[Fe(CH2SiMe3)2(iPrBIP)] | 862169-55-9

• 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: [Fe(CH2SiMe3)2(iPrBIP)]
• 英文别名: [Fe(CH₂SiMe₃)₂(^iPrBIP)]；iron(II)(bis(2,6-(i-Pr)2-phenyl-iminomethyl)pyridine)(CH2SiMe3)2；([2,6-[2,6(i-Pr)2PhN=C(CH3)]2)(C5H3N)Fe(CH2SiMe3)2]；[2,6-(2,6-(iPr)2PhNC(CH3)]2(C5H3N))Fe(CH2SiMe3)2；((iPr)PDI)Fe(CH2SiMe3)2
• CAS: 862169-55-9
• 化学式: C₄₁H₆₅FeN₃Si₂
• 分子量: 712.005
• InChiKey: YPHJPVAJEFRFOZ-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：

  [Fe(CH2SiMe3)2(iPrBIP)] 在 三甲基铝 作用下， 以 甲苯 为溶剂， 反应 0.08h， 以77%的产率得到[Fe(CH₂SiMe₃)(^iPrBIP)]
  参考文献：
  名称：

  Sequential Reduction and Alkyl Exchange Reactions of Bis(imino)pyridine Dialkyliron(II) with Trimethylaluminum

  摘要：

  DOI：

  10.1021/om500167r
• 作为产物：
  描述：

  (2-[2,6(i-Pr)2PhN=C(CH3)]-6-[2,6-(i-Pr)2PhNC(CH3)(CH2SiMe3)](C5H3N))Fe(CH2SiMe3) 以 乙醚 为溶剂， 以62%的产率得到[Fe(CH2SiMe3)2(iPrBIP)]
  参考文献：
  名称：

  Metal versus Ligand Alkylation in the Reactivity of the (Bis-iminopyridinato)Fe Catalyst

  摘要：

  The alkylation of the Brookhart-Gibson {2,6-[2,6-(i-Pr)(2)PhN=C(CH3)](2)(C5H3N)} FeCl2 precatalyst with 2 equiv of LiCH2Si(CH3)(3) led to the isolation of several catalytically very active products depending on the reaction conditions. The expected dialkylated species {2,6-[2,6-(i-Pr)2PhN=C(CH3)](2)](C5H3N)Fe(CH2-SiMe3)(2) (2) was indeed the major component of the reaction mixture. However, other species in which alkylation occurred at the pyridine ring ortho position, {2,6-[2,6-(i-Pr)(2)PhN=C(CH3)](2)-2-CH2SiMe3}(C5H3N)Fe(CH2SiMe3) (1), and at the imine C atom, {2-[2,6-(i-Pr)(2)PhN=C(CH3)]-6-[2,6-(i-Pr)(2)PhNC(CH3)(CH2 SiMe3)](C5H3N)}Fe(CH2SiMe3) (3), have also been isolated and fully characterized. In addition, deprotonation of the methyl-imino functions and formation of a new divalent Fe catalyst 1[2,6-[2,6-(i-Pr)(2)PhNC=(CH2)](2)(C5H3N)}Fe(mu-Cl)Li(THF)(3) (4) also occurred depending on the reaction conditions. In turn, the formation of 4 might trigger the reductive coupling of two units through the methyl-carbon wings. This process resulted in the one-electron reduction of the metal center, affording a dinuclear Fe(I) alkyl catalyst 1[1[2,6(i-Pr)(2)C6H5]N=C(CH3)](C5H3N) f [2,6-(i-Pr)(2)C6H5]N=CCH2}Fe(CH2SiMe3)]}2 (5). Different from other metal derivatives, complex 5 could not be prepared from the monodeprotonated version of the ligand. Its reaction with a mixture of FeCl2 and RLi afforded instead [12,6-[2,6-(i-Pr)(2)PhN-C=(CH2)](2)(C5H3N)}FeCH2Si(CH3)(3)][Li(THF)(4)] (6) which is also catalytically active. All of these high-spin species have been shown to have high catalytic activity for olefin polymerization, producing polymers of two distinct natures, depending on the formal oxidation state of the metal center.

  DOI：

  10.1021/ja054152b

文献信息

• Synthesis of Bis(imino)pyridine Iron Di- and Monoalkyl Complexes: Stability Differences between FeCH₂SiMe₃ and FeCH₂CMe₃ Derivatives
  作者：Ignacio Fernández、Ryan J. Trovitch、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/om700913g

  日期：2008.1.1

  plane. Ligand substitution reactions where the terdentate bis(imino)pyridine is used to displace pyridine from py2Fe(R)X (R = CH2SiMe3, CH2CMe3; X = Cl, CH2SiMe3, CH2CMe3) further demonstrated the relative stability of five-coordinate FeCH2SiMe3 versus FeCH2CMe3 complexes. For the neopentyl compounds, ejection of a neopentyl radical or alkylation of the p-pyridine position of the chelate was observed

  已经用LiCH 2 SiMe 3，LiCH 2 CME 3和LiPh探索了芳基取代的双（亚氨基）吡啶二卤化铁烷基化和芳基化反应的范围。仅当用2当量的LiCH 2 SiMe 3处理2，6-二异丙基芳基取代的铁络合物时才观察到二烷基化。在所有其他情况下，发生还原性烷基化反应以形成四配位双（亚氨基）吡啶铁单烷基络合物。其中的一个产品，（的Et PDI）FECH 2 CME 3 [的Et PDI = 2,6-（2,6-ET 2 ç 6 ħ 3 N═CME）2 Ç6 H 3 N）]已经通过晶体学表征并且显示出由于烷基的空间位置而引起的扭曲的正方形平面几何形状。从用3当量的芳基锂处理相应的二卤化物中分离出带有弱活化的二氮配体的五配位双（亚氨基）吡啶铁芳基“酸酯”配合物。甲苯基衍生物通过X射线衍射进行表征，并建立了扭曲的方形锥体结构，其中二氮配体完成了理想化的基础平面。配体取代反应，其中使用叔齿双（亚氨基）吡啶从py
• Square planar bis(imino)pyridine iron halide and alkyl complexes
  作者：Marco W. Bouwkamp、Suzanne C. Bart、Eric J. HawrelakPresent address: Department、Ryan J. Trovitch、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1039/b504063a

  日期：——

  Square planar iron methyl complexes containing bis(imino)pyridine (PDI) ligands have been prepared by reductive alkylation of the corresponding ferrous dichloride; dialkylation is observed upon treatment with a larger alkyl lithium.

  通过对相应的二氯化亚铁进行还原烷基化，制备出了含有双（亚氨基）吡啶（PDI）配体的方形平面甲基铁络合物；在使用较大的烷基锂进行处理时，可观察到二烷基化现象。
• Bis(imino)pyridine Ligand Deprotonation Promoted by a Transient Iron Amide
  作者：Marco W. Bouwkamp、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ic051839o

  日期：2006.1.1

  Addition of 2 equiv of LiNMe2 to the bis(imino)pyridine ferrous dichloride, ((PDI)-P-iPr)FeCl2 ((PDI)-P-iPr = (2,6-Pr-i(2)-C6H3N=CMe)(2)C5H3N), resulted in deprotonation of the chelate methyl groups, yielding the bis(enamide)pyridine iron dimethylamine adduct, ((iPr)PDEA)Fe-(NHMe2) ((iPr)PDEA = (2,6-Pr-i(2)-C6H3NC=CH2)(2)C5H3N). Performing a similar procedure with KN(SiMe3)(2) in THF solution afforded the corresponding bis(THF) adduct, ((iPr)PDEA)Fe(THF)(2). ((iPr)PDEA)Fe-(NHMe2) has also been prepared by addition of the free amine to the iron dialkyl complex, ((PDI)-P-iPr)Fe(CH2SiMe3)(2), implicating formation of a transient iron amide that is sufficiently basic to deprotonate the bis(imino)pyridine methyl groups. Deprotonation of the amine ligand in ((iPr)PDEA)Fe(NHMe2) has been accomplished by addition of amide bases to afford the ferrous amide-ate complexes, [((iPr)PDEA)Fe(mu-NMe2)M] (M = Li, K).
• Bis(imino)pyridine Iron(II) Alkyl Cations for Olefin Polymerization
  作者：Marco W. Bouwkamp、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ja0524447

  日期：2005.7.13

  Treatment of the five-coordinate ferrous dialkyl complex, (iPrPDI)Fe(CH2SiMe3)2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N), with [PhMe2NH][BPh4] in the presence of diethyl ether or tetrahydrofuran furnished the corresponding alkyl cations, where the donor ligand is coordinated in the basal plane of a distorted square pyramidal iron(II) alkyl cation. Performing the same reaction with the neutral Lewis acid, B(C6F5)3, induced methide abstraction from a silicon atom followed by rearrangement to afford the base free ferrous alkyl cation, [(iPrPDI)Fe(CH2SiMe2CH2SiMe3)][MeB(C6F5)3]. This complex is active for the polymerization of ethylene and yields polymers that are of higher molecular weight and narrower polydispersity than traditional methylalumoxane-activated catalysts.
• Formation of a Paramagnetic Al Complex and Extrusion of Fe during the Reaction of (Diiminepyridine)Fe with AlR₃ (R = Me, Et)
  作者：Jennifer Scott、Sandro Gambarotta、Ilia Korobkov、Quinten Knijnenburg、Bas de Bruin、Peter H. M. Budzelaar

  DOI：10.1021/ja056135s

  日期：2005.12.1

  The reaction of the 2,6-[2,6-(iPr)2PhN=C(CH3)]2(C5H3N)}FeCl2 catalyst precursor with R3Al [R = Me, Et] afforded 2,6-[2,6-(iPr)2PhN=C(CH3)]2(C5H3N)}AlMe2 (1) and [eta4-LAl2Et3(mu-Cl)]Fe-(eta6-C7H8) (2), respectively. These paramagnetic species arises from both transmetalation, during which the strong terdentate ligand loses the Fe center, and reduction. The extent of reduction depends on the nature of the Al alkylating agent. The electrons necessary for the reduction are likely to be provided by cleavage of Fe-C bond of transient low-valent organo-Fe species.