bromodimethylsilylbis(trimethylsilyl)methane | 86932-21-0

• 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: bromodimethylsilylbis(trimethylsilyl)methane
• 英文别名: [(Me3Si)2(Me2SiBr)CH]；bis(trimethylsilyl)methyl-bromo-dimethylsilane
• CAS: 86932-21-0
• 化学式: C₉H₂₅BrSi₃
• 分子量: 297.458
• InChiKey: XMKQBIVUEVMKLN-UHFFFAOYSA-N

物化性质

• 沸点：
  151.8±20.0 °C(Predicted)
• 密度：
  0.998±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.71
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  bromodimethylsilylbis(trimethylsilyl)methane 在 三乙基硼氢化钠 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.5h， 生成 (Me3Si)2(Me2SiSePh)CLi*2THF
  参考文献：
  名称：

  Synthesis and deprotonation of (phenylselenolatodimethylsilyl)bis(trimethylsilyl) methane: The crystal structure of (Me3Si)2(Me2SiBr)CH

  摘要：

  The moisture-sensitive compound [{bromodimethylsilyl)bis(trimethylsilyl)methane] [(Me3Si)(2)(Me2SiBr)CH] 1 has been synthesized by the bromination of the hydride [(Me3Si)(2)(Me2SiH)CH] in CCl4 in good yield. Compound 1 has been characterized by multinuclear NMR and a single crystal X-ray diffraction studies. The average Si-C and BrMe2Si-C distances are, respectively, 1.894(2) and 1.886(2) angstrom. The SiC-Si angle is 114.98(13)degrees. Treatment of 1 with NaSePh (obtained from the sodium triethylborohydride reduction of diphenyldiselenide) in benzene at room temperature resulted in the isolation of light yellow oil, [{phenylselenatodimethylsilyl)bis(trimethylsilyl)methane], [(Me3Si)(2)(Me2SiSePh)CH] 2. Compound 2 has been metallated with methyllithium as well as lithium diisopropylamide (LDA) in THF to give [(Me3Si)(2)(Me2SiSePh)CLi center dot 2THF] 3. Compounds 2 and 3 have been characterized by elemental analysis, mass and multinuclear NMR studies. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2012.03.004
• 作为产物：
  描述：

  Brom(bromdimethylsilyl)bis(trimethylsilyl)methan 在 PhLi 作用下， 以 乙醚 为溶剂， 反应 0.25h， 以100%的产率得到bromodimethylsilylbis(trimethylsilyl)methane
  参考文献：
  名称：

  的二聚体ethenes我2 EC（森达3）2（E =硅，锗，锡）：如何做他们从我出现2 EXCM（森达3）2？它们的结构如何？

  摘要：

  碱金属有机基甲硅烷基或MR（例如石灰，李Ñ卜，李吨卜，LIPH，使用LiCH（森达3）2，LIC（森达3）3，的NaSi吨卜3）转换等摩尔量的bromomethanes我2 EXCBr（ SiMe 3）2在有机溶剂（例如戊烷，乙醚，四氢呋喃）中通过E = Si，Ge，Sn和带负电的取代基X（例如F，Br，OPh）（i）通过非常快的Br / M交换成'金属化的产品我2 EXCM（森达3）2，其下形成的thermolyze '环丁烷'[Me 2 EC（森达3）2 ] 2，和（ii）由X / R交换进入'取代产物'我在较小程度上2 ERCBr（森达3）2。如图所示通过捕获实验中，不饱和化合物我2 EC（森达3）2播放在上述两个反应短命中间体的作用。它们是从我形成2 EXCM（森达3）2由MX消除和Me添加本碱金属化合物2（森达EXCM 3）2 ≡MR'或MR，分别。该产品我2 ER'CM（森达3）2与R'=

  DOI：

  10.1016/s0022-328x(99)00727-5

文献信息

• Synthesis and characterization of intramolecularly coordinated alanes with new sterically demanding trisyl-based ligands
  作者：Clinton L Lund、Olimpiu Stanga、J Wilson Quail、Jens Müller

  DOI：10.1139/v07-063

  日期：2007.7.1

  Five new intramolecularly coordinated aluminum species, whose molecular structures have been elucidated in solution by NMR spectroscopy and in the solid state by single crystal X-ray analysis, are described. All species are equipped with a trisyl-based ligand with a pyridyl donor group [Pytsi stands for -C(SiMe₃)₂SiMe₂(2-C₅H₄N)]. While the compound (Pytsi)AlMeCl was accessible either from Li(THF)(Pytsi) and MeAlCl₂ or from (Pytsi)AlCl₂ and LiMe, the tert-butyl derivative (Pytsi)AltBuCl could only be obtained from Li(THF)(Pytsi) and tBuAlCl₂. Attempted synthesis of (Pytsi)AltBuCl from (Pytsi)AlCl₂ and LitBu or from (Pytsi)AlCl₂ and tBuMgCl failed. Three other compounds (3-5) were synthesized and can be described as derivatives of (Pytsi)AlMe₂ with additional groups in the ortho position of the pyridyl group. Compound 3 carried a Me group in the ortho position, while compounds 4 and 5 were equipped with Ph and 2,6-diisopropylphenyl moieties, respectively.Key words: aluminum, trisyl ligands, methyl alanes.

  本文介绍了五种新的分子内配位铝化合物，通过核磁共振光谱分析和单晶 X 射线分析阐明了它们在溶液和固态中的分子结构。所有物种都配备了带有吡啶供体基团的三硅基配体[Pytsi 代表 -C(SiMe3)2SiMe2(2-C5H4N)]。化合物 (Pytsi)AlMeCl 可以从 Li(THF)(Pytsi) 和 Me 或 (Pytsi)AlCl2 和 LiMe 中得到，而叔丁基衍生物 (Pytsi)AltBuCl 只能从 Li(THF)(Pytsi) 和 tBu 中得到。从 (Pytsi) 和 LitBu 或 (Pytsi) 和 tBuMgCl 合成 (Pytsi)AltBuCl 的尝试均告失败。合成的另外三种化合物（3-5）可以说是(Pytsi)AlMe2 的衍生物，在吡啶基的正交位置带有额外的基团。化合物 3 在正交位置带有一个 Me 基团，而化合物 4 和 5 则分别带有 Ph 基团和 2,6- 二异丙基苯基基团。
• Crowded organometallic compounds of the alkali metals with diphenylphosphino substituents in the organic group
  作者：Anthony G. Avent、Dominique Bonafoux、Colin Eaborn、Michael S. Hill、Peter B. Hitchcock、J. David Smith

  DOI：10.1039/b002488k

  日期：——

  The lithium compound [LiC(SiMe2CH2PPh2)3] 1, obtained by metallation of the precursor HC(SiMe2CH2PPh2)3I with LiMe, crystallised from benzene as a solvate 1·1.5C6H6 that both in solution and in the solid state has an unusual tricyclic structure, with lithium bound to the carbanionic centre and the three phosphorus atoms. Lithiation of the related precursor HC(SiMe3)2(SiMe2CH2PPh2) II under similar conditions gave the dilithium compound [Li(thf)C(SiMe3)2SiMe2CH[Li(thf)2]PPh2}] 2, which has a fluxional structure in solution. Metallation of the precursor HC(SiMe3)2(SiMe2PPh2) III gave the compounds MC(SiMe3)2(SiMe2PPh2) (M = Li 3 or Na 4). Compound 3 is fluxional in benzene with interchange of methyl groups between SiMe2 and SiMe3 fragments. Compound 4, in contrast, has a non-fluxional molecular structure. In the solid the molecules of 4 form chains in which the sodium is bound intramolecularly to the carbanionic centre and to phenyl and intermolecularly to phenyl and phosphorus. Attempts to make the potassium analogue of 3 or 4 led to cleavage of the P–Si bond and formation of KPPh2. This has a complicated polymeric crystal structure in which molecules are linked by potassium–phenyl interactions.

  锂化合物 [LiC(SiMe2CH2PPh2)3] 1 是由前驱体 HC(SiMe2CH2PPh2)3I 与 LiMe 发生金属化反应而得到的，它从苯中结晶成溶胶 1-1.5C6H6，在溶液和固态中都具有不寻常的三环结构，锂与碳离子中心和三个磷原子结合在一起。在类似条件下对相关前体 HC(SiMe3)2(SiMe2CH2PPh2) II 进行锂化反应，得到了二锂离子化合物 [Li(thf)C(SiMe3)2SiMe2CH[Li(thf)2]PPh2}] 2，该化合物在溶液中具有通性结构。将前体 HC(SiMe3)2(SiMe2PPh2) III 金属化后，得到 MC(SiMe3)2(SiMe2PPh2) （M = Li 3 或 Na 4）化合物。化合物 3 在苯中具有通性，SiMe2 和 SiMe3 片段之间的甲基相互交换。相反，化合物 4 具有非通性分子结构。在固体中，4 的分子形成链，其中钠在分子内与碳离子中心和苯基结合，在分子间与苯基和磷结合。试图制造 3 或 4 的钾类似物会导致 P-Si 键断裂，形成 KPPh2。KPPh2 具有复杂的聚合晶体结构，其中的分子通过钾-苯基相互作用连接在一起。
• An alkylzinc bromide and a lithium alkyldibromozincate containing tris(organosilyl)methyl groups
  作者：Davood Azarifar、Martyn P. Coles、Salima M. El-Hamruni、Colin Eaborn、Peter B. Hitchcock、J.David Smith

  DOI：10.1016/j.jorganchem.2004.02.018

  日期：2004.5

  The lithium reagent (3) reacts with a molar equivalent of anhydrous zinc bromide to give the dimeric compound (2a), in which zinc is four-coordinate. The product from a similar reaction with LiC(SiMe3)2(SiMe2NPhMe)} is the lithium zincate [Li(THF)2(μ-Br)2ZnC(SiMe3)2(SiMe2NPhMe)}] (4), in which the zinc is only three-coordinate. The crystal structures of 2a and 4 have been determined.

  锂试剂（3）与摩尔当量的无水溴化锌反应，得到锌为四配位的二聚化合物（2a）。与Li C（SiMe 3）2（SiMe 2 NPhMe）}类似反应的产物是锌酸锂[Li（THF）2（μ-Br）2 Zn C（SiMe 3）2（SiMe 2 NPhMe） }]（4），其中锌仅是三坐标。已经确定了2a和4的晶体结构。
• Alkali metal complexes of sterically hindered mono- and di-carbanions containing Si–O bonds
  作者：Lyndsey J. Bowman、Keith Izod、William Clegg、Ross W. Harrington、J. David Smith、C. Eaborn

  DOI：10.1039/b510692c

  日期：——

  The oxygen-bridged, silicon-substituted alkane (Me3Si)2CH(SiMe2)}2O (1) may be prepared by the reaction of (Me3Si)2CH}Li with ClSiMe2OSiMe2Cl in refluxing THF. Similarly, the alkane (Me3Si)(Me2MeOSi)CH(SiMe2CH2)}2 (2) is readily accessible from the reaction between (Me3Si)(Me2MeOSi)CH}Li and ClSiMe2CH2CH2SiMe2Cl under the same conditions. Compound 1 reacts with two equivalents of MeK to give the

  氧桥接的硅取代的烷烃（Me 3 Si）2 CH（SiMe 2）} 2 O（1）可以通过（Me 3 Si）2 CH} Li与ClSiMe 2 OSiMe 2 Cl的反应来制备。在回流的THF中。类似地， Me 3 Si）（Me 2 MeOSi）CH} Li与ClSiMe之间的反应很容易获得烷烃（Me 3 Si）（Me 2 MeOSi）CH（SiMe 2 CH 2）} 2 （2）。2 CH 2 CH 2森达在相同条件下为2 Cl。化合物1与两当量的MeK反应生成聚合物络合物[[（（Me 3 Si） 2 C（SiMe 2）} 2 O] K 2（OEt 2）] ∞ [ 5（OEt 2）]重结晶。用两个等价的任意一个对2进行处理梅里或MeK给出相应的络合物[（Me 3 Si）（Me 2 MeOSi）C（SiMe 2 CH 2）} 2 Li] [Li（DME）3 ] [ 7（DME）3 ]和[（Me
• A Suite of Sterically-Demanding Hybrid Alkyl/Cyclopentadienyl Ligands
  作者：Keith Izod、Claire F. Jones、Elizabeth P. Wildman、Ross W. Harrington、Paul G. Waddell

  DOI：10.1021/acs.organomet.7b00662

  日期：2017.11.13

  PhCH2K to give the dipotassium salt [(Me3Si)CPMe2(BH3)}SiMe2(C5Me4)}]K2(THF). X-ray crystallography revealed that the dipotassium salts of these hybrid ligands crystallize as zigzag polymers or three-dimensional networks. The suitability of the dipotassium salts as ligand transfer reagents for the synthesis of lanthanide complexes was probed through the synthesis of the lanthanum(III) complex [(Me3S

  杂烷基/环戊二烯基“约束几何”配体（Me 3 Si）2 CH SiMe 2（C 5 H 5）}，（Me 3 Si）2 CH SiMe 2（C 5 Me 4 H）}和（Me通过溴硅烷（Me 3 Si）2 CH（SiMe 2）反应合成了3 Si）2 CH SiMe 2（C 5 H 4 -3-SiMe 3）}Br）与相应的环戊二烯酸锂。这些配体与过量的MeK金属化可得到相应的二钾盐[（Me 3 Si）2 C SiMe 2（C 5 H 4）}] K 2（OEt 2）0.5，[（Me 3 Si）2 C SiMe 2（C 5 Me 4）}] K 2（OEt 2）和[[（Me 3 Si）2 C SiMe 2（C 5 H 3 -3-SiMe 3）}] K 2（C6 H 6）] 2 ·2C 6 H 6重结晶后。同样，膦-硼烷取代的氯硅烷（Me 3 Si）CH PMe 2（BH 3）}（SiMe