[Fe{N(SiMe₃)₂}₂(PCy₃)] | 1334702-01-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [Fe{N(SiMe₃)₂}₂(PCy₃)]
• 英文别名: bis(trimethylsilyl)azanide;iron(2+);tricyclohexylphosphane
• CAS: 1334702-01-0
• 化学式: C₃₀H₆₉FeN₂PSi₄
• 分子量: 657.054
• InChiKey: OHULRUTXCMHSLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.52
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  硼烷铵络合物 、 [Fe{N(SiMe₃)₂}₂(PCy₃)] 以 not given 为溶剂， 生成 Fe₉(PCy₃)6
  参考文献：
  名称：

  Iron Complex-Catalyzed Ammonia–Borane Dehydrogenation. A Potential Route toward B–N-Containing Polymer Motifs Using Earth-Abundant Metal Catalysts

  摘要：

  Ammonia-borane (NH3BH3, AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H-2 release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy3)[N(SiMe3)(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe3)(2)](2) (2) yield a mixture of (NH2BH2) and (NHBH)(n) products with up to 1.7 equiv of H-2 released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH2BH2) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0).

  DOI：

  10.1021/ja210542r
• 作为产物：
  描述：

  iron(II) bis(trimethylsilyl)amide 、 三环己基膦 以 not given 为溶剂， 生成 [Fe{N(SiMe₃)₂}₂(PCy₃)]
  参考文献：
  名称：

  Iron Complex-Catalyzed Ammonia–Borane Dehydrogenation. A Potential Route toward B–N-Containing Polymer Motifs Using Earth-Abundant Metal Catalysts

  摘要：

  Ammonia-borane (NH3BH3, AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H-2 release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy3)[N(SiMe3)(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe3)(2)](2) (2) yield a mixture of (NH2BH2) and (NHBH)(n) products with up to 1.7 equiv of H-2 released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH2BH2) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0).

  DOI：

  10.1021/ja210542r
• 作为试剂：
  描述：

  硼烷铵络合物 、 三环己基膦 在 [Fe{N(SiMe₃)₂}₂(PCy₃)] 作用下， 以 二乙二醇二甲醚 为溶剂， 生成 ammonia borane 、 poly(p-borazylene) 、 氢气 、 (tricyclohexylphosphine)*BH3
  参考文献：
  名称：

  Iron Complex-Catalyzed Ammonia–Borane Dehydrogenation. A Potential Route toward B–N-Containing Polymer Motifs Using Earth-Abundant Metal Catalysts

  摘要：

  Ammonia-borane (NH3BH3, AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H-2 release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy3)[N(SiMe3)(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe3)(2)](2) (2) yield a mixture of (NH2BH2) and (NHBH)(n) products with up to 1.7 equiv of H-2 released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH2BH2) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0).

  DOI：

  10.1021/ja210542r

文献信息

• Two‐Coordinate Iron(I) Complex [Fe{N(SiMe ₃ ) ₂ } ₂ ] ⁻ : Synthesis, Properties, and Redox Activity
  作者：C. Gunnar Werncke、Philip C. Bunting、Carine Duhayon、Jeffrey R. Long、Sébastien Bontemps、Sylviane Sabo‐Etienne

  DOI：10.1002/anie.201408802

  日期：2015.1.2

  First‐row two‐coordinate complexes are attracting much interest. Herein, we report the high‐yield isolation of the linear two‐coordinate iron(I) complex salt [K(L)][FeN(SiMe3)2}2] (L=18‐crown‐6 or crypt‐222) through the reduction of either [FeN(SiMe3)2}2] or its three‐coordinate phosphine adduct [FeN(SiMe3)2}2(PCy3)]. Detailed characterization is gained through X‐ray diffraction, variable‐temperature

  第一排两坐标复合体引起了人们的极大兴趣。在此，我们报告了线性二配位铁（I）复盐[K（L）] [Fe N（SiMe 3）2 } 2 ]（L = 18-crown-6或crypt- 222）通过还原[Fe N（SiMe 3）2 } 2 ]或其三配位膦加合物[Fe N（SiMe 3）2 } 2（PCy 3）]还原。通过X射线衍射，变温NMR光谱和磁化率研究可以获得详细的表征。通过与I 2的反应进行一电子和二电子氧化 进一步发现其可提供相应的碘铁（II）和二碘铁（III）配合物。
• Slow Magnetic Relaxation in Trigonal-Planar Mononuclear Fe(II) and Co(II) Bis(trimethylsilyl)amido Complexes—A Comparative Study
  作者：Andreas Eichhöfer、Yanhua Lan、Valeriu Mereacre、Tilmann Bodenstein、Florian Weigend

  DOI：10.1021/ic401677j

  日期：2014.2.17

  Alternating current magnetic investigations on the trigonal-planar high-spin Co2+ complexes [Li(15-crown-5)] [CoN(SiMe3)2}3], [CoN(SiMe3)2}2(THF)] (THF = tetrahydrofuran), and [CoN(SiMe3)2}2(PCy3)] (Cy = −C6H13 = cyclohexyl) reveal that all three complexes display slow magnetic relaxation at temperatures below 8 K under applied dc (direct current) fields. The parameters characteristic for their

  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
• Importance of Out-of-State Spin–Orbit Coupling for Slow Magnetic Relaxation in Mononuclear Fe^II Complexes
  作者：Po-Heng Lin、Nathan C. Smythe、Serge I. Gorelsky、Steven Maguire、Neil J. Henson、Ilia Korobkov、Brian L. Scott、John C. Gordon、R. Tom Baker、Muralee Murugesu

  DOI：10.1021/ja203845x

  日期：2011.10.12

  Two mononuclear high-spin Fe-II complexes with trigonal planar ([Fe-II(N(TMS)(2))(2)(PCy3)] (1) and distorted tetrahedral ([Fe-II(N(TMS)(2))(2)(depe)] (2) geometries are reported (TMS = SiMe3, Cy = cyclohexyl, depe = 1,2-bis(diethylphosphino)ethane). The magnetic properties of 1 and 2 reveal the profound effect of out-of-state spin-orbit coupling (SOC) on slow magnetic relaxation. Complex 1 exhibits slow relaxation of the magnetization under an applied optimal dc field of 600 Oe due to the presence of low-lying electronic excited states that mix with the ground electronic state. This mixing re-introduces orbital angular momentum into the electronic ground state via SOC, and 1 thus behaves as a field-induced single. molecule magnet. In complex 2, the lowest-energy excited states have higher energy due to the ligand field of the distorted tetrahedral geometry. This higher energy gap minimizes out-of-state SOC mixing and zero-field splitting, thus precluding slow relaxation of the magnetization for 2.