[Fe{N(SiMe₃)₂}₂(THF)] | 133984-10-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [Fe{N(SiMe₃)₂}₂(THF)]
• 英文别名: Bis(trimethylsilyl)azanide;iron(2+);oxolane
• CAS: 133984-10-8
• 化学式: C₁₆H₄₄FeN₂OSi₄
• 分子量: 448.727
• InChiKey: GWYMRASPIVELSA-UHFFFAOYSA-N

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：

  N-(2-pyridylmethyl)-2-pyridylmethanimine 、 [Fe{N(SiMe₃)₂}₂(THF)] 以 乙醚 为溶剂， 反应 3.0h， 生成 (1,3-di-(2-pyridyl)-2-azaallyl)Fe{bis(trimethylsilyl)amide}
  参考文献：
  名称：

  C–C Bond Formation and Related Reactions at the CNC Backbone in (smif)FeX (smif = 1,3-Di-(2-pyridyl)-2-azaallyl): Dimerizations, 3 + 2 Cyclization, and Nucleophilic Attack; Transfer Hydrogenations and Alkyne Trimerization (X = N(TMS)₂, dpma = (Di-(2-pyridyl-methyl)-amide))

  摘要：

  Molecular orbital analysis depicts the CNCnb backbone of the smif (1,3-di-(2-pyridy1)-2-azaally1) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)(2)} (1) to [{(Me3Si)(2)N}Fe](2)(mu-K-3,K-3-N,py(2)-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me(2)(0)Me(2)smif)Fe-N(SiMe3)(2) (8) provides a route to [{(Me3Si)(2)N}Fe](2)(mu-K-4,K-4-N,py(2),C-(Me-b,(CH2)-C-b,Me-0(2)(smif)H))(2) (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN-(SiMe3)(2))(2) (11), and the collateral discovery of allcyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)(2)(THF) as an effective catalyst. Nucleophilic attack by (smif)(2)Fe (13) on 'BuNCO and (2,6-Pr2C6H3)NCO afforded (RNHCO-smif)(2)Fe (14a, R = 'Bu; 14b, 2,6-' PrC6H3). Calculations suggested that (dpma)(2)Fe (15) would favorably lose dihydrogen to afford (smif)(2)Fe (13). H-2-transfer to allcynes, olefins, imines, PhN=NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

  DOI：

  10.1021/ic302783y
• 作为产物：
  描述：

  四氢呋喃 、 [Fe{N(SiMe3)2}2]2 以97%的产率得到[Fe{N(SiMe₃)₂}₂(THF)]
  参考文献：
  名称：

  三角形平面单核Fe（II）和Co（II）双（三甲基甲硅烷基）酰胺基络合物的慢磁弛豫—对比研究

  摘要：

  三角平面高自旋Co 2+络合物[Li（15-crown-5）] [Co {N（SiMe 3）2 } 3 ]，[Co {N（SiMe 3）2 } 2（THF）]（THF =四氢呋喃）和[Co {N（SiMe 3）2 } 2（PCy 3）]（Cy = -C 6 H 13 =环己基）表明，所有三种络合物在低于25摄氏度的温度下均显示出缓慢的磁弛豫在施加的dc（直流电）场下为8K。它们各自的弛豫过程的特征参数，例如有效能垒U eff（16.1（2），17.1（3），和19.1（7）厘米-1）和弛豫时间τ 0（3.5（3）×10 -7，9.3（8）×10 -8和3.0（8）×尽管配体性质存在明显差异，但10 – 7 s）几乎相同。相反，同构的高自旋Fe 2+络合物[Li（15-crown-5）] [Fe {N（SiMe 3）2 } 3 ]和[Fe {N（SiMe 3）2 } 2（THF）]在相似条件

  DOI：

  10.1021/ic401677j
• 作为试剂：
  描述：

  2-丁炔 在 [Fe{N(SiMe₃)₂}₂(THF)] 作用下， 以 氘代苯 为溶剂， 生成 六甲基苯
  参考文献：
  名称：

  C–C Bond Formation and Related Reactions at the CNC Backbone in (smif)FeX (smif = 1,3-Di-(2-pyridyl)-2-azaallyl): Dimerizations, 3 + 2 Cyclization, and Nucleophilic Attack; Transfer Hydrogenations and Alkyne Trimerization (X = N(TMS)₂, dpma = (Di-(2-pyridyl-methyl)-amide))

  摘要：

  Molecular orbital analysis depicts the CNCnb backbone of the smif (1,3-di-(2-pyridy1)-2-azaally1) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)(2)} (1) to [{(Me3Si)(2)N}Fe](2)(mu-K-3,K-3-N,py(2)-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me(2)(0)Me(2)smif)Fe-N(SiMe3)(2) (8) provides a route to [{(Me3Si)(2)N}Fe](2)(mu-K-4,K-4-N,py(2),C-(Me-b,(CH2)-C-b,Me-0(2)(smif)H))(2) (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN-(SiMe3)(2))(2) (11), and the collateral discovery of allcyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)(2)(THF) as an effective catalyst. Nucleophilic attack by (smif)(2)Fe (13) on 'BuNCO and (2,6-Pr2C6H3)NCO afforded (RNHCO-smif)(2)Fe (14a, R = 'Bu; 14b, 2,6-' PrC6H3). Calculations suggested that (dpma)(2)Fe (15) would favorably lose dihydrogen to afford (smif)(2)Fe (13). H-2-transfer to allcynes, olefins, imines, PhN=NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

  DOI：

  10.1021/ic302783y

文献信息

• N‐Heterocyclic Carbene Complexes of Iron as Photosensitizers for Light‐Induced Water Reduction
  作者：Peter Zimmer、Patrick Müller、Lukas Burkhardt、Rahel Schepper、Adam Neuba、Jakob Steube、Fabian Dietrich、Ulrich Flörke、Stefan Mangold、Markus Gerhards、Matthias Bauer

  DOI：10.1002/ejic.201700064

  日期：2017.3.17

  time, the potential of noble-metal-free iron-based photosensitizers for photocatalytic water reduction by using homo- and heteroleptic carbene complexes was proven. The development of a facile synthesis route for such carbene complexes was delineated. The complexes were investigated by UV/Vis and fluorescence spectroscopy, DFT calculations, cyclic voltammetry, and X-ray absorption spectroscopy. Their

  首次证明了不含贵金属的铁基光敏剂通过使用均配和杂配卡宾配合物进行光催化水还原的潜力。描述了这种卡宾配合物的简便合成路线的开发。通过紫外/可见光和荧光光谱、DFT 计算、循环伏安法和 X 射线吸收光谱研究了配合物。将它们的催化性能与已建立的含贵金属的光敏剂（如 [Ir(ppy)2(bpy)][PF6]（Hppy = 2-苯基吡啶，bpy = 2,2'-联吡啶）的催化性能进行了比较。
• Synthesis and Characterization of Novel Iron(II) Complexes with Tetradentate Bis(N-heterocyclic carbene)–Bis(pyridine) (NCCN) Ligands
  作者：Andreas Raba、Mirza Cokoja、Stefan Ewald、Korbinian Riener、Eberhardt Herdtweck、Alexander Pöthig、Wolfgang A. Herrmann、Fritz E. Kühn

  DOI：10.1021/om2010673

  日期：2012.4.9

  coordinate—in addition to the NCCN ligands—two acetonitrile ligands in the solid state as well as in solution. The alkylene bridge connecting the two NHCs has an influence on the coordination mode of the NCCN ligands. Whereas the methylene- and ethylene-bridged NHC moieties lead to a nearly planar geometry of the NCCN ligand and two trans-positioned acetonitrile ligands, the propylene-bridged complex 2c

  合成了三种新颖的带有四齿配位体的吡啶-双（N-杂环卡宾）-吡啶（NCCN）铁配合物。化合物反式-二乙腈[双（邻咪唑-2-亚吡啶基吡啶）烷]铁（II）六氟磷酸酯（烷=甲烷（2a），乙烷（2b））和顺式-二乙腈[1,3-双（邻咪唑） -2-亚吡啶基丙烷]六氟磷酸铁（II）（2c已经通过单晶X射线衍射（XRD），核磁共振光谱（NMR）和红外光谱（IR）进行了表征。循环伏安法（CV）测量显示Fe（II）可逆氧化为Fe（III）。桥的旋转势垒已通过2b的变温NMR（VT-NMR）研究确定。在所有络合物中，除NCCN配体外，Fe中心还配成固态和溶液中的两个乙腈配体。连接两个NHC的亚烷基桥对NCCN配体的配位方式有影响。而亚甲基和乙烯桥连的NHC部分导致NCCN配体和两个易位乙腈配体的近似平面几何形状，而丙烯桥连的配合物2c表现出锯齿型配位模式，带有两个顺式乙腈配体。研究了合成配合物对溶剂配体取代的反
• Synthesis, Characterization, and Reactivity of Furan- and Thiophene-Functionalized Bis(N-heterocyclic carbene) Complexes of Iron(II)
  作者：Julia Rieb、Andreas Raba、Stefan Haslinger、Manuel Kaspar、Alexander Pöthig、Mirza Cokoja、Jean-Marie Basset、Fritz E. Kühn

  DOI：10.1021/ic500959m

  日期：2014.9.15

  The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (2a) and tetrak

  报道了带有新的杂原子官能化的亚甲基桥双（N-杂环卡宾）配体的铁（II）配合物的合成。所有复合物的特征在于单晶X射线衍射（SC-XRD），核磁共振（NMR）光谱和元素分析。四（乙腈） -顺式- [双（ø咪唑-2- ylidenefuran）甲烷]铁（II）六氟磷酸盐（图2a）和四（乙腈） -顺式- [双（ø咪唑-2- ylidenethiophene）甲烷]铁（II）通过[Fe N（SiMe 3）2 } 2的氨解获得六氟磷酸盐（2b）（THF）]与呋喃和噻吩官能化的双（咪唑鎓）盐1a和1b在乙腈中。2a和2b的SC-XRD结构显示双（卡宾）配体以二齿形式配位，而不是可能的四齿配位。这些扭曲的八面体络合物的其他四个配位位点被乙腈配体占据。Et 2 O缓慢扩散在丙酮溶液中结晶2a导致形成顺式-二乙腈三[二（邻咪唑-2-亚甲基呋喃）甲烷]六氟磷酸铁（II）（3a）具有两个双齿配位的双（卡宾）配体
• Aryl−Oxazoline Chelates of First-Row Transition Metals: Structures of {κ-<i>C</i>,<i>N</i>-(<i>o</i>-C₆H₄)CMe₂(COCH₂CMe₂N)}FeCl(py) and [(κ-<i>C</i>,<i>N</i>-(<i>o</i>-C₆H₄)CMe₂(COCH₂CMe₂N)}Cr(μ-Cl)]₂
  作者：Emily C. Volpe、David R. Manke、Erika R. Bartholomew、Peter T. Wolczanski、Emil B. Lobkovsky

  DOI：10.1021/om100420z

  日期：2010.12.27

  (Me2N)3Ti(η-N-(4,4-dimethyl-(2-CHPh)oxazoline)) (2) and bis-N,N′-(4,4-dimethyl-(2-pyridylmethylyl)oxazoline)Fe (3). Oxidative addition of 4,4-dimethyl-2-(2-bromophenylpropan-2-yl)oxazoline (BrPhCMe2Ox) to Ni(COD)2 provided [κ-C,N-(o-C6H4)CMe2(COCH2CMe2N)}Ni]2(μ-Br)2 (42). With 4,4-dimethyl-2-(2-lithiophenylpropan-2-yl)oxazoline (LiPhCMe2Ox), salt (FeBr2) metathesis proved uncompetitive with oxazoline ring-opening

  芳基-恶唑啉合成子已被研究用于制备强场第一行过渡金属螯合物。使用4,4-二甲基-2-苯基恶唑啉（HPhOx）时，除Zn（κ - C，N -4,4-Me 2 -2-（o -C 6 H 4）恶唑啉之外，没有CH键活化作用可提供络合作用。）2（Zn（PhOx）2），注意到芳基偶联反应与4,4-二甲基-2-（2-lithiophenyl）恶唑啉（LiPhOx）和MX 2 ; [κ- N，N- 4,4-Me 2-（2- o -C 6 H 4）-2-恶唑啉} 2 ] CoCl 2（1 -Co）的结构表征。以（Me 2 N）3 Ti（η - N-（4,4-二甲基-（2-CHPh）恶唑啉）为例，4,4-二甲基-2-苄基恶唑啉（PhCH 2 Ox）的金属化易于去质子化。）（2）和双-N，N ′-（4，4-二甲基-（2-吡啶基甲基甲酰基）恶唑啉）Fe（3）。将氧化的4,4-二甲基-2-（2-溴苯基丙烷-2-基）恶唑啉（BrPhCMe
• Catalytic Nitrene Homocoupling by an Iron(II) Bis(alkoxide) Complex: Bulking Up the Alkoxide Enables a Wider Range of Substrates and Provides Insight into the Reaction Mechanism
  作者：Maryam Yousif、Duleeka Wannipurage、Caleb D. Huizenga、Elizabeth Washnock-Schmid、Nicholas J. Peraino、Andrew Ozarowski、Sebastian A. Stoian、Richard L. Lord、Stanislav Groysman

  DOI：10.1021/acs.inorgchem.8b01418

  日期：2018.8.6

  The reaction of HOR′ (OR′ = di-t-butyl-(3,5-diphenylphenyl)methoxide) with an iron(II) amide precursor forms the iron(II) bis(alkoxide) complex Fe(OR′)2(THF)2 (2). 2 (5–10 mol %) serves as a catalyst for the conversion of aryl azides into the corresponding azoarenes. The highest yields are observed for aryl azides featuring two ortho substituents; other substitution patterns in the aryl azide precursor

  HOR'（OR'=二叔丁基-（3,5-二苯基苯基）甲醇）与铁（II）酰胺前体的反应形成铁（II）双（醇盐）配合物Fe（OR'）2（ THF）2（2）。2（5-10 mol％）用作将芳基叠氮化物转化为相应的偶氮芳烃的催化剂。对于具有两个邻位取代基的芳基叠氮化物，观察到最高的收率。芳基叠氮化物前体中的其他取代方式导致中等或低产率。的反应2与相应的芳基叠氮化物显示化学计量的量（2当量）azoarenes的形成作为唯一的有机产品为笨重芳基叠氮化（AR =三甲苯基，2,6-二乙基苯基）。相反，四烯配合物Fe（OR'）的形成2（ArNNNNAr）（3 - 6）观察到的体积较小芳基叠氮化（AR =苯基，4-甲基苯基，4-甲氧基苯基，3,5-二甲基苯基）。通过光谱法（依赖于场的57 FeMössbauer和高频EPR）和密度泛函理论计算来探究所选四烯配合物的电子结构。这些研究表明，Fe（OR'）2（ArNNNNAr）配合物包含高自旋（S