tricarbonyl[η5-(2-oxo-2-(2-pyridinyl)ethyl)cyclopentadienyl]manganese(I) | 1006062-07-2

• 英文名称: tricarbonyl[η5-(2-oxo-2-(2-pyridinyl)ethyl)cyclopentadienyl]manganese(I)
• 英文别名: tricarbonyl[η5-((2-oxo-2-pyridyl)ethyl)cyclopentadienyl]manganese
• CAS: 1006062-07-2
• 化学式: C₁₅H₁₀MnNO₄
• 分子量: 323.187
• InChiKey: ZWFPVVPLHMCHSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tricarbonyl[η5-(2-oxo-2-(2-pyridinyl)ethyl)cyclopentadienyl]manganese(I) 以 四氢呋喃 为溶剂， 以93%的产率得到dicarbonyl[2-oxo-2-(2-pyridinyl)-κN-ethyl(η5-cyclopentadienyl)]manganese
  参考文献：
  名称：

  Linkage Isomerization as a Mechanism for Photochromic Materials: Cyclopentadienylmanganese Tricarbonyl Derivatives with Chelatable Functional Groups

  摘要：

  Two, bifunctional side-chain cyclopentadienylmanganese tricarbonyl complexes, 7 (pyridine and ketone side chain) and 14 (thioamide and pyridine side chain), were prepared and converted to chelates following CO dissociation by UV irradiation. Both pyridine (8) and carbonyl (9) chelates are observed following irradiation of 7. In contrast, only thioamide chelate (16) is observed following irradiation of 14 even though a pyridine group was available. Visible irradiation isomerizes the pyridine chelate 8 to the carbonyl chelate 9, which thermally isomerizes back to 8 at 25 degrees C in a few minutes, demonstrating a photochromic response from a cyclopentadienyl-manganese complex based on a linkage isomerization of a tethered functional group. DFT calculations predicted that the activation enthalpy of thermal linkage isomerization would be 20.8 kcal/mol and that the mechanism is likely an associative process that does not involve a simple dissociation of the manganese bond to the side-chain ketone. The DFT calculations were supported by subsequent dynamic NMR experiments that yielded an activation enthalpy and entropy of 21.4 +/- 0.8 kcal/mol and 3.5 +/- 0.1 eu, respectively. The studies indicate that a compound with a tethered, coordinated functional group, which is otherwise not labile, can isomerize by a low-energy pathway if there is an appropriate "conduit" to another functional group with a stronger metal-ligand bond. Thus, the preparation of photochromic organometallic complexes based on linkage isomerization will require a bridge that inhibits an associative walk between functional groups if they are to be bistable.

  DOI：

  10.1021/om701101h
• 作为产物：
  描述：

  2-吡啶甲酸乙酯 、 methylcyclopentadienyl manganese(I) tricarbonyl 在 potassium tert-butoxide 、 HCl 、 sodium bicarbonate 作用下， 以 二甲基亚砜 为溶剂， 以30%的产率得到tricarbonyl[η5-(2-oxo-2-(2-pyridinyl)ethyl)cyclopentadienyl]manganese(I)
  参考文献：
  名称：

  飞秒工程有机金属化学：带有侧苯羰基和吡啶羰基的环戊二烯基锰三羰基衍生物的光化学和超快螯合动力学

  摘要：

  已研究了CO光解后具有双官能侧链的环戊二烯基锰三羰基衍生物的螯合作用。以前的研究表明的那稳态辐照1（锰{η 5 -C 5 H ^ 4 CH 2 COR}（CO）3，R = 2-吡啶基）导致CO解离和形成的ö螯合物2与较少量的N-螯合物3。随后，2热重排为3。报道了一种新的制备1的方法，而类似物4（R =苯基）和5首次制备（R ＝ 4-吡啶基）。庚烷中4和5的稳态UV-vis，FTIR和NMR研究表明，O-螯合物6和7分别与侧链氧形成，但在微小的时间尺度上衰减。O-螯合物2至3的键合异构化比O-螯合物6所观察到的衰减更快（R = 2-吡啶基对Ph），即使后者存在0.1 M吡啶也是如此。在庚烷中的时间分辨红外研究中辐照4次后，超快O观察到螯合，但没有超快的溶剂配位。超快ø -chelation也用于观察5与一个身份不明的瞬态沿。辐照1后，观察到超快O-和N-螯合，但不包括超快溶剂配位。该结果表

  DOI：

  10.1021/om2003656