fac-(η4-norbornadiene)(η2-norbornadiene)Mo(CO)3 | 124816-59-7

• 英文名称: fac-(η4-norbornadiene)(η2-norbornadiene)Mo(CO)3
• 英文别名: fac-(η2-norbornadiene)(η4-norbornadiene)Mo(CO)3
• CAS: 124816-59-7
• 化学式: C₁₇H₁₆MoO₃
• 分子量: 364.252
• InChiKey: CZYVDMQHTFNWJB-SEGRDSFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  (bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum(0) 在 2,5-降冰片二烯 作用下， 以 polyethylene 为溶剂， 生成 fac-(η4-norbornadiene)(η2-norbornadiene)Mo(CO)3 、 fac-(η4-norbornadiene)(η2-norbornadiene)Mo(CO)3
  参考文献：
  名称：

  A New Approach To Studying the Mechanism of Catalytic Reactions:  An Investigation into the Photocatalytic Hydrogenation of Norbornadiene and Dimethylfumarate Using Polyethylene Matrices at Low Temperature and High Pressure

  摘要：

  This paper presents a new method for investigating the mechanisms of homogeneously catalyzed reactions involving gases, particularly H-2. We show how the combination of polyethylene (PE) matrices and high pressure-low temperature (HPLT) experiments can be used to provide new mechanistic information on hydrogenation processes. In particular, we show how we are able to generate reaction intermediates at low temperature, and then to extract the contents of the PE film at room temperature to characterize the organic products using GC-MS, We have used our new technique to probe both the hydrogenation of dimethyl fumarate (DF), using Fe(CO)(4)(eta (2)-DF) as the catalytic species, and the hydrogenation of norbornadiene (NBD), using (NBD)M(CO)(4) (M = Cr or Mo) as the catalytic species. Irradiation of Fe(CO)(4)(eta (2)-DF) in a PE matrix at 150 K resulted in the formation of an intermediate complex tentatively assigned Fe(CO)(3)(eta (4)-DF). Warming this complex to 260 K under H-2 leads to the formation of Fe(CO)(3)(eta (2)-DF)(eta (2)-H-2). Further warming of the reaction system results in the hydrogenation of the coordinated DF, to generate dimethyl succinate (DS), Characterization of the intermediate species was obtained using FTIR spectroscopy. Formation of DS was confirmed using both FTIR spectroscopy and GC-MS analysis. UV photolysis of (NBD)M(CO)I in PE under H-2 in the presence of excess NBD results in the formation of the hydrogenated products norbornene (NBN) and nortricyclene (NTC), with trace amounts of norbornane (NBA) being observed. These products were in similar ratios to those observed in fluid solution. However, for (NBD)Mo(CO)(4), the relative amounts of the organic products change considerably when the reaction is repeated in PE under H-2 in the absence of free NBD, with NEA being the major product. The use of our HPLT cell allows us to vent and exchange high pressures of gases with ease, and as such we have performed gas exchange reactions with H-2 and D-2. Analysis of the reaction products from these exchange reactions with GC-MS provides evidence for the mechanism of formation of NEA, in both the presence and absence of excess NBD, a reaction which has been largely ignored in previous studies.

  DOI：

  10.1021/ja004345t

文献信息

• Infrared spectroscopic studies on the photocatalytic hydrogenation of norbornadiene by Group 6 metal carbonyls. 2. The role of the diene and the characterization of (.eta.4-norbornadiene)(.eta.2-norbornadiene)M(CO)3 complexes
  作者：P. Michael Hodges、Sarah A. Jackson、Juergen Jacke、Martyn Poliakoff、James J. Turner、Friedrich Wilhelm Grevels

  DOI：10.1021/ja00159a052

  日期：1990.1

  components of the catalytic hydrogenation mixture (e.g., Hsub 2}, NBD, CO, etc.). The measurements show that, for a particular intermediate, the rates of reaction with Hsub 2} and NBD are quite similar. Thus, in a typical catalytic reaction mixture, intermediates are more likely to react with NBD than Hsub 2}, because the concentration of NBD is considerably higher than that of Hsub 2}. Fourier-transform

  M(CO)sub 6} 和 (NBD)M(CO)sub 4}（NBD = 降冰片二烯）的紫外激光闪光光解分别用于生成中间体 M(CO)sub 5}(s) (s = 正庚烷；M = Cr、Mo 和 W) 和 (eta}sup 4}-NBD)M(CO)sub 3}(s) fac 和 mer 异构体；M = Mo 和 W。然后使用快速 (μ}s) 时间分辨 IR 光谱来测量这些中间体与可能是催化氢化混合物组分的物种（例如，Hsub 2}， NBD、CO 等）。测量表明，对于特定的中间体，与 Hsub 2} 和​​ NBD 的反应速率非常相似。因此，在典型的催化反应混合物中，中间体比 Hsub 2} 更可能与 NBD 反应，因为 NBD 的浓度明显高于 Hsub 2} 的浓度。傅里叶变换 IR 用于监测室温下光催化氘化过程中溶液中存在的羰基物质。这些包括以前未知的复合物 fac-