(iPrPDI)Fe(N2)2 | 799270-28-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (iPrPDI)Fe(N2)2
• CAS: 799270-28-3
• 化学式: C₃₃H₄₃FeN₇
• 分子量: 593.598
• InChiKey: LIJSTOCEXNCQMY-HNZPQQFJSA-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：

  (iPrPDI)Fe(N2)2 在 hexamethyldisiloxane 作用下， 以 氘代苯 为溶剂， 以78%的产率得到[Fe(2,6-(2,6-(i-Pr)2-C6H3NCMe)2C5H3N)]
  参考文献：
  名称：

  双（亚氨基）吡啶铁化合物的碳-氧键裂解：催化剂失活途径和酯中酰基C-O键裂解的观察。

  摘要：

  对双（亚氨基）吡啶铁催化的加氢和[2π+2π]二烯环化反应的底物范围的研究确定了C-O键断裂是主要的失活途径。将二烯丙基或烯丙基乙醚加至双（亚氨基）吡啶铁二氮配合物（iPr PDI）Fe（N 2）2（iPr PDI = 2,6-（2,6- i Pr 2 -C 6 H 3 N MeCMe）2 C 5 H 3 N，1-（N 2）2），在二氮气氛下导致C-O键的轻松裂解，并生成相应的顺磁性烯丙基铁和醇盐配合物的混合物。对于乙基乙烯基醚，观察到清洁和选择性形成乙醇铁，同时损失了乙烯基片段。肉桂酸反丁酯的催化加氢的原位监测建立了酯C-O键断裂的过程。1-（N 2）2之间的化学计量反应烯丙基和乙酸乙烯酯也产生了简便的C-O氧化加成反应。对于后者，获得六配位抗磁性双（亚氨基）吡啶乙酰氧基铁乙烯基化合物，并通过X射线衍射表征。乙酸苯酯进行独家的C-O键裂解，而烷基取代的酯（例如乙基，戊基，苄基，异丙基，环

  DOI：

  10.1021/om8005596
• 作为产物：
  描述：

  [(2,6-(i-Pr)2C6H3N=CMe)2C5H3N)Fe(2,6-Et2C6H3N)] 以 氘代苯 为溶剂， 生成 (iPrPDI)Fe(N2)2
  参考文献：
  名称：

  Synthesis and Hydrogenation of Bis(imino)pyridine Iron Imides

  摘要：

  Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3N=CMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with Mössbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N-H bond formation as the rate-determining step in aniline formation.

  DOI：

  10.1021/ja057165y
• 作为试剂：
  描述：

  3-甲基-2-丁烯酸乙酯 在 (iPrPDI)Fe(N2)2 、 氢气 作用下， 以 氘代苯 为溶剂， 23.0 ℃ 、405.33 kPa 条件下， 反应 24.0h， 生成 异戊酸乙酯
  参考文献：
  名称：

  Synthesis of Aryl-Substituted Bis(imino)pyridine Iron Dinitrogen Complexes

  摘要：

  The synthesis and characterization of dimeric, aryl-substituted bis(imino)pyridine iron dinitrogen complexes is described. In contrast to reduction with sodium amalgam where bis(chelate) iron compounds were isolated, stirring ((PDI)-P-Ar)FeBr2 or ((BPDI)-B-Me)FeBr2 (PDI = 2,6-(ArN=CMe)(2)C5H3N; Ar = 2,6-Et-2-C6H3N ((PDI)-P-Et), 2,6-Me-2-C6H3N ((PDI)-P-Me), 2-Pr-i,6-Me-C6H3N (Me,(PDI)-P-iPr); (BPDI)-B-Me = 2,6-(2,6-Me-2-C6H3N=CPh)(2)C5H3N) with sodium naphthalenide resulted in isolation of the desired iron dinitrogen compounds as diamagnetic solids, Two examples, [((PDI)-P-Et)Fe(N-2)](2)(mu(2)-N-2) and [((BPDI)-B-Me)Fe(N-2)](2)(mu(2)-N-2), were characterized by X-ray diffraction. The solid state metrical parameters, in combination with infrared and Mossbauer spectroscopic data, establish ferrous compounds with doubly reduced chelates. Each new bis(imino)pyridine iron dinitrogen compound was screened for the catalytic hydrogenation of ethyl-3-methylbut-2-enoate, and the compound bearing the smallest aryl substituent, [((PDI)-P-Me)Fe(N-2)](2)(mu(2)-N-2), offers significant improvement over the original ((PDI)-P-iPr)Fe(N-2)(2) pre-catalyst and is one of the most active iron pre-catalysts known.

  DOI：

  10.1021/ic902162z

文献信息

• Iron-Catalyzed, Hydrogen-Mediated Reductive Cyclization of 1,6-Enynes and Diynes: Evidence for Bis(imino)pyridine Ligand Participation
  作者：Kevin T. Sylvester、Paul J. Chirik

  DOI：10.1021/ja902478p

  日期：2009.7.1

  The bis(imino)pyridine iron dinitrogen complex (((i)Pr)PDI)Fe(N(2))(2) catalyzes the hydrogen-mediated reductive cyclization of enynes and diynes with turnover frequencies comparable to those of established precious metal catalysts. Amino, oxygenated, and carbon-based substrates are readily cyclized to the corresponding hetero- and carbocycles with 5 mol % iron and 4 atm H(2) at 23 degrees C. Stoichiometric

  双（亚氨基）吡啶铁二氮配合物（（（i）Pr）PDI）Fe（N（2））（2）催化氢介导的烯炔和二炔的还原环化，其周转频率与已建立的贵金属催化剂相当. 氨基、含氧和碳基底物很容易环化为相应的杂环和碳环，在 23 摄氏度时含有 5 mol % 铁和 4 atm H(2)。选定的底物与 N(2) 下的铁化合物之间的化学计量反应) 气氛建立了从异丙基芳基取代基到烯炔或二炔底物的转移脱氢。通过 (1) H NMR 光谱结合氘标记实验对催化反应进行原位监测，建立了快速环化，然后是限制营业额的氢化。
• Neutral-Ligand Complexes of Bis(imino)pyridine Iron:  Synthesis, Structure, and Spectroscopy
  作者：Suzanne C. Bart、Emil Lobkovsky、Eckhard Bill、Karl Wieghardt、Paul J. Chirik

  DOI：10.1021/ic700869h

  日期：2007.8.1

  S = 1 excited state via spin-orbit coupling. Metrical data from X-ray diffraction establish bis(imino)pyridine chelate reduction for each structural type, while Mossbauer parameters and NMR spectroscopic data differentiate the spin states of the iron and identify contributions from paramagnetic excited states.

  一族双（亚氨基）吡啶铁中性配体衍生物（（iPr）PDI）FeL（n）（（iPr）PDI = 2,6-（2,6-iPr2-C6H3N = CMe）2 ）由相应的双（二氮）配合物（（iPr）PDI）Fe（N2）2合成。当L是强磁场配体（例如tBuNC）或螯合的烷基二膦（例如DEPE）（DEPE = 1,2-双（二乙基膦基）乙烷）时，会形成五配位的反磁性化合物，而没有光谱证据证明顺磁态混合。将中性施主的电场强度降低至主要为sigma型配体（例如tBuNH2或THT（THT =四氢噻吩）），也会产生抗磁性化合物。然而，平面内双（亚氨基）吡啶氢的1H NMR化学位移表现出较大的化学位移分散，指示通过自旋轨道耦合混合S = 1激发态而产生的与温度无关的顺磁性（TIP）。来自X射线衍射的度量数据确定了每种结构类型的双（亚氨基）吡啶螯合物还原，而Mossbauer参数和NMR光谱数据区分了铁的自旋态并确定了顺磁激发态的贡献。
• Preparation and Molecular and Electronic Structures of Iron(0) Dinitrogen and Silane Complexes and Their Application to Catalytic Hydrogenation and Hydrosilation
  作者：Suzanne C. Bart、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ja046753t

  日期：2004.10.1

  of the five-coordinate iron(II) dihalide complexes (iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, (iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2). Both dinitrogen compounds serve as effective precatalysts

  五配位铁 (II) 二卤化物络合物 (iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N; X = Cl, Br) 在 1 个大气压的二氮下用钠汞合金还原得到正方形金字塔形，高自旋铁（0）双（二氮）络合物（iPrPDI）Fe（N2）2。在溶液中，(iPrPDI)Fe(N2)2 失去 1 当量的 N2 以提供单（二氮）加合物 (iPrPDI)Fe(N2)。这两种二氮化合物都可作为烯烃和炔烃加氢和硅氢化的有效预催化剂。在环境温度下，在非极性介质中使用低催化剂负载量（< 或 = 0.3 mol%）观察到有效的催化反应。催化氢化硅烷化在形成抗马尔科夫尼科夫产物方面具有选择性。
• Bis(imino)pyridine Iron Alkyls Containing β-Hydrogens: Synthesis, Evaluation of Kinetic Stability, and Decomposition Pathways Involving Chelate Participation
  作者：Ryan J. Trovitch、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ja803296f

  日期：2008.9.3

  Bis(imino)pyridine iron alkyl complexes bearing beta-hydrogens, ((iPr)PDI)FeR (((iPr)PDI = 2,6-(2,6-(i)Pr2-C6H3N=CMe)2C5H3N; R = Et, (n)Bu, (i)Bu, CH2 (cyclo)C5H 9; 1-R), were synthesized either by direct alkylation of ((iPr)PDI)FeCl (1-Cl) with the appropriate Grignard reagent or more typically by oxidative addition of the appropriate alkyl bromide to the iron bis(dinitrogen) complex, ((iPr)PDI)Fe(N2)2

  在氧化加成过程中，正式的氧化过程是基于双（亚氨基）吡啶配体的（从每个螯合物中正式去除一个电子，而不是铁）。在苯-d6 溶液中测定了每种 1-R 化合物的动力学稳定性，发现产生相应的烷烃和烯烃的混合物。烷基铁配合物的动力学稳定性与存在的 β-氢的数量成反比。例如，铁乙基配合物 1-Et 在三个小时内完全失去乙烷，而相应的 1-(i)Bu 化合物在相同条件下的半衰期超过 12 小时。通过一系列氘标记实验研究了分解的机制，并支持了一条途径，包括初始β-氢消除，然后是异丙基甲基的环金属化，展示了整体转移氢化途径。还介绍了这种途径与双（亚氨基）吡啶铁催化的烯烃聚合反应中链转移的相关性。
• Iron-Mediated Coupling of Carbon Dioxide and Ethylene: Macrocyclic Metallalactones Enable Access to Various Carboxylates
  作者：Stephan M. Rummelt、Hongyu Zhong、Ilia Korobkov、Paul J. Chirik

  DOI：10.1021/jacs.8b07558

  日期：2018.9.19

  subsequent ethylene insertions to generate macrocyclic metallalactones. Competitive β-hydride elimination, CO2 insertion, or reaction with H2 determines the fate of the metallalactone, the latter accounting for formation of iron complexes with saturated carboxylates. Similar reactivity was observed upon addition of propiolactone and ethylene to (iPrPDI)Fe(N2)2, supporting C-O oxidative addition and

  用 CO2 和乙烯处理 (iPrPDI)Fe(N2)2 (iPrPDI, 2,6-(2,6-iPr2C6H3N=CMe)2C5H3N) 导致形成一系列同系的饱和和不饱和羧酸铁产物，(iPrPDI )Fe(O2CR)，其分布取决于试剂的比例。阐明了饱和产物 (iPrPDI)Fe(O2CC2H5) 的固态和电子结构。产物分布、氘标记研究和化学计量实验支持五元金属内酯中间体的初始形成，该中间体经过随后的乙烯插入以生成大环金属内酯。竞争性 β-氢化物消除、 插入或与 H2 反应决定了金属内酯的命运，后者解释了铁与饱和羧酸盐络合物的形成。