1-trimethylsilylacetylenehexacarbonyldicobalt | 57032-12-9

• 分子结构分类: 有机化合物 - 乙炔化物 - 金属乙炔化物
• 英文名称: 1-trimethylsilylacetylenehexacarbonyldicobalt
• 英文别名: hexacarbonyl (η²-trimethylsilyl ethyne) dicobalt；(μ-HCCTMS)Co2(CO)6；Co₂(CO)₆(μ²-trimethylsilylacetylene)；Co2(CO)6(μ-trimethylsilylacetylene)；η2-(((CH3)3Si)acetylene)dicobalt hexacarbonyl；(trimethylsilylacetylene)hexacarbonyldicobalt；trimethylsilylacetylene dicobalt hexacarbonyl；(μ2-trimethylsilylacetylene)Co2(CO)6；[Co2(CO)6(trimethylsilylacetylene)]；carbon monoxide;cobalt;ethynyl(trimethyl)silane
• CAS: 57032-12-9
• 化学式: C₁₁H₁₀Co₂O₆Si
• 分子量: 384.269
• InChiKey: WUQMAQSIEPQLEF-UHFFFAOYSA-N

物化性质

• 熔点：
  29 °C

计算性质

• 辛醇/水分配系数(LogP)：
  1.27
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-trimethylsilylacetylenehexacarbonyldicobalt 以 丙酮 为溶剂， 以12%的产率得到
  参考文献：
  名称：

  Ring Opening of a Cobalt-Stabilized Bornyl Cation:  Mechanistic Study of the Alkyne−Dicobalt/Carbynyl−Tricobalt Cluster Transformation

  摘要：

  Upon protonation with HBF4, [2-endo-((allyldimethylsilyl)ethynyl)borneol]CO2(CO)(6) (2) suffers elimination of water or propene, to yield [2-((allyldimethylsilyl)ethynyl)born-2-enel-CO2(CO)(6) (11) and [2-endo-((dimethylfluorosilyl)ethynyl)borneol]CO2(CO)(6) (12), respectively, and, surprisingly, the tricobalt complex (2-norbornylidene)CHCCo3(CO)(9) (13). In contrast, protonation of the terminal alkyne (2-endo-ethynylborneol)CO2(CO)(6) (19), an anticipated precursor to 13, led instead to (2-ethynyl-2-bornene)CO2(CO)(6) (21) and the ring-opened species (2-ethynyl-4-isopropyl-l-methylcyclohexa-1,3-diene)CO2(CO)(6) (22). However, conversion of 19 to 13 was achievable upon prolonged heating at reflux in acetone, thereby also affording the corresponding alcohol [2-(2-hydroxybornyl)]CH2CCo3(CO)(9) (20). A mechanistic rationale is offered for the formation of RCH2CCo3(CO)(9) clusters upon protonation of alkyne complexes of the type (RCdropCH)Co-2(CO)(6).

  DOI：

  10.1021/om020727r
• 作为产物：
  描述：

  [(trimethylsilyl)(allyldimethylsilyl)ethyne]Co2(CO)6 在 HBF₄ 作用下， 以 乙醚 为溶剂， 生成 1-trimethylsilylacetylenehexacarbonyldicobalt
  参考文献：
  名称：

  Ring Opening of a Cobalt-Stabilized Bornyl Cation:  Mechanistic Study of the Alkyne−Dicobalt/Carbynyl−Tricobalt Cluster Transformation

  摘要：

  Upon protonation with HBF4, [2-endo-((allyldimethylsilyl)ethynyl)borneol]CO2(CO)(6) (2) suffers elimination of water or propene, to yield [2-((allyldimethylsilyl)ethynyl)born-2-enel-CO2(CO)(6) (11) and [2-endo-((dimethylfluorosilyl)ethynyl)borneol]CO2(CO)(6) (12), respectively, and, surprisingly, the tricobalt complex (2-norbornylidene)CHCCo3(CO)(9) (13). In contrast, protonation of the terminal alkyne (2-endo-ethynylborneol)CO2(CO)(6) (19), an anticipated precursor to 13, led instead to (2-ethynyl-2-bornene)CO2(CO)(6) (21) and the ring-opened species (2-ethynyl-4-isopropyl-l-methylcyclohexa-1,3-diene)CO2(CO)(6) (22). However, conversion of 19 to 13 was achievable upon prolonged heating at reflux in acetone, thereby also affording the corresponding alcohol [2-(2-hydroxybornyl)]CH2CCo3(CO)(9) (20). A mechanistic rationale is offered for the formation of RCH2CCo3(CO)(9) clusters upon protonation of alkyne complexes of the type (RCdropCH)Co-2(CO)(6).

  DOI：

  10.1021/om020727r

文献信息

• PNSO Ligands as a Tool to Study Metal Bonding of Electron‐Deficient Sulfinyl Groups
  作者：Marc Revés、Antoni Riera、Xavier Verdaguer

  DOI：10.1002/ejic.200900521

  日期：2009.10

  N-phosphanylsulfinamide (PNSO) ligands with electron-deficient sulfinyl groups was synthesized. Reaction with Co2–alkyne complexes yields P,S-bridged complexes. These complexes were used to study the metal bonding of different sulfinyl groups. IR spectroscopy, X-ray analysis, and Pauson–Khand reactivity studies indicated that electrondeficient sulfinyl groups provide enhanced S metal bonding.

  合成了一系列具有缺电子亚磺酰基的 N-膦酰基亚磺酰胺 (PNSO) 配体。与 Co2-炔烃配合物反应生成 P,S 桥连配合物。这些配合物用于研究不同亚磺酰基的金属键合。IR 光谱、X 射线分析和 Pauson-Khand 反应性研究表明缺电子亚磺酰基提供增强的 S 金属键合。
• The Pauson–Khand reaction of medium sized trans-cycloalkenes
  作者：Agustí Lledó、Aida Fuster、Marc Revés、Xavier Verdaguer、Antoni Riera

  DOI：10.1039/c3cc41005f

  日期：——

  Medium sized trans-cycloalkenes are unusually reactive in the intermolecular Pauson-Khand reaction (PKR) with regard to typical monocyclic alkenes. This is due to the ring strain imparted by the E stereochemistry. The PKR of these alkenes offers a modular, regioselective and straightforward entry to trans fused [n.3.0] bicyclic scaffolds (n = 6-8).

  就典型的单环烯烃而言，中型反式环烯烃在分子间Pauson-Khand反应（PKR）中具有异常的反应性。这是由于E立体化学赋予的环应变。这些烯烃的PKR为反式[n.3.0]双环支架（n = 6-8）提供了模块化，区域选择性和直接进入的途径。
• Acetylene−Dicobaltcarbonyl Complexes with Chiral Phosphinooxazoline Ligands:  Synthesis, Structural Characterization, and Application to Enantioselective Intermolecular Pauson−Khand Reactions
  作者：Jaume Castro、Albert Moyano、Miquel A. Pericàs、Antoni Riera、Angel Alvarez-Larena、Joan F. Piniella

  DOI：10.1021/ja001143o

  日期：2000.8.23

  of the diastereomer nonchelated complexes 11a,b−15a,b. The interconversion rate between diastereomeric pairs is dependent on the steric bulk of the alkyne substituent, and neither 3 nor 5 epimerize at room temperature. The structures of both kinds of complexes have been ascertained by a combination of spectroscopical (IR, NMR), X-ray diffraction, and chiroptical methods; this has allowed the development

  苯乙炔-二钴六羰基配合物 (2) 与 4-R-2-(2-二苯基膦基苯基) 恶唑啉 1 (R = Ph) 和 4 (R = CH2CH2SCH3) 的反应导致螯合配合物 3 和 5 的选择性形成， 分别。另一方面，叔丁基取代的膦基恶唑啉 6 作为单齿配体，它与几个 1-炔烃衍生的配合物 (2,7-10) 的反应提供了非对映异构体非螯合配合物 11a,b- 的易于分离的混合物15a，b。非对映体对之间的相互转化率取决于炔烃取代基的空间体积，并且在室温下既不是 3 也不是 5 差向异构化。两种配合物的结构已经通过光谱（IR、NMR）、X射线衍射和手光学方法的组合确定；
• Ethylene Glycol Assisted Intermolecular Pauson–Khand Reaction
  作者：Albert Cabré、Xavier Verdaguer、Antoni Riera

  DOI：10.1055/s-0036-1588813

  日期：2017.9

  N-oxide-promoted intermolecular Pauson–Khand reaction (PKR) has been studied. The addition of 15% ethylene glycol to the reaction mixture consistently increased (from 20% up to 2–4-fold) the reaction yields. The use of ethylene glycol as additive in the N-oxide-promoted intermolecular Pauson–Khand reaction (PKR) has been studied. The addition of 15% ethylene glycol to the reaction mixture consistently

  作为有机合成中的专题钴的一部分出版 抽象的 研究了在N氧化物促进的分子间Pauson-Khand反应（PKR）中使用乙二醇作为添加剂。向反应混合物中添加15％的乙二醇始终可以提高反应产率（从20％到2-4倍）。 研究了在N氧化物促进的分子间Pauson-Khand反应（PKR）中使用乙二醇作为添加剂。向反应混合物中添加15％的乙二醇始终可以提高反应产率（从20％到2-4倍）。
• Carbamate as an accelerating group in intermolecular Pauson-Khand reaction
  作者：Shota Asano、Kaori Itto-Nakama、Hirokazu Arimoto

  DOI：10.1016/j.tetlet.2020.151974

  日期：2020.6

  The Pauson-Khand reaction (PKR) is a powerful means for the construction of cyclopentenones. However, its applications have been limited to the intramolecular version of this reaction because poor yield and regioselectivity are often the major problems in intermolecular PKR. Here we describe that a carbamate moiety in alkene substrate accelerates this intermolecular PKR. The reaction of N-4-dimethylaminophenyl

  Pauson-Khand反应（PKR）是构建环戊烯酮的有力手段。然而，由于不良的产率和区域选择性通常是分子间PKR的主要问题，其应用仅限于该反应的分子内形式。在这里，我们描述了烯烃底物中的氨基甲酸酯部分会加速这种分子间PKR。N -4-二甲基氨基苯基O-烯丙基氨基甲酸酯与炔-钴配合物的反应以高产率（高达90％）和区域选择性（＞ 9∶1）得到环戊烯酮。