(η4-C,C'-(cyclohexadiene)2)Fe2(CO)6 | 57378-64-0

• 英文名称: (η4-C,C'-(cyclohexadiene)2)Fe2(CO)6
• CAS: 57378-64-0
• 化学式: C₁₈H₁₄Fe₂O₆
• 分子量: 438.0
• InChiKey: BGVWCIBBARYQFX-RAUDNFPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 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

• 作为产物：
  描述：

  (η5-cyclohexadienyl)2Fe2(CO)4 在 CO 作用下， 以 甲苯 为溶剂， 生成 (η4-C,C'-(cyclohexadiene)2)Fe2(CO)6
  参考文献：
  名称：

  Thermal and photochemical reactions of (.eta.5-cyclohexadienyl)2Fe2(CO)4 in the presence of 2e- donor ligands: isolation and characterization of (.eta.4-C,C'-(cyclohexadiene)2)Fe2(CO)4L2

  摘要：

  DOI：

  10.1021/ja00185a056

文献信息

• 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
• Electrochemical behaviour and reactivity of cyclohexadienyl iron complexes
  作者：M.Fernanda N.N. Carvalho、Armando J.L. Pombeiro、Ian M. Shrophire、G. Richard Stephenson

  DOI：10.1016/0020-1693(95)04992-4

  日期：1996.7

  Abstract The electrochemical behaviour of the monosubstituted cyclohexadienyl complexes [Fe( η 5 -2-R-cyclohexadienyl)(CO) 3 ][PF 6 ] (R  H, Me, n-Bu, MeO, Ph, MeOC 6 H 4 , CF 3 C 6 H 4 ), [Fe( η 5 -1-EtO-cyclohexadienyl)(CO) 3 ][PF 6 ], the disubstituted species [Fe( η 5 -R,R′-cyclohexadienyl)(CO) 3 ][PF 6 ] (R R′  MeO or Me; R  Me, R′  MeO), and [Fe( η 5 -R-cyclohexadienyl)(CO) 2 (PPh 3 )][PF

  摘要单取代的环己二烯基配合物[Fe（η5 -2-R-环己二烯基）（CO）3] [PF 6]（R H，Me，n-Bu，MeO，Ph，MeOC 6 H 4， CF 3 C 6 H 4），[Fe（η5 -1-EtO-环己二烯基）（CO）3] [PF 6]，双取代物质[Fe（η5 -R，R'-环己二烯基）（CO）3 ] [PF 6]（RR'MeO或Me； RMe，R'MeO）和[Fe（η5 -R-环己二烯基）（CO）2（PPh 3）] [PF 6]（通过循环伏安法和受控电势电解法研究了RH，Ph）。它们以取决于环己二烯基取代基和在金属上的共配体的电子性质的电势经历单电子不可逆的阴极过程。特别是，具有芳族取代基的三羰基铁络合物的还原电位明显高于具有脂肪族取代基的三羰基铁络合物，而羰基被三苯基膦配体取代会降低阴极电位。通过阴极控制电位的电解，它们进行CC偶联，在某些情况下（未取代或烷氧基取
• Powell, John; Horvath, Michael J., Organometallics, 1993, vol. 12, # 10, p. 4073 - 4076
  作者：Powell, John、Horvath, Michael J.

  DOI：——

  日期：——
• 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.