Me₃Si(OPO)

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Me₃Si(OPO)
• 英文别名: Me₃Si(1-oxo-2-pyridinone)；Sjfbk12；1-trimethylsilyloxypyridin-2-one
• 化学式: C₈H₁₃NO₂Si
• 分子量: 183.282
• InChiKey: SFABBPNOGWKCEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.11
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Me₃Si(OPO) 、 苯基三氯硅烷 以 氯仿 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  1-羟基-2-吡啶酮的中性和阳离子型双螯合单有机硅（IV）配合物

  摘要：

  A series of spirocyclic rnonoorganosilicon compounds of the form RSi(OPO)(2)Cl (R = phenyl (1), p-tolyl (2), benzyl (3), Me (4), Bu (5), thexyl (6); OPO = 1-oxo-2-pyridinone) was synthesized and characterized by H-1, C-13, and Si-29 NMR spectroscopy, X-ray crystallography, and elemental analysis. In the solid state, complexes 1-3 are neutral and possess cis-OPO ligands in an octahedral arrangement and complexes 4-6 are cationic and possess effectively trans-OPO ligands in nearly ideal square-pyramidal geometries along the Berry pseudorotation coordinate. In 4-6, chloride dissociation is attributed to the additive effect of multiple intermolecular C H center dot center dot center dot CI interactions in their crystals. In DMSO-d(6) solution, compounds 1-6 form cationic hexacoordinate DMSO adducts with trans-OPO ligands, all of which undergo dynamic isomerization with energy barriers of similar to 18-19 kcal/mol. Compounds with better leaving groups, (p-tolyl)Si(OPO)(2)X (X = I (7), X = triflate (8)), exhibit solution NMR spectra identical with those of 2, supporting anion dissociation in each. The fluoride derivatives RSi(OPO)(2)F (R = benzyl (9), Me (10)) exhibit hexacoordinate geometries with cis-OPO ligands in the solid state and exhibit dynamic isomerization in solution. Overall, these studies indicate, in both the solid and solution states, that the trans-OPO ligand arrangement is favored when anions are dissociated and a cis-OPO ligand arrangement when anions are coordinated.

  DOI：

  10.1021/acs.organomet.6b00796
• 作为产物：
  描述：

  羟吡啶酮 、 三甲基氯硅烷 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以92%的产率得到Me₃Si(OPO)
  参考文献：
  名称：

  Chelation and Stereodynamic Equilibria in Neutral Hypercoordinate Organosilicon Complexes of 1-Hydroxy-2-pyridinone

  摘要：

  A series of neutral organosilicon compounds, R3Si(OPO) (R = Me (1), Et (2), Ph (3)), cis-R2Si(OPO)(2) (R = Me (4), Et (5), Pr-i (6), Bu-t (7), Ph (9)), (CH2)(3)Si(OPO)(2) (8), and cis-R2Si(OPO)Cl (R = Me (10), Et (11)) (OPO = 1-oxo-2-pyridinone) have been prepared and fully characterized. X-ray crystallographic analyses show 1 to be tetracoordinate, 3, 7, and 10 to be pentacoordinate, and 4-6, 8, and 9 to be hexacoordinate. In the hexacoordinate structures, a mixture of diastereomers is observed in the form of C/N site disorder in each OPO ligand. Variable-temperature C-13 and Si-29 NMR studies indicate reversible Si <- OC bond, dissociation occurring in all pentacoordinate and hexacoordinate complexes to a varying degree with greater tendency toward dissociation in hydrogen-bonding donor solvents. Significant weakening of the dative Si <- OC bond in 3 is observed in the cocrystallized adduct solvate 3 center dot Ph3SiOH center dot(1)/2C5H12, providing structural evidence for the decrease in coordination number of the OPO ligand by hydrogen-bonding donors. In the hexacoordinate complexes, increasing steric bulk of ancillary ligands also was found to promote dissociation. H-1 and C-13 VT-NMR studies of 4, 6, 8, and 9 indicate stereoisomerization equilibria concurrent with Si <- OC bond dissociation proposed to occur through trigonal-bipyramidal intermediates.

  DOI：

  10.1021/om400907s

文献信息

• Bailly, Theodorine; Burgada, Ramon, Phosphorus, Sulfur and Silicon and the Related Elements, 1991, vol. 63, # 1/2, p. 33 - 43
  作者：Bailly, Theodorine、Burgada, Ramon

  DOI：——

  日期：——
• Neutral and Cationic Bis-Chelate Monoorganosilicon(IV) Complexes of 1-Hydroxy-2-pyridinone
  作者：James G. Koch、William W. Brennessel、Bradley M. Kraft

  DOI：10.1021/acs.organomet.6b00796

  日期：2017.2.13

  A series of spirocyclic rnonoorganosilicon compounds of the form RSi(OPO)(2)Cl (R = phenyl (1), p-tolyl (2), benzyl (3), Me (4), Bu (5), thexyl (6); OPO = 1-oxo-2-pyridinone) was synthesized and characterized by H-1, C-13, and Si-29 NMR spectroscopy, X-ray crystallography, and elemental analysis. In the solid state, complexes 1-3 are neutral and possess cis-OPO ligands in an octahedral arrangement and complexes 4-6 are cationic and possess effectively trans-OPO ligands in nearly ideal square-pyramidal geometries along the Berry pseudorotation coordinate. In 4-6, chloride dissociation is attributed to the additive effect of multiple intermolecular C H center dot center dot center dot CI interactions in their crystals. In DMSO-d(6) solution, compounds 1-6 form cationic hexacoordinate DMSO adducts with trans-OPO ligands, all of which undergo dynamic isomerization with energy barriers of similar to 18-19 kcal/mol. Compounds with better leaving groups, (p-tolyl)Si(OPO)(2)X (X = I (7), X = triflate (8)), exhibit solution NMR spectra identical with those of 2, supporting anion dissociation in each. The fluoride derivatives RSi(OPO)(2)F (R = benzyl (9), Me (10)) exhibit hexacoordinate geometries with cis-OPO ligands in the solid state and exhibit dynamic isomerization in solution. Overall, these studies indicate, in both the solid and solution states, that the trans-OPO ligand arrangement is favored when anions are dissociated and a cis-OPO ligand arrangement when anions are coordinated.
• Chelation and Stereodynamic Equilibria in Neutral Hypercoordinate Organosilicon Complexes of 1-Hydroxy-2-pyridinone
  作者：Bradley M. Kraft、William W. Brennessel

  DOI：10.1021/om400907s

  日期：2014.1.13

  A series of neutral organosilicon compounds, R3Si(OPO) (R = Me (1), Et (2), Ph (3)), cis-R2Si(OPO)(2) (R = Me (4), Et (5), Pr-i (6), Bu-t (7), Ph (9)), (CH2)(3)Si(OPO)(2) (8), and cis-R2Si(OPO)Cl (R = Me (10), Et (11)) (OPO = 1-oxo-2-pyridinone) have been prepared and fully characterized. X-ray crystallographic analyses show 1 to be tetracoordinate, 3, 7, and 10 to be pentacoordinate, and 4-6, 8, and 9 to be hexacoordinate. In the hexacoordinate structures, a mixture of diastereomers is observed in the form of C/N site disorder in each OPO ligand. Variable-temperature C-13 and Si-29 NMR studies indicate reversible Si <- OC bond, dissociation occurring in all pentacoordinate and hexacoordinate complexes to a varying degree with greater tendency toward dissociation in hydrogen-bonding donor solvents. Significant weakening of the dative Si <- OC bond in 3 is observed in the cocrystallized adduct solvate 3 center dot Ph3SiOH center dot(1)/2C5H12, providing structural evidence for the decrease in coordination number of the OPO ligand by hydrogen-bonding donors. In the hexacoordinate complexes, increasing steric bulk of ancillary ligands also was found to promote dissociation. H-1 and C-13 VT-NMR studies of 4, 6, 8, and 9 indicate stereoisomerization equilibria concurrent with Si <- OC bond dissociation proposed to occur through trigonal-bipyramidal intermediates.