tricarbonyl[chloromethyl(η5-cyclopentadienyl)]manganese | 12152-62-4

• 英文名称: tricarbonyl[chloromethyl(η5-cyclopentadienyl)]manganese
• 英文别名: chloromethylcymantrene
• CAS: 12152-62-4
• 化学式: C₉H₆ClMnO₃
• 分子量: 252.536
• InChiKey: VFTCKZMGQJHNKV-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[chloromethyl(η5-cyclopentadienyl)]manganese 、 1-(2,4,6-三甲基苯基)-咪唑 在 potassium iodide 作用下， 以 乙腈 为溶剂， 反应 120.0h， 以84%的产率得到
  参考文献：
  名称：

  含Cp链状N杂环碳原子配体的半三明治锰配合物：催化酮氢化硅烷化反应的合成及机理研究

  摘要：

  DOI：

  10.1021/acs.organomet.6b00785
• 作为产物：
  描述：

  tricarbonyl[hydroxymethyl(η5-cyclopentadienyl)]manganese 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 生成 tricarbonyl[chloromethyl(η5-cyclopentadienyl)]manganese
  参考文献：
  名称：

  光学活性的单取代的cymantrene衍生物。化合物的手性特征与绝对构型的关系

  摘要：

  首次总结了十四种具有手性中心直接与Cp环相连的旋光性单取代cymantrene衍生物的手性（CD，ORD和[α]）的研究结果。已经发现，这些化合物的（R）-对映异构体对CD光谱中310-360 nm范围内的“茂金属”转变表现出负的Cotton效应，与取代基和溶剂的性质无关。

  DOI：

  10.1016/0022-328x(86)80008-0

文献信息

• Chelate cyclopentadienylmanganese dicarbonyl complexes
  作者：M.I. Rybinskaya、L.M. Korneva

  DOI：10.1016/s0022-328x(00)89224-4

  日期：1982.5

  Cyclopentadienylmanganese tricarbonyl complexes with allyloxymethyl- and propargyloxymethyl substituents have been synthesized. Under UV irradiation, they give new chelate cyclopentadienylmanganese dicarbonyl complexes with coordinated vinyl and ethinyl groups. In the case of cyclopentadienylmanganese-cricarbonyl complexes having two such substituents, only mono-bridged chelate dicarbonyl compounds

  已经合成了具有烯丙氧基甲基-和炔丙基氧基甲基取代基的环戊二烯基锰三羰基配合物。在紫外线照射下，它们产生具有配位的乙烯基和亚乙烯基的新的螯合的环戊二烯基锰二羰基配合物。在具有两个这样的取代基的环戊二烯基锰-羰基羰基配合物的情况下，仅获得了单桥螯合物二羰基化合物。环戊二烯基三羰基锰的α-Oxo-ω-氰基烷基衍生物在紫外线照射下，得到氰基的金属和氮原子之间具有σ-配位的新螯合物。通过相同方法从环戊二烯基锰三羰基的ω-氰基烷基衍生物获得螯合物的尝试失败。
• Linkage Isomerization as a Mechanism for Photochromic Materials: Cyclopentadienylmanganese Tricarbonyl Derivatives with Chelatable Functional Groups
  作者：Tung T. To、Charles B. Duke III、Christopher S. Junker、Casey M. O’Brien、Charles R. Ross II、Craig E. Barnes、Charles Edwin Webster、Theodore J. Burkey

  DOI：10.1021/om701101h

  日期：2008.1.1

  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.