{(η4-cycloheptadiene)Fe(CO)3}2 | 73482-12-9

• 英文名称: {(η4-cycloheptadiene)Fe(CO)3}2
• CAS: 73482-12-9
• 化学式: C₂₀H₁₈Fe₂O₆
• 分子量: 466.053
• InChiKey: BCRYTYMGWADEFG-QISDOMOMSA-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：

  tricarbonyl(cycloheptadienyl)iron(II) tetrafluoroborate 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到{(η4-cycloheptadiene)Fe(CO)3}2
  参考文献：
  名称：

  Niemer, Burkhard; Breimair, Josef; Wagner, Barbara, Chemische Berichte, 1991, vol. 124, # 10, p. 2227 - 2236

  摘要：

  DOI：

文献信息

• Natural products synthesis using organoiron complexes
  作者：A. J. Pearson

  DOI：10.1351/pac198355111767

  日期：1983.1.1

  utilisation of cyclohexadienyl—Fe(CO)3 complexes of type 1 which we have now established as synthetic equivalents of cyclohexenone— y—cations (1), e.g. 2. Thus, reaction of lwith nucleophiles usually occurs regioselectively to give complexes of type 3, which are readily converted to cyclohexenones 4. It is appropriate to discuss the application of this concept to a total synthesis of the Aspidosperma alkaloid

  综述了二烯基-Fe(CO)2L 配合物作为天然产物合成中间体的应用，基于 (a) 作为环己烯酮 y-阳离子等价物的配合物，和 (b) 金属直接立体化学的能力七元环中的 CC 键形成。本文提供了一个机会，简要回顾我们在 1981-82 年间在英国剑桥大学开展的一些工作，以及一份关于 1982 年 10 月启动的一些新项目的进度报告，这些新项目是在搬到凯斯西预备大学。剑桥的工作基于使用 1 型环己二烯基-Fe(CO) 3 配合物，我们现在已将其确定为环己烯酮-y-阳离子的合成等价物 (1)，例如 2。因此，
• Concurrent one- and two-electron processes in electrophile/nucleophile interactions of organometallic ion pairs
  作者：R. E. Lehmann、T. M. Bockman、J. K. Kochi

  DOI：10.1021/ja00157a076

  日期：1990.1

  Interaction electrophyle/nucleophile entre CpMo(CO) 3 − et (η 5 -L)Fe(CO) 3 + , L=cyclohexadienyl, cycloheptadienyl, pentadienyl, hexadienyl

  亲电体/亲核体相互作用 entre CpMo(CO) 3 − et (η 5 -L)Fe(CO) 3 + , L=环己二烯基、环庚二烯基、戊二烯基、己二烯基
• Organoiron complexes in organic synthesis. 30. Approach to stereochemically defined cycloheptadiene derivatives using organoiron chemistry
  作者：Anthony J. Pearson、Sandra H. Kole、Bruce Chen

  DOI：10.1021/ja00351a064

  日期：1983.6
• Nucleophilic and electron-transfer processes in the ion-pair annihilation of cationic iron complexes (dienyl)Fe(CO)3+ with CpMo(CO)3-
  作者：R. E. Lehmann、Jay K. Kochi

  DOI：10.1021/om00047a049

  日期：1991.1

  Spontaneous electron transfer occurs upon the addition of the cationic electrophile (eta-5-cyclohexadienyl)Fe(CO)3+ to the anionic nucleophile CpMo(CO)3- in solution to afford the transient 19-electron radical (eta-5-cyclohexadienyl)Fe(CO)3. and the 17-electron radical CpMo(CO)3., which is isolated as the homo dimers [(eta-4-cyclohexadiene)Fe(CO)3]2 and [CpMo(CO)3]2, respectively, in quantitative yields. Under identical conditions, the open-chain analogue (eta-5-hexadienyl)Fe(CO)3+ leads to the nucleophilic adduct (OC)3Fe(eta-4-hexadienyl)Mo(CO)3Cp (5b) as the predominant product (75%). The structural characterization of 5b by X-ray crystallography (monoclinic space group P2(1)/n and a = 10.642 (2) angstrom, b = 7.658 (1) angstrom, c = 22.440 (4) angstrom, beta = 93.44 (1)-degrees, V = 1825 angstrom-3, Z = 4, R = 0.025, and R(w) = 0.025 for 2435 reflections with I > 3-sigma having 2-theta < 50-degrees) establishes the nucleophilic addition of CpMo(CO)3- to occur at the terminus of the coordinated dienyl ligand. The subsequent thermal decomposition of the nucleophilic adduct proceeds readily at 25-degrees-C by rate-limiting homolysis (DELTA-H-double-ended-dagger-almost-equal-to-28 kcal mol-1 and DELTA-S-double-ended-dagger = 14 eu) to the radical pair Fe(CO)3L. and CpMo(CO)3.. The overall electron transfer (proceeding as it does via the nucleophilic adduct) is shown to be a general mechanism for the ion-pair annihilation of the cationic dienyliron complexes. This circuitous pathway for electron transfer is discussed in terms of the relatively large intrinsic reorganization energy associated with the reduction of Fe(CO)3L+ to its 19-electron radical in the outer-sphere mechanism. Such a mechanistic conclusion presents a working format to account generally for the apparent dual pathways that commonly appear as concurrent nucleophilic-electrophilic and electron-transfer processes during the annihilation of organometallic ion pairs.