Bis(trimethylsilyl)(dimethylphosphino)methan | 78312-99-9

• 物质功能分类: 有机原料 - 有机膦化合物
• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: Bis(trimethylsilyl)(dimethylphosphino)methan
• 英文别名: [Bis(trimethylsilyl)methyl](dimethyl)phosphane；bis(trimethylsilyl)methyl-dimethylphosphane
• CAS: 78312-99-9
• 化学式: C₉H₂₅PSi₂
• 分子量: 220.442
• InChiKey: RITNPRKCLDCWSF-UHFFFAOYSA-N

物化性质

• 沸点：
  216.8±20.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  三氯化铝 、 Bis(trimethylsilyl)(dimethylphosphino)methan 以 正戊烷 为溶剂， 以98.2%的产率得到((bis(trimethylsilyl)methyl)dimethyl-l5-phosphaneyl)aluminum(IV) chloride
  参考文献：
  名称：

  (Phosphinomethyl)aluminum compounds: the role of coligands and x-ray structure determinations of the heterocycles (TMEDA)LiClAlMe2C(SiMe3)2PMe2 and (Me)(Cl)AlC(SiMe3)2PMe2SiMe2C(SiMe3)PMe2

  摘要：

  From the 1:1 reaction of R2AlCl (a, R = Cl; b, R = Me) with {Li[C(SiMe3)2(PMe2)]}2, six-membered heterocycles [R2AlC(SiMe3)2(PMe2)]2 (1a,b) are obtained. The 1:2 reaction for R = Cl involves a facile methyl migration from the silicon to aluminum and leads to the novel heterocycle (Me)(Cl)Al activated C-(SiMe3)2PMe2SiMe2C(SiMe3)PMe2 (2), exhibiting a number of unusual structural features, as shown by the X-ray structure determination of 2, which crystallizes from pentane (colorless crystals, triclinic, space group P1, a = 9.161 (1), b = 15.280 (2), and c = 11.832 (1) angstrom, alpha = 109.62 (1), beta = 74.57 (1), and gamma = 98.39 (1)-degrees, V = 1500.9 angstrom 3, Z = 2, R = 0.035 for 283 refined parameters and 4841 observables). A formal [3 + 2] cycloaddition is observed in the same 1:1 reaction in the presence of tetramethylethylenediamine (TMEDA) to give five-membered heterocycles (TMEDA)L activated iClAlR2C(SiMe3)2PMe2 (3a,b), incorporating five different elements within the ring. 3b crystallizes from pentane (colorless crystals, monoclinic, space group P2(1)/n, a = 8.915 (1), b = 18.887 (2), and c = 16.558 (2) angstrom, alpha = 90.0 (1), beta = 92.52 (1), gamma = 90.0 (1)-degrees, V = 2785.3 angstrom 3, Z = 4, R = 0.064 for 268 refined parameters and 3830 observables). An X-ray structure determination shows the ambidentate phosphinomethanide ligand to be bound to the lithium atom via phosphorus and to the aluminum atom via carbon. 3b thermally is converted to 1b by loss of TMEDA, whereas 3a is stable to thermolysis. In the presence of tetrahydrofuran (THF), the 1:1 reaction for R = Me gives rise to Me2(THF)Al[C(SiMe3)2(PMe2)] (4), which is also obtained from 3b and THF. As a byproduct, due to some traces of HCl, in the 1:1 reaction (R = Cl) the ylide complex Cl3AlC(SiMe3)2PMe2H (5) is identified spectroscopically and eventually can be isolated. 5 either is converted by further addition of HCl to [HC(SiMe3)2PMe2H][AlCl4] (6) or rearranges to its tautomer Cl3AlPMe2C(SiMe3)2H (7), thus constituting a novel example for an ylide half-arrow-right-over-half-arrow-left phosphane diadic relationship. 7 is also obtained directly from AlCl3 and HC(SiMe3)2(PMe2).

  DOI：

  10.1021/om00054a064
• 作为产物：
  描述：

  三甲基氯硅烷 、 (trimethyl-silyl)-methyl-dimethyl-phosphine 在 叔丁基锂 作用下， 生成 Bis(trimethylsilyl)(dimethylphosphino)methan
  参考文献：
  名称：

  Karsch, Hans H.; Appelt, Armin; Deubelly, Brigitte, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1988, vol. 43, # 11, p. 1416 - 1426

  摘要：

  DOI：

文献信息

• Karsch, Hans H.; Richter, Roland; Schier, Annette, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1993, vol. 48, # 11, p. 1533 - 1543
  作者：Karsch, Hans H.、Richter, Roland、Schier, Annette

  DOI：——

  日期：——
• Einfluß der Co-Liganden auf die Lithiumkoordination von Phosphinomethaniden und Molekülstructur von {(THF)Li[C(SiMe3)2(PMe2]}2
  作者：Hans H. Karsch、Karin Zellner、Siegfried Gamper、Gerhard Müller

  DOI：10.1016/0022-328x(91)86107-2

  日期：1991.8

  The first lithium monophosphinomethanide complex with a monodentate co-ligand, (THF)Li[C(SiMe3)2(PMe2)]}2 is obtained from the solvate-free complex and tetrahydrofuran (THF), and shown by X-ray crystallography to consist of a dinuclear, six-membered ring in a chair conformation with lithium atoms of coordination number three.
• (Phosphinomethyl)aluminum compounds: the role of coligands and x-ray structure determinations of the heterocycles (TMEDA)LiClAlMe2C(SiMe3)2PMe2 and (Me)(Cl)AlC(SiMe3)2PMe2SiMe2C(SiMe3)PMe2
  作者：Hans H. Karsch、Karin Zellner、Gerhard Mueller

  DOI：10.1021/om00054a064

  日期：1991.8

  From the 1:1 reaction of R2AlCl (a, R = Cl; b, R = Me) with Li[C(SiMe3)2(PMe2)]}2, six-membered heterocycles [R2AlC(SiMe3)2(PMe2)]2 (1a,b) are obtained. The 1:2 reaction for R = Cl involves a facile methyl migration from the silicon to aluminum and leads to the novel heterocycle (Me)(Cl)Al activated C-(SiMe3)2PMe2SiMe2C(SiMe3)PMe2 (2), exhibiting a number of unusual structural features, as shown by the X-ray structure determination of 2, which crystallizes from pentane (colorless crystals, triclinic, space group P1, a = 9.161 (1), b = 15.280 (2), and c = 11.832 (1) angstrom, alpha = 109.62 (1), beta = 74.57 (1), and gamma = 98.39 (1)-degrees, V = 1500.9 angstrom 3, Z = 2, R = 0.035 for 283 refined parameters and 4841 observables). A formal [3 + 2] cycloaddition is observed in the same 1:1 reaction in the presence of tetramethylethylenediamine (TMEDA) to give five-membered heterocycles (TMEDA)L activated iClAlR2C(SiMe3)2PMe2 (3a,b), incorporating five different elements within the ring. 3b crystallizes from pentane (colorless crystals, monoclinic, space group P2(1)/n, a = 8.915 (1), b = 18.887 (2), and c = 16.558 (2) angstrom, alpha = 90.0 (1), beta = 92.52 (1), gamma = 90.0 (1)-degrees, V = 2785.3 angstrom 3, Z = 4, R = 0.064 for 268 refined parameters and 3830 observables). An X-ray structure determination shows the ambidentate phosphinomethanide ligand to be bound to the lithium atom via phosphorus and to the aluminum atom via carbon. 3b thermally is converted to 1b by loss of TMEDA, whereas 3a is stable to thermolysis. In the presence of tetrahydrofuran (THF), the 1:1 reaction for R = Me gives rise to Me2(THF)Al[C(SiMe3)2(PMe2)] (4), which is also obtained from 3b and THF. As a byproduct, due to some traces of HCl, in the 1:1 reaction (R = Cl) the ylide complex Cl3AlC(SiMe3)2PMe2H (5) is identified spectroscopically and eventually can be isolated. 5 either is converted by further addition of HCl to [HC(SiMe3)2PMe2H][AlCl4] (6) or rearranges to its tautomer Cl3AlPMe2C(SiMe3)2H (7), thus constituting a novel example for an ylide half-arrow-right-over-half-arrow-left phosphane diadic relationship. 7 is also obtained directly from AlCl3 and HC(SiMe3)2(PMe2).
• Karsch, Hans H.; Appelt, Armin; Deubelly, Brigitte, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1988, vol. 43, # 11, p. 1416 - 1426
  作者：Karsch, Hans H.、Appelt, Armin、Deubelly, Brigitte、Zellner, Karin、Riede, Juergen、Mueller, Gerhard

  DOI：——

  日期：——