trans-FeHCl(dmpe)2 | 96471-65-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: trans-FeHCl(dmpe)2
• 英文别名: trans-[(1,2-bis(dimethylphosphino)ethane)2Fe(H)(Cl)]；[trans-(1,2-bis(dimethylphosphino)ethane)2Fe(H)Cl]；trans-[FeH(Cl)(1,2-bis(dimethylphosphino)ethane)2]；trans-(1,2-bis(dimethylphosphino)ethane)2Fe(H)Cl；trans-[FeH(Cl)(dmpe)2]
• CAS: 96471-65-7
• 化学式: C₁₂H₃₃ClFeP₄
• 分子量: 392.589
• InChiKey: SOVPNRVPPGIYNN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.36
• 重原子数：
  18.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  trans-FeHCl(dmpe)2 、 肼 以 四氢呋喃 为溶剂， 以76%的产率得到trans-[FeH(hydrazine)(1,2-bis(dimethylphosphino)ethane)2]Cl
  参考文献：
  名称：

  Synthesis and Characterization of Iron(II) and Ruthenium(II) Hydrido Hydrazine Complexes

  摘要：

  Treatment of trans-[MHCl(dmpe)(2)] (M = Fe, Ru) with hydrazine afforded the hydrido hydrazine complexes cis- and trans-[MH(N2H4)(dmpe)(2)](+) which have been characterized by NMR spectroscopy (H-1, P-31, and N-15). Both cis and trans isomers of the Fe complex and the trans isomer of the Ru complex were characterized by X-ray crystallography. Reactions with acid and base afforded a range of N2Hx complexes, including several unstable hydrido hydrazido complexes.

  DOI：

  10.1021/ic102519f
• 作为产物：
  描述：

  FeH(η2-H2)(dppm)2(1+) 在 lithium chloride 作用下， 以 乙醇 为溶剂， 以>99的产率得到trans-FeHCl(dmpe)2
  参考文献：
  名称：

  通过二氢化铁与醇的可逆质子化作用形成铁的分子氢配合物

  摘要：

  的可逆的质子化的顺式-FeH 2（PP）2 [PP = R 2 PCH 2 CH 2 PR 2 ]由乙醇络合物产生η 2 -CO-统筹分子氢配合物的反式-FeH（H 2）（PP）2 +，其易发生H 2损失的取代。

  DOI：

  10.1039/c39880000546

文献信息

• Iron-Catalyzed C–H Borylation of Arenes
  作者：Thomas Dombray、C. Gunnar Werncke、Shi Jiang、Mary Grellier、Laure Vendier、Sébastien Bontemps、Jean-Baptiste Sortais、Sylviane Sabo-Etienne、Christophe Darcel

  DOI：10.1021/jacs.5b00895

  日期：2015.4.1

  Well-defined iron bis(diphosphine) complexes are active catalysts for the dehydrogenative C-H borylation of aromatic and heteroaromatic derivatives with pinacolborane. The corresponding borylated compounds were isolated in moderate to good yields (25-73%) with a 5 mol% catalyst loading under UV irradiation (350 nm) at room temperature. Stoichiometric reactivity studies and isolation of an original tran

  明确定义的双（二膦）铁配合物是芳烃和杂芳烃衍生物与频哪醇硼烷脱氢 CH 硼酸化的活性催化剂。相应的硼化化合物以中等至良好的产率 (25-73%) 在室温下紫外线照射 (350 nm) 下以 5 mol% 的催化剂负载分离。化学计量反应性研究和原始反式氢化（硼基）铁络合物 Fe(H)(Bpin)(dmpe)2 的分离使我们能够提出一种机制，显示一些关键催化物质的作用。
• Synthesis of an Iron Parent Amido Complex and a Comparison of Its Reactivity with the Ruthenium Analog
  作者：Daniel J. Fox、Robert G. Bergman

  DOI：10.1021/om0499660

  日期：2004.4.1

  complex (dmpe)2Fe(H)(NH2) (2; dmpe = 1,2-bis(dimethylphosphino)ethane) has been prepared from the hydrido chloride complex using sodium amide in a liquid ammonia/THF solvent mixture. The complex is a mixture of trans and cis isomers in solution, although it crystallizes as the trans isomer exclusively. Complex 2 is a strong base, although somewhat weaker than the ruthenium amido complex trans-(dmpe)2Ru(H)(NH2)

  氨基酰胺铁配合物（dmpe）2 Fe（H）（NH 2）（2 ; dmpe = 1,2-双（二甲基膦基）乙烷）是使用氨化钠在液态氨/ THF溶剂混合物中由氢化氯配合物制备的。该络合物是溶液中反式和顺式异构体的混合物，尽管它仅以反式异构体形式结晶。配合物2是强碱，尽管比钌酰胺基配合物反式-（dmpe）2 Ru（H）（NH 2）（1）弱。酰胺基络合物2使几种弱酸去质子化，其中一些去质子化导致氨的置换，而另一些则不会。复合物2的基本性用酸性底物可逆地去质子化的系统进一步证明了这一点。配合物2与甲苯d 8进行H / D交换，并催化甲苯d 8与其他几种极弱酸之间的H / D交换。了调查的H / d交换的机制和异构化反应的反式-9,10-二异丙基-9,10-二氢蒽（反式- 4）使用1，2，和顺式- （PME 3）4的Ru（H） （NH 2）（5）作为催化剂证明了H / D交换反应是通过形成离子对而进行的
• Synthesis of a First-Row Transition Metal Parent Amido Complex and Carbon Monoxide Insertion into the Amide N−H Bond
  作者：Daniel J. Fox、Robert G. Bergman

  DOI：10.1021/ja035707a

  日期：2003.7.1

  The parent amido iron complex (dmpe)2Fe(H)(NH2) (dmpe = 1,2-bis(dimethylphosphino)ethane), the first such first-row transition metal complex, has been synthesized and characterized spectroscopically and crystallographically. This complex has been found to insert carbon monoxide into the amide N-H bond (rather than the M-N bond) to give trans-(dmpe)2Fe(H)(NHCHO). The mechanism of this transformation

  母体氨基铁络合物 (dmpe)2Fe(H)(NH2)（dmpe = 1,2-双（二甲基膦基）乙烷）是第一个这样的第一行过渡金属络合物，已合成并在光谱和晶体学上表征。已发现该复合物将一氧化碳插入酰胺 NH 键（而不是 MN 键）中，得到反式-(dmpe)2Fe(H)(NHCHO)。已经研究了这种转变的机制，并认为是通过一种不寻常的机制发生的，其中 CO 表现为明显的亲电子试剂。
• Ferralactone formation from iron acetylides and carbon dioxide
  作者：Peter M. Jurd、Hsiu L. Li、Mohan Bhadbhade、James D. Watson、Leslie D. Field

  DOI：10.1016/j.jorganchem.2021.122252

  日期：2022.3

  O)(dmpe)2] where the phenyl substituent is attached to the carbon adjacent to the carbonyl group of the metalalactone. Remarkably, reaction of CO2 with the side-on-bound complex Fe(η2-HC≡CPh)(dmpe)2] forms a different phenyl-substituted metalalactone cis- [Fe(OC(=O)CHC(Ph)-κ2C,O)(dmpe)2] where the phenyl substituent is attached to the metal-bound carbon of the metalalactone ring.

  CO 2与乙炔化铁氢化物反式反应迅速- [FeH(C≡CH)(dmpe) 2 ] 通过插入金属氢化物键。然而，该反应是可逆的，反应的最终产物是 ferralactones cis - [Fe(OC(=O)CHCH-κ 2 C,O )(dmpe) 2 ] 和cis - [Fe(OC(=O) C(C(=O)OH)CH-κ 2 C,O )(dmpe) 2 ]由单和双CO 2 分别加成到配位乙炔的β-碳上，然后环化。叔丁基乙炔络合物反式的反应- [FeH(C≡C t Bu)(dmpe) 2 ] 与 CO 2得到叔丁基取代的铁内酯cis - [Fe(OC(=O)C( t Bu)CH-κ 2 C,O )(dmpe) 2 ]。CO 2与反式- [FeH(C≡CPh)(dmpe) 2 ] 形成苯基取代的铁内酯cis - [Fe(OC(=O)C(Ph)CH-κ 2 C,O )(dmpe) 2 ]，其中苯基取
• Nitrogen Fixation Revisited on Iron(0) Dinitrogen Phosphine Complexes
  作者：Leslie D. Field、Nilay Hazari、Hsiu L. Li

  DOI：10.1021/acs.inorgchem.5b00211

  日期：2015.5.18

  A reinvestigation of the treatment of [Fe(N-2)(PP)(2)] (PP = depe, dmpe) with acid revealed no ammonium formation. Instead, rapid protonation at the metal center to give hydride Complexes was observed. Treatment of [Fe(N-2)(dmpe)(2)] with methylating agents such as methyl triflate or methyl tosylate resulted methylation of the metal center to afford [FeMe(N-2)(dmpe)(2)](+). Treatment of [Fe(N-2)(dmpe)(2)] With trimethylsilyl triflate, however, resulted in reactibn at dinitrogen affording NH4+ on subsequent treatment with acid. The side-on bound hydrazine complex [Fe-(N2H4)(dmpe)(2)](2+) and bis(ammonia) complex [Fe(NH3)(2)(dmpe)(2)](2+) were identified by N-15 NMR spectroscopy as other species formed in the reaction mixture.