iron(III) (hexafluoroacetylacetonate)₃ | 17786-67-3

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机铁
• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: iron(III) (hexafluoroacetylacetonate)₃
• 英文别名: Fe(III)(hexafluoroacetylacetonate)₃；Fe(III)(hfac)₃；Fe(CF₃COCHCOCF₃)₃；Fe(hfaa)₃；tris(1,1,1,5,5,5-hexafluoro 2,4-pentanodionate) iron(III)；tris(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)iron(III)；Fe(hexafluoroacetylacetonate)₃；iron(III) hexafluoroacetylacetonate；Fe(hfac)₃；tris-(hexafluoroacetylacetonato)iron(III)；Iron III hexafluoropentanedionate；(Z)-1,1,1,5,5,5-hexafluoro-4-oxopent-2-en-2-olate;iron(3+)
• CAS: 17786-67-3
• 化学式: C₁₅H₃F₁₈FeO₆
• 分子量: 677.003
• InChiKey: NBPRJLXRDBDIFS-JVUUZWNBSA-K

物化性质

• 熔点：
  52 °C

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  40
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  24

安全信息

• TSCA：
  No

反应信息

• 作为反应物：
  描述：

  iron(III) (hexafluoroacetylacetonate)₃ 在 甲醇 作用下， 以 四氯化碳 为溶剂， 生成
  参考文献：
  名称：

  Nekipelov, V. M.; Nosov, A. V.; Ivanchenko, V. A., Doklady Physical Chemistry, 1983, vol. 269, p. 165 - 170

  摘要：

  DOI：
• 作为产物：
  描述：

  六氟乙酰丙酮 、 三氯化铁 以 四氯化碳 为溶剂， 生成 iron(III) (hexafluoroacetylacetonate)₃
  参考文献：
  名称：

  The heat capacity and vibration spectra of tris(1,1,1,5,5,5-hexafluoro 2,4-pentanodionate) iron(III)

  摘要：

  The heat capacity of compound tris(1,1,1,5,5,5-hexafluoro 2,4-pentanodionate) iron(III) has been measured by the adiabatic method within the temperature range 4.8-321 K. The thermodynamic functions: entropy, enthalpy and reduced Gibbs' energy have been calculated. The components of heat capacity related to intermolecular and intramolecular vibrations have been analyzed.An anomaly has been discovered in the heat capacity with a maximum at 44.6 K. A critical change in spectral density of phonon states has been marked at the same temperature. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.tca.2005.03.016

文献信息

• Rate and Mechanism of Ligand Exchange of Several Tris(β-diketonato)iron(III) Complexes with 4-Isopropyltropolone in Carbon Tetrachloride
  作者：Tatsuya Sekine、Kazuho Inaba

  DOI：10.1246/bcsj.58.1125

  日期：1985.4

  seven tris(β-diketonato)iron(III) in carbon tetrachloride with 4-isopropyltropolone was measured by a spectrometric method in order to determine the effect of the chemical properties of the leaving ligand on the reaction mechanism. It was found from the dependence of the rate on the leaving and entering ligands and also from the values of ΔH\eweq and ΔS\eweq that the exchange reaction of iron(III) complexes

  为了确定离去配体的化学性质对反应机理的影响，通过光谱法测量了四氯化碳中的七三（β-二酮基）铁（III）与 4-异丙基托酚酮的配体交换速率。由离开和进入配体的速率的依赖性以及ΔH\eweq和ΔS\eweq的值发现，铁(III)与乙酰丙酮及其两个苯基取代的衍生物的络合物的交换反应通过解离机制。还发现与三氟乙酰丙酮及其苯基和 2-噻吩基取代衍生物的反应通过缔合机制进行。六氟乙酰丙酮络合物在反应的第一阶段与进入的配体形成中间体，然后发生配体交换。从这些结果得出结论，更稳定的复合物的配体交换受离去配体的断裂控制。不太稳定的被控制了......
• Fluorinated β-Diketonates of the First Row Divalent Transition Metals: New Approach to the Synthesis of Unsolvated Species
  作者：Haitao Zhang、Bo Li、Jinyu Sun、Rodolphe Clérac、Evgeny V. Dikarev

  DOI：10.1021/ic801320p

  日期：2008.11.3

  solid-state route for the preparation of metal beta-diketonates in their unsolvated forms has been suggested. Four new first row divalent transition metal beta-diketonates, M(hfac)2 (M = Mn (1), Fe (2), Co (3), and Ni (4); hfac = hexaluoroacetylacetonate), have been isolated in quantitative yield. Compounds 1-3 have been obtained by comproportionation reaction between the corresponding M(hfac)3 and

  已经提出了用于制备未溶剂化形式的金属β-二酮酸盐的原始低温固态路线。定量分离了四种新的第一排二价过渡金属β-二酮酸盐M（hfac）2（M = Mn（1），Fe（2），Co（3）和Ni（4）; hfac =六氟乙酰丙酮酸盐）屈服。化合物1-3是通过相应的M（hfac）3与金属粉末之间的配位反应获得的。Ni（hfac）2（4）是通过用Cu（hfac）2氧化金属镍而合成的。所有产品均已通过X射线粉末分析和单晶衍射技术进行了光谱表征。1-4的固态结构具有多核分子，其中配位不饱和金属中心通过路易斯酸碱与以螯合桥联方式起作用的二酮酸酯配体的氧原子相互作用而满足八面体环境。已经显示出标题过渡金属二酮酸酯在升华-沉积过程以及在非配位溶剂的溶液中保留其多核结构。在配位溶剂中，1-4分子迅速形成单核M（hfac）2L2（L =供体溶剂）复合物。
• Mixed-Ligand Approach to Design of Heterometallic Single-Source Precursors with Discrete Molecular Structure
  作者：Craig M. Lieberman、Anantharamulu Navulla、Haitao Zhang、Alexander S. Filatov、Evgeny V. Dikarev

  DOI：10.1021/ic5004885

  日期：2014.5.5

  [Pb(β-dik)2] units that are held together by bridging M–O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments. In order to design the heterometallic precursor with a proper metal/metal ratio and with a discrete molecular structure, we used a combination of two different diketonate ligands. Heteroleptic

  Pb / Fe = 1：1氧化物材料，PbFe（β-dik）4（β-dik=六氟乙酰丙酮（hfac，1），乙酰丙酮酸酯（acac，2）和三氟乙酰丙酮酸酯（tfac，4）的杂金属单源前体），已通过三种不同的固态合成方法进行了分离。杂金属二酮酸盐的晶体结构1，2，和4被发现含有建立在交替的聚合物链的[Fe（β-DIK）2 ]和[铅（β-DIK）2]通过桥接M–O相互作用而结合在一起的单元。杂金属前体具有高挥发性，但仅溶于配位溶剂中，在其中它们分解成溶剂化的均金属片段。为了设计具有适当金属/金属比和离散分子结构的杂金属前体，我们使用了两种不同的二酮酸酯配体的组合。杂多配合物Pb 2 Fe 2（hfac）6（acac）2（5）已通过将均铁（acac）2加入异金属Pb 2 Fe（hfac）6（3）的优化化学计量反应获得）可以在溶液中大规模运行的二酮酸酯。两个配体与吸电子和供电子基团的组合允许改变异金
• Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials
  作者：Craig M. Lieberman、Matthew C. Barry、Zheng Wei、Andrey Yu. Rogachev、Xiaoping Wang、Jun-Liang Liu、Rodolphe Clérac、Yu-Sheng Chen、Alexander S. Filatov、Evgeny V. Dikarev

  DOI：10.1021/acs.inorgchem.7b01032

  日期：2017.8.21

  single-source precursors for the low-temperature preparation of MxM′3–xO4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic

  可以使用的作为预期挥发性单一来源前体M的低温制备了一系列混合价，异金属（混合的过渡金属）的二酮X M' 3- X Ò 4报道尖晶石氧化物材料。使用固相和溶液反应，通过几种方法合成了三种Fe / Co比为1：1、1：2和2：1的铁-铁配合物。根据近乎定量的反应收率，元素分析以及金属氧键与同金属类似物中金属氧键的比较，将杂金属化合物配制成[Fe III（acac）3 ] [Co II（hfac）2 ]（1）， [Co II（hfac）2 ] [Fe III（acac）3 ] [Co II（hfac）2 ]（2）和[Fe II（hfac）2 ] [Fe III（acac）3 ] [Co II（hfac）2 ] （3）。在上述杂配物络合物中，路易斯酸，配位不饱和的Co II / Fe II中心被两个六氟乙酰丙酮酸酯（hfac）配体螯合，与桥接相邻的Fe III的乙酰丙酮酸酯（acac）基团的氧原子
• Immobilisation of iron tris(β-diketonates) on a two-dimensional flat amine functionalised silicon wafer: A catalytic study of the formation of urethane, from ethanol and a diisocyanate derivative
  作者：M.M. Conradie、J. Conradie、E. Erasmus

  DOI：10.1016/j.poly.2014.04.054

  日期：2014.9

  A series of immobilised iron tris(beta-diketonato) catalysts on a Si-wafer was prepared, by covalently anchoring the Fe(beta-diketonato)(3) complexes [where beta-diketonato = (RCOCHCORT')(-), with 1 = acac (R = CH3; R' = CH3), 2 = dbm (R=C6H5; R' = C6H5), 3 = tfaa (R = CH3; R' = CF3), and 4 = hfaa (R = CF3; R' = CF3)], onto an aminated functionalised Si-wafer. These new catalysts were characterised by X-ray photo-electron spectroscopy (XPS) and atomic force microscopy (AFM). XPS data revealed that ca. 27-91% of all the amine groups anchored the catalyst, Fe(beta-diketonato)(3 center dot) Different Gaussian peaks could be fitted into the F 1s peak, due to the fluorine either being positioned adjacent to the -C-O-Fe-, or to the -C-N-Fe-. The binding energy of the Fe 2p(3/2) peak varied between ca. 710.4 and 711.0 eV, depending on the electron donating properties of the R-groups on the beta-diketonato ligands, expressed as the sum of the Gordy group electronegativities of the R-groups in the beta-diketonato ligands. The AFM photographs showed that the surface changed dramatically after each treatment: after amination (binding of the aminate silane onto the hydroxylate Si-wafer) the Si-wafer turned from flat with a few spikes, to a very wavy surface with smooth lumps. The surface topography again changed, after covalent anchoring of the iron tris(beta-diketonato) complexes, to a nodular surface with poorly defined grain boundaries. These immobilised iron tris(beta-diketonato) on Si-wafer catalysts, were evaluated for their catalytic activity, during the formation of hexamethylenediurethane from hexamethylenediisocyanate and ethanol. The TOF varied between 15 and 46 s(-1), depending on the electron donating properties of the R-groups on the beta-diketonato ligands. The more electron donating the R groups, the higher the TOF. (C) 2014 Elsevier Ltd. All rights reserved.

表征谱图