η3-anti-methallyl iron tricarbonyl SnMe3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: η3-anti-methallyl iron tricarbonyl SnMe3
• 化学式: C₁₀H₁₆FeO₃Sn
• 分子量: 358.792
• InChiKey: ZQFJBUFAGDPGQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  η3-anti-methallyl iron tricarbonyl SnMe3 、 potassium hydride 以 四氢呋喃 为溶剂， 以>99的产率得到anti-methallyl iron tricarbonyl potassium
  参考文献：
  名称：

  （二烯）三羰基铁络合物的氢化物还原反应，以取代取代的（烯丙基）三羰基铁阴离子。用Et3BH-检测甲酰中间体在氢化（1,3-丁二烯）三羰基铁中的甲酰中间体

  摘要：

  Reactions of (butadiene)iron tricarbonyl or (1-phenylbutadiene)iron tricarbonyl with Et3BH-in tetrahydrofuran monitored by IR spectroscopy showed efficient conversion to the corresponding (allyl)iron tricarbonyl anions (CH3CH---CH---CH2)Fe(CO)3- and (CH3CH---CH-CHC6H5)Fe(CO)3-. Treatment of these solutions with (CH3)3SnCl resulted in formation of (anti-methallyl)Fe(CO)3-SnMe3, anti-12 and (anti-1-methyl-syn-3-phenylallyl)Fe(CO)3-SnMe3, anti,syn-13. These anti isomers thermally isomerize to their syn isomers by clean first-order kinetics (anti-12 to syn-12, k = 2.6 x 10(-5) s-1, 55-degrees-C; anti,syn-13 to syn,syn-13, k = 5.8 x 10(-6) s-1, 25-degrees-C). The sterochemistry of syn,syn-13 was confirmed by X-ray analysis (monoclinic, P2(1/n), a = 14.830(3) angstrom, b = 7.5651(18) angstrom, c = 15.7202(18) angstrom, beta = 102.001(13)-degrees, Z = 4). Treatment of the (allyl)iron tin complexes anti-12, syn-12, anti,syn-13, and syn,syn-13 with KH results in clean formation of the corresponding (allyl)iron tricarbonyl anions which can be isolated in good yields as their potassium salts. The configuration of the allyl unit is maintained in the reduction reaction. Low temperature H-1, H-2, and C-13 NMR experiments reveal that the anionic formyl complex (C4H6)(CO)2FeCHO- is an intermediate in the formation of (anti-methallyl)Fe(CO)3- from Et3BH- and (butadiene)iron tricarbonyl. Hydride migration from formyl to C1 of the butadiene ligand occurs at -50-degrees-C, k = 8.3 x 10(-5) s-1, DELTAG(double dagger) = 17 kcal/mol.

  DOI：

  10.1021/om00033a041
• 作为产物：
  描述：

  tricarbonyl(η(4)-buta-1,3-diene)iron 、 三甲基氯化锡 、 三乙基氢硼化钾 以 四氢呋喃 为溶剂， 以79%的产率得到η3-anti-methallyl iron tricarbonyl SnMe3
  参考文献：
  名称：

  （二烯）三羰基铁络合物的氢化物还原反应，以取代取代的（烯丙基）三羰基铁阴离子。用Et3BH-检测甲酰中间体在氢化（1,3-丁二烯）三羰基铁中的甲酰中间体

  摘要：

  Reactions of (butadiene)iron tricarbonyl or (1-phenylbutadiene)iron tricarbonyl with Et3BH-in tetrahydrofuran monitored by IR spectroscopy showed efficient conversion to the corresponding (allyl)iron tricarbonyl anions (CH3CH---CH---CH2)Fe(CO)3- and (CH3CH---CH-CHC6H5)Fe(CO)3-. Treatment of these solutions with (CH3)3SnCl resulted in formation of (anti-methallyl)Fe(CO)3-SnMe3, anti-12 and (anti-1-methyl-syn-3-phenylallyl)Fe(CO)3-SnMe3, anti,syn-13. These anti isomers thermally isomerize to their syn isomers by clean first-order kinetics (anti-12 to syn-12, k = 2.6 x 10(-5) s-1, 55-degrees-C; anti,syn-13 to syn,syn-13, k = 5.8 x 10(-6) s-1, 25-degrees-C). The sterochemistry of syn,syn-13 was confirmed by X-ray analysis (monoclinic, P2(1/n), a = 14.830(3) angstrom, b = 7.5651(18) angstrom, c = 15.7202(18) angstrom, beta = 102.001(13)-degrees, Z = 4). Treatment of the (allyl)iron tin complexes anti-12, syn-12, anti,syn-13, and syn,syn-13 with KH results in clean formation of the corresponding (allyl)iron tricarbonyl anions which can be isolated in good yields as their potassium salts. The configuration of the allyl unit is maintained in the reduction reaction. Low temperature H-1, H-2, and C-13 NMR experiments reveal that the anionic formyl complex (C4H6)(CO)2FeCHO- is an intermediate in the formation of (anti-methallyl)Fe(CO)3- from Et3BH- and (butadiene)iron tricarbonyl. Hydride migration from formyl to C1 of the butadiene ligand occurs at -50-degrees-C, k = 8.3 x 10(-5) s-1, DELTAG(double dagger) = 17 kcal/mol.

  DOI：

  10.1021/om00033a041

文献信息

• Chang, Seok; Yoon, Jaeyon; Brookbart, Maurice, Journal of the American Chemical Society, 1994, vol. 116, # 5, p. 1869 - 1879
  作者：Chang, Seok、Yoon, Jaeyon、Brookbart, Maurice

  DOI：——

  日期：——
• Hydride reduction of (diene)iron tricarbonyl complexes as a route to substituted (allyl)iron tricarbonyl anions. Detection of a formyl intermediate in the hydride reduction of (1,3-butadiene)iron tricarbonyl by Et3BH-
  作者：Seok Chang、Peter S. White、Maurice Brookhart

  DOI：10.1021/om00033a041

  日期：1993.9

  Reactions of (butadiene)iron tricarbonyl or (1-phenylbutadiene)iron tricarbonyl with Et3BH-in tetrahydrofuran monitored by IR spectroscopy showed efficient conversion to the corresponding (allyl)iron tricarbonyl anions (CH3CH---CH---CH2)Fe(CO)3- and (CH3CH---CH-CHC6H5)Fe(CO)3-. Treatment of these solutions with (CH3)3SnCl resulted in formation of (anti-methallyl)Fe(CO)3-SnMe3, anti-12 and (anti-1-methyl-syn-3-phenylallyl)Fe(CO)3-SnMe3, anti,syn-13. These anti isomers thermally isomerize to their syn isomers by clean first-order kinetics (anti-12 to syn-12, k = 2.6 x 10(-5) s-1, 55-degrees-C; anti,syn-13 to syn,syn-13, k = 5.8 x 10(-6) s-1, 25-degrees-C). The sterochemistry of syn,syn-13 was confirmed by X-ray analysis (monoclinic, P2(1/n), a = 14.830(3) angstrom, b = 7.5651(18) angstrom, c = 15.7202(18) angstrom, beta = 102.001(13)-degrees, Z = 4). Treatment of the (allyl)iron tin complexes anti-12, syn-12, anti,syn-13, and syn,syn-13 with KH results in clean formation of the corresponding (allyl)iron tricarbonyl anions which can be isolated in good yields as their potassium salts. The configuration of the allyl unit is maintained in the reduction reaction. Low temperature H-1, H-2, and C-13 NMR experiments reveal that the anionic formyl complex (C4H6)(CO)2FeCHO- is an intermediate in the formation of (anti-methallyl)Fe(CO)3- from Et3BH- and (butadiene)iron tricarbonyl. Hydride migration from formyl to C1 of the butadiene ligand occurs at -50-degrees-C, k = 8.3 x 10(-5) s-1, DELTAG(double dagger) = 17 kcal/mol.