trans-[Fe(II)(CN)4(CO)2](2-) | 355806-54-1

• 英文名称: trans-[Fe(II)(CN)4(CO)2](2-)
• 英文别名: trans-[Fe(CN)4(CO)2](2-)；trans-Fe(CN)4(CO)2(2-)
• CAS: 355806-54-1；363179-49-1
• 化学式: C₆FeN₄O₂
• 分子量: 215.939
• InChiKey: ROQPWFKCCKULHM-UHFFFAOYSA-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：

  [tetraethylammonium]2[Fe(CN)2(CO)3] 在 air 作用下， 以 not given 为溶剂， 生成 trans-[Fe(II)(CN)4(CO)2](2-) 、 pentacyanocarbonylferrate(II)(3-)
  参考文献：
  名称：

  Protonation Studies of the New Iron Carbonyl Cyanide trans-[Fe(CO)₃(CN)₂]^2-:  Implications with Respect to Hydrogenases

  摘要：

  The new iron carbonyl cyanide trans-[Fe(CN)(2)(CO)(3)](2-), [2](2-), forms in high yield via photosubstitution of Fe(CO)(5) with 2 equiv of Et4NCN. Protonation of [2](2-) generated [HFe(CN)(2)(CO)(3)](-), [2H](-), the first H-Fe-CN-CO species. Further protonation gives dihydrogen. This simple system provides insights into hydrogen evolution by the hydrogenase enzymes, which also feature H-Fe-CN-CO centers.

  DOI：

  10.1021/ic034455b

文献信息

• The Influence of Cyanide on the Carbonylation of Iron(II):  Synthesis of Fe−SR−CN−CO Centers Related to the Hydrogenase Active Sites
  作者：Thomas B. Rauchfuss、Stephen M. Contakes、Sodio C. N. Hsu、Michael A. Reynolds、Scott R. Wilson

  DOI：10.1021/ja015948n

  日期：2001.7.1

  Michael A. Reynolds, and Scott R. WilsonDepartment of ChemistryUniVersity of Illinois at Urbana-ChampaignUrbana, Illinois 61801ReceiVed April 4, 2001ReVised Manuscript ReceiVed May 30, 2001Recently iron sulfides have been proposed as being central tothe emergence of life.

  Thomas B. Rauchfuss,* Stephen M. Contakes, Sodio CN Hsu, Michael A. Reynolds, and Scott R. WilsonDepartment of Illinois University at Urbana-Champaign, Illinois 61801ReceiVed April 4, 2001 Revised Manuscript Receed21V被认为是生命出现的核心。
• Coordination Chemistry of [HFe(CN)₂(CO)₃]⁻ and Its Derivatives: Toward a Model for the Iron Subsite of the [NiFe]-Hydrogenases
  作者：C. Matthew Whaley、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/ic900200s

  日期：2009.5.18

  Reaction of dppv with [MeFe(CN)2(CO)3]− gives the acetyl complex, [Fe(CN)2(COMe)(CO)(dppv)]−. Whereas [Fe(CN)2(CO)3]2− undergoes protonation and methylation at Fe, acid chlorides give the iron(0) N-acylisocyanides [Fe(CN)(CO)3(CNCOR)]− (R = Ph, CH3). The solid state structures of [K(18-crown-6)][HFe(CN)2(CO)(dppv)], Fe(CN)2(NCMe)(CO)(dppv), and [K(18-crown-6)]2[HFe(CN)3(CO)2] were confirmed crystallographically

  Fe(CO) 5和氰化物盐在 MeCN 溶液中的光反应得到二价阴离子 [Fe(CN) 2 (CO) 3 ] 2−，方便地分离为 [K(18-crown-6)] 2 [Fe(CN) 2 (CO) 3 ]。[Fe(CN) 2 (CO) 3 ] 2- 的溶液在-600 mV（相对于Ag/AgCl）下不可逆地氧化，主要生成[Fe(CN) 3 (CO) 3 ] -。二价阴离子的质子化，得到氢化物[K（18-冠-6）] [HFE（CN）2（CO）3 ]与AP ķ一个≈ 17 (MeCN)。与抗取代的双阴离子前体相比，氢化亚铁表现出增强的亲电性。[K(18-crown-6)][Fe(CN) 2 (CO) 3 ] 用叔膦和亚磷酸酯处理得到 [HFe(CN) 2 (CO) 2 L] - (L = P( OPh) 3和 PPh 3 )。[ 1 H(CO) 2 ] -上的羰基被 P(OPh) 3取代在亚磷酸酯和铁中是一级的（k
• Further Study of the Reaction of Fe²⁺ with CN^-:  Synthesis and Characterization of <i>cis</i> and <i>trans</i> [Fe^II,III(CN)₄L₂]<i>ⁿ</i>^- Complexes
  作者：Gina M. Chiarella、Doris Y. Melgarejo、Stephen A. Koch

  DOI：10.1021/ja0571951

  日期：2006.2.1

  The reaction of Fe2+ with CN-, which was first performed in 1704, has been used to synthesize a new series of basic [FeII,III(CN)4L2]n- complexes, where L is a monodentate ligand. trans-Na2[FeII(CN)4(DMSO)2] and cis-[NEt4]2[FeII(CN)4(pyridine)2] are synthesized by the direct reaction of FeCl2 with 4 equiv of CN- in DMSO or pyridine. Air oxidation of the latter compound gives cis-[NEt4][FeIII(CN)4(pyridine)2]. The non-cyanide ligands in these complexes undergo facile ligand exchange reactions with solvent. Reaction of cis-[NEt4]2[FeII(CN)4(pyridine)2] with CO at room temperature gives trans-[NEt4]2[FeII(CN)4(pyridine)(CO)].
• <i>fac</i>-[Fe^II(CN)₃(CO)₃]^- and <i>cis</i>-[Fe^II(CN)₄(CO)₂]²^-:  New Members of the Class of [Fe^II(CN)<i>_x</i>(CO)<i>_y</i>] Compounds
  作者：Jianfeng Jiang、Stephen A. Koch

  DOI：10.1021/ic015604y

  日期：2002.1.1

  The reaction of Fe(CO)(4)I(2) with NaCN or KCN in methanol gives M[Fe(II)(CN)(3)(CO)(3)] (M = Na, K), which can be converted to [Ph(4)E][Fe(II)(CN)(3)(CO)(3)] (E = P, As). The structure of the fac-[Fe(II)(CN)(3)(CO)(3)](-) (1) anion was established by the X-ray crystal structures of K-1 and [Ph(4)As]-1.H(2)O. Compound 1 has also been characterized by IR, Raman, and (13)C NMR. The coupling of the CO and CN stretching modes in the vibrational spectra of 1 have been analyzed. The reaction of Na-1 with NaCN gives Na(2) cis-[Fe(II)(CN)(4)(CO)(2)] (Na-2), which has been structurally characterized as [Ph(4)P][Et(4)N]-2. Compounds 1 and 2 are additional members of the series of compounds of general formula [Fe(II)(CN)((6-x))(CO)(x)](x-4). [Fe(CN)(x)(CO)(y)] compounds are of interest due to the occurrence of such coordination modes in hydrogenase enzymes.
• Effect of solvent environment on the CO band position in the infrared spectrum of trans-[FeII(CN)4(CO)2]2−
  作者：R. Viswanathan、A.M. Etra、J. Jiang

  DOI：10.1016/j.ica.2008.12.015

  日期：2009.6

  Density functional theory (DFT) is used to understand the effect of hydrogen bonding solvents on the CO band position in the infrared (IR) spectrum of a mono-iron complex, trans-[Fe-II(CN)(4)(CO)(2)](2). This mono-iron complex has received much attention recently due its potential relation to the biosynthesis of Fe-only hydrogenase enzymes. Our calculations show that the polar solvent molecules preferentially hydrogen bond to the cyano ligands in this complex. The effect of such hydrogen bonding on the electron density distribution is analyzed in terms of the population in natural bond orbitals (NBO). Our results show that the presence of hydrogen bonding to the cyano ligands decreases the extent of back bonding from the metal to the carbonyl ligand. This results in decreased electron density in the pi* orbitals of the carbonyl bond leading to a strengthening of the CO bond and a consequent blue shift in the IR band position of the carbonyl group. We also show that the extent of blue shift correlates with the number of nearest neighbor solvent molecules. (C) 2008 Elsevier B.V. All rights reserved.