2,5-bis(trimethylsilyl)-1-bromo-3,4-dimethylphosphole | 247594-17-8

• 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: 2,5-bis(trimethylsilyl)-1-bromo-3,4-dimethylphosphole
• 英文别名: (1-Bromo-3,4-dimethyl-5-trimethylsilylphosphol-2-yl)-trimethylsilane
• CAS: 247594-17-8
• 化学式: C₁₂H₂₄BrPSi₂
• 分子量: 335.371
• InChiKey: TUOMZCUIIKJYFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,5-bis(trimethylsilyl)-1-bromo-3,4-dimethylphosphole 、 三甲基氯化锡 在 Li 作用下， 以 四氢呋喃 为溶剂， 以91%的产率得到2,5-bis(trimethylsilyl)-3,4-dimethyl-1-trimethylstannylphosphole
  参考文献：
  名称：

  Straightforward synthesis of phosphametallocenium cations of Rh and Ir

  摘要：

  Reaction of 3,4-dimethylphospholylthallium (Tl-1) with [Cp* MCl(2)](2) (M = Rh, Ir) leads to the formation of the dimeric species [(Cp* M)(2)(Me(2)C(4)H(2)P)(3)](+) 2 and 3 with bridging mu-eta(1): eta(1)-phospholyl ligands. The phosphametallocenium sandwich complexes [Cp* M(Me(2)C(4)(SiMe(3))(2)P)](+) 7 (M = Rh) and 8 (M = Ir) could be obtained from the reaction of [Cp* MCl(2)](2) and the 2,5-bis(trimethylsilyl)-1-trimethylstannylphosphole 6, with the bulky trimethylsilyl groups preventing the phosphole from eta(1)-and enforcing a eta(5)-coordination. The structures of phospharhodocenium cation 7 and a byproduct 9 containing a phosphairidocenium moiety could be determined by X-ray diffraction. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.04.042
• 作为产物：
  描述：

  1,1-bis(cyclopentadienyl)-3,4-dimethyl-2,5-bis(trimethylsilyl)zirconacyclopenta-2,4-diene 在 三溴化磷 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 2,5-bis(trimethylsilyl)-1-bromo-3,4-dimethylphosphole
  参考文献：
  名称：

  氧化锆环戊二烯和PBr 3介导的磷脂和1,1'-双膦的合成

  摘要：

  已经开发了通过格氏试剂与原位生成的1-溴磷脂反应来有效合成磷脂的方法。该方法允许在磷的磷原子上容易的取代基变化。1，1'-双膦也可通过Zn促进的1-溴磷的脱溴二聚而方便地制备。还合成了LAuCl的金-磷配合物，发现它们在金与4,5-二氢-1,2,4-恶二唑的金催化的酰胺的[3 + 2]环加成中起有效的催化剂的作用。

  DOI：

  10.1016/j.tetlet.2019.151388

文献信息

• Synthesis, Structure and Reactivity of Trimethylsilyl‐Substituted Phosphametallocenes
  作者：Rebekka Loschen、Christoph Loschen、Walter Frank、Christian Ganter

  DOI：10.1002/ejic.200600914

  日期：2007.2

  New sterically crowded phosphaferrocene and -ruthenocene derivatives were synthesized via the 2,5-bis(trimethylsilyl)phospholide anion 5. Their reactivity with regard to the exchange of the Me3Si groups for other functional groups was examined. X-ray structures were determined for the mono- (6) and the 1,1′-diphosphaferrocene (8). The activation barrier for ring–ring rotation in 8 was determined by

  通过 2,5-双（三甲基甲硅烷基）磷化物阴离子 5 合成了新的空间拥挤的磷酸二茂铁和 - 钌茂衍生物。研究了它们在 Me3Si 基团与其他官能团交换方面的反应性。确定了单- (6) 和 1,1'-二磷酸二茂铁 (8) 的 X 射线结构。8 中环-环旋转的激活势垒由核磁共振光谱确定并得到 DFT 计算的支持。通过亲电取代制备 2,5-双功能磷酸二茂铁的尝试未成功，但在途中产生了一种新的双齿 P,P 配体 (3) 及其 Mo(CO)4 配合物，它们均通过 X 射线衍射表征。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Synthesis of phospholes and 1,1′-biphospholes mediated by zirconacyclopentadienes and PBr3
  作者：Chunxiang Qin、Xin Xie、Gaonan Wang、Xueshun Jia、Yuanhong Liu

  DOI：10.1016/j.tetlet.2019.151388

  日期：2020.1

  The efficient synthesis of phospholes through the reactions of Grignard reagents with in situ-generated 1-bromophospholes has been developed. This method allows the easy substituent variation at the phosphorus atom of the phospholes. The 1,1’-biphospholes can also be conveniently prepared through Zn-promoted debromo-dimerization of 1-bromophospholes. The gold-phosphole complexes of LAuCl were also

  已经开发了通过格氏试剂与原位生成的1-溴磷脂反应来有效合成磷脂的方法。该方法允许在磷的磷原子上容易的取代基变化。1，1'-双膦也可通过Zn促进的1-溴磷的脱溴二聚而方便地制备。还合成了LAuCl的金-磷配合物，发现它们在金与4,5-二氢-1,2,4-恶二唑的金催化的酰胺的[3 + 2]环加成中起有效的催化剂的作用。
• Straightforward synthesis of phosphametallocenium cations of Rh and Ir
  作者：Verena Schnitzler、Walter Frank、Christian Ganter

  DOI：10.1016/j.jorganchem.2008.04.042

  日期：2008.7

  Reaction of 3,4-dimethylphospholylthallium (Tl-1) with [Cp* MCl(2)](2) (M = Rh, Ir) leads to the formation of the dimeric species [(Cp* M)(2)(Me(2)C(4)H(2)P)(3)](+) 2 and 3 with bridging mu-eta(1): eta(1)-phospholyl ligands. The phosphametallocenium sandwich complexes [Cp* M(Me(2)C(4)(SiMe(3))(2)P)](+) 7 (M = Rh) and 8 (M = Ir) could be obtained from the reaction of [Cp* MCl(2)](2) and the 2,5-bis(trimethylsilyl)-1-trimethylstannylphosphole 6, with the bulky trimethylsilyl groups preventing the phosphole from eta(1)-and enforcing a eta(5)-coordination. The structures of phospharhodocenium cation 7 and a byproduct 9 containing a phosphairidocenium moiety could be determined by X-ray diffraction. (C) 2008 Elsevier B.V. All rights reserved.