或稳定的甲硅烷基-异氰化物络合物（3a）插入双（频哪醇）二硼的BB键，B2（pin）2（4）以及由此产生的硼-锂交换反应用二硼烷基硅烷得到第一硼硅烷基阴离子。
• Reaction of Stable Silylene–Isocyanide Complexes with Boranes: Synthesis and Properties of the First Stable Silylborane–Isocyanide Complexes
  作者：Nobuhiro Takeda、Takashi Kajiwara、Norihiro Tokitoh

  DOI：10.1246/cl.2001.1076

  日期：2001.11

  Stable silylene–isocyanide complexes [Tbt(Mes)SiCNAr (Ar = Tbt, Mes*; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Mes = mesityl; Mes* = 2,4,6-tri-t-butylphenyl)] reacted with BH3·THF to give the first stable silylborane–isocyanide complexes [Tbt(Mes)SiHBH2CNAr]. The thermal equilibrium between Tbt(Mes)SiHBH2CNAr and TbtSiH2BH(Mes)CNAr was observed.

  稳定的亚硅烷-异氰化物配合物 [Tbt(Mes)SiCNAr (Ar = Tbt, Mes*; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Mes = mesityl; Mes* = 2,4,6-三叔丁基苯基）]与 BH3·THF 反应得到第一个稳定的甲硅烷基硼烷 - 异氰化物配合物 [Tbt(Mes)SiHBH2CNAr]。观察到 Tbt(Mes)SiHBH2CNAr 和 TbtSiH2BH(Mes)CNAr 之间的热平衡。