[Cp(dppe)Fe(MeCN)]Br | 70459-84-6

• 英文名称: [Cp(dppe)Fe(MeCN)]Br
• 英文别名: (C₅H₅)(bis(diphenylphosphino)ethane)Fe(NCCH₃)Br；Cp(1,2-bis(diphenyl-phosphino)ethane)Fe(NCCH3)Br；Cp(dppe)Fe(NCCH₃)Br；Cp(dppe)Fe(NCCH3)Br；[Fe(C5H5)(dppe)CH3CN)]Br
• CAS: 70459-84-6
• 化学式: Br*C₃₃H₃₂FeNP₂
• 分子量: 640.322
• InChiKey: CMDBHATZFQRXKV-UHFFFAOYSA-M

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：

  potassium dicyanoargentate(I) 、 [Cp(dppe)Fe(MeCN)]Br 以 甲醇 为溶剂， 以52%的产率得到Cp(dppe)Fe-CN-Ag-CN
  参考文献：
  名称：

  Oligonuclear cyanide complexes from silver containing building blocks

  摘要：

  The complexes LnM-CN-Ag-CN with LnM=Cp(dppe)Fe or Cp(PPh3)(2)Ru are available from [Ag(CN)(2)](-) and [LnM](+) or LnM-CN. They are precursors of [LnM-CN-Ag-NC-MLn](+). Likewise the trinuclear complexes [LnM'-CN-Ag-NC-M'L-n](+) with LnM'=(TPA)Cu and cis-(bpy)(2)FeCN have been prepared. Irrespective of the CN attachment in the starting materials the cyanide-bridged compounds always contain M-CN-Ag arrays, i.e. silver-isocyanide coordination, thereby proving the lability of the silver-cyanide linkage. Electrochemical measurements have shown that there is no electronic communication between the outer metal centers in the trinuclear complexes. (C) 2000 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00626-4

文献信息

• Synthesis, spectral and redox switchable cubic NLO properties of chiral dinuclear iron cyanide/isocyanide-bridged complexes
  作者：Xiao Ma、Chen-Sheng Lin、Hui Zhang、Yi-Ji Lin、Sheng-Min Hu、Tian-Lu Sheng、Xin-Tao Wu

  DOI：10.1039/c3dt51197a

  日期：——

  Two chiral dinuclear cyanide/isocyanide-bridged complexes (R)-[Cp(dppe)Fe–CN–Fe(dppp)Cp]PF6 (1[PF6]) and (R)-[Cp(dppe)Fe–NC–Fe(dppp)Cp]PF6 (2[PF6]), and their mono-oxidation products (R)-[Cp(dppe)FeII–CN–FeIII(dppp)Cp] [PF6]2 (1[PF6]2) and (R)-[Cp(dppe)FeIII–NC–FeII(dppp)Cp][PF6]2 (2[PF6]2) were synthesized and fully characterized. The electronic spectra of both the mixed-valence complexes 1[PF6]2 and 2[PF6]2 exhibit a strong and broad absorption band with two discernable peaks in the NIR region, which are attributed to Fe(II)–Fe(III) IVCT transitions. The attributions are supported by the DFT calculations. Under irradiation with a nanosecond laser at 1064 nm, the measured third-order NLO results of all four cyanide-bridged complexes showed that complexes 1+ and 2+ do not exhibit an NLO response, but their one-electron oxidation complexes 12+ and 22+ exhibit a strong NLO response due to a resonance enhanced effect. In addition, both complexes 12+ and 22+ display RSA and self-defocusing effects and show good optical limiting behavior in a broadband range.

  两种手性双核氰化物/异氰化物桥式配合物 (R)-[Cp(dppe)Fe-CN-Fe(dppp)Cp]PF6 (1[PF6]) 和 (R)-[Cp(dppe)Fe-NC-Fe(dppp)Cp]PF6 (2[PF6])、及其单氧化产物 (R)-[Cp(dppe)FeII-CN-FeIII(dppp)Cp][PF6]2 (1[PF6]2) 和 (R)-[Cp(dppe)FeIII-NC-FeII(dppp)Cp][PF6]2 (2[PF6]2) 的合成和全面表征。混合价配合物 1[PF6]2 和 2[PF6]2 的电子能谱都显示出一个强而宽的吸收带，在近红外区域有两个明显的峰，这两个峰归因于 Fe(II)-Fe(III) IVCT 转变。DFT 计算证实了这一结论。在波长为 1064 纳米的纳秒激光照射下，所有四种氰化物桥接配合物的三阶 NLO 测量结果表明，配合物 1+ 和 2+ 没有表现出 NLO 响应，但它们的单电子氧化配合物 12+ 和 22+ 由于共振增强效应而表现出强烈的 NLO 响应。此外，12+ 和 22+ 复合物都显示出 RSA 和自聚焦效应，并在宽带范围内表现出良好的光学限制行为。
• Syntheses, crystal structures and MMCT properties of cyanide-bridged binuclear Ru–Fe complexes
  作者：Su-Hua Li、Yang Liu、Yu-Ying Yang、Yu-Xiao Zhang、Qing-Dou Xu、Sheng-Min Hu、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1016/j.poly.2019.114109

  日期：2019.11

  Abstract In this report, two new binuclear mixed-valence (MV) compounds and their one-electron oxidation products, [MeCpLRu(μ-CN)Fe(dppe)Cp][PF6]n (L = dppe, (PPh3)2) (n = 1, 2), were synthesized and thoroughly characterized by single-crystal X-ray diffraction analysis. Complexes 12+ and 22+ are one-electron oxidation products of 11+ and 2+, respectively. The electronic absorption results indicate that there

  摘要在本报告中，提出了两种新的双核混合价（MV）化合物及其单电子氧化产物[MeCpLRu（μ-CN）Fe（dppe）Cp] [PF6] n（L = dppe，（PPh3）2）合成（n = 1，2），并通过单晶X射线衍射分析对其进行了全面表征。络合物12+和22+分别是11+和2+的单电子氧化产物。电子吸收结果表明，单电子氧化产物中存在金属间的电荷转移（MMCT），这在理论计算中得到了有力的支持。可以将复合物12+和22+定义为II类MV化合物。研究发现，由于（PPh3）2的给电子能力强于dppe，因此MMCT带在从12+到22+时明显发生了红移。
• Synthesis, structural and metal-to-metal charge transfer properties of cyanide-bridged compound [Fe^II/III-NC-Ru^II-CN-Fe^II/III]
  作者：Yong Wang

  DOI：10.1039/d1nj05900a

  日期：——

  one-electron oxidation product 2 is mainly attributed to RuII and FeII → FeIII MMCT transitions, and the MMCT of the two-electron oxidation product 3 is mainly attributed to RuII → FeIII MMCT transitions. The IR, EPR, Mössbauer spectroscopy and magnetic properties indicate electron delocalization in complexes 2 and 3, and that of 3 is much stronger than that of 2. The two-electron oxidation product 3

  氰化物桥接配合物反式-[Cp(dppe)Fe(NC)Ru II ( t bupy) 4 (CN)Fe(dppe)Cp][PF 6 ] n ( t bupy = 4-叔丁基吡啶, n = 2, 3 和 4 分别为1-3, ) 被系统地合成和表征为三种不同的氧化还原状态。单晶 X 射线衍射分析、IR、电化学、电子吸收光谱、EPR 和穆斯堡尔光谱清楚地揭示了配合物1-3的详细电子结构，这些发现使我们能够了解伴随氧化还原态变化的结构和电子态的系统变化。一电子氧化产物2的金属间电荷转移 (MMCT)主要归因于 Ru II和 Fe II → Fe III MMCT 跃迁，二电子氧化产物3的 MMCT主要归因于 Ru II → Fe III MMCT 跃迁。IR、EPR、穆斯堡尔光谱和磁性表明配合物2和3中的电子离域，并且3比2强得多. 就EPR、穆斯堡尔光谱和磁性而言，双电子氧化产物3可以在低温下定位，但在室温下离域。
• Long Range Metal‐Metal Interactions Along Fe−NC−Ru−CN−Fe Chains
  作者：Tianlu Sheng、Heinrich Vahrenkamp

  DOI：10.1002/ejic.200300656

  日期：2004.3

  Trinuclear complexes with linear FeII−NC−RuII−CN−FeII arrays were obtained by attachment of FeCp(dppe) units to the cyanoruthenium complexes trans-[Ru(CN)2(Py)4] (Py = pyridine, 4-methylpyridine, 4-ethylpyridine) . From their cyclic voltammograms it can be concluded that there are long-range metal−metal interactions between their external iron centers. Partial oxidation led to the isolation of the corresponding

  具有线性 FeII-NC-RuII-CN-FeII 阵列的三核配合物是通过将 FeCp(dppe) 单元连接到氰基钌配合物反式-[Ru(CN)2(Py)4]（Py = 吡啶，4-甲基吡啶， 4-乙基吡啶）。从它们的循环伏安图可以得出结论，它们的外部铁中心之间存在长程金属-金属相互作用。部分氧化导致相应的混合价 FeII-NC-RuII-CN-FeIII 复合物的分离。对于这些，从 NIR 光谱中的宽 MMCT 波段可以明显看出长距离金属 - 金属相互作用。MMCT 特性通过使用 Hush 形式主义的分析进行量化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(<scp>iii</scp>)–M(<scp>ii</scp>)–Fe(<scp>iii</scp>) complexes
  作者：Yong Wang、Chensheng Lin、Xiao Ma、Zhenzhen Xue、Xiaoquan Zhu、Wenhai Cao、Shengmin Hu、Tianlu Sheng、Xintao Wu

  DOI：10.1039/c5dt00383k

  日期：——

  This work shows that for the investigated Fe^III–NC–M^II–CN–Fe^III complexes the magnetic coupling strength between the distant Fe^III ions increases with the diamagnetic cyanidometal bridge in the order of Fe < Ru < Os.

  这项研究表明，对于研究的Fe^III–NC–M^II–CN–Fe^III配合物，远离的Fe^III离子之间的磁耦合强度随着无磁性氰配体金属桥的增加而增强，顺序为Fe < Ru < Os。