[chromium(IV)(methyl)(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)(THF)] | 1333117-62-6

• 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: [chromium(IV)(methyl)(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)(THF)]
• 英文别名: carbanide;chromium(4+);[2,6-di(propan-2-yl)phenyl]-[[3-[[2,6-di(propan-2-yl)phenyl]azanidylmethyl]benzene-2-id-1-yl]methyl]azanide;oxolane
• CAS: 1333117-62-6
• 化学式: C₃₇H₅₂CrN₂O
• 分子量: 592.829
• InChiKey: IHWRPORVQXIYEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.64
• 重原子数：
  41
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.49
• 拓扑面积：
  11.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [chromium(IV)(methyl)(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)(THF)] 、 三(五氟苯基)硼烷 以 氘代苯 为溶剂， 生成 [chromium(IV)(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)(THF)](B(Me)(C6F5)3)
  参考文献：
  名称：

  A neutral trianionic pincer [NCN]CrIV–Me complex as a highly active ethylene polymerization precatalyst

  摘要：

  Trianionic pincer ligands are a new class of ligands that constrain three anionic metal-ligand bonds to the meridional plane and are capable of supporting highly reactive metal species exploitable for alkene polymerization. The previously reported NCN3- trianionic pincer Cr-IV-Me complex [2,6-(PrNCN)-Pr-i]Cr-IV(Me) THF (1), upon activation by triisobutylaluminum (TIBA), catalyzes the polymerization of ethylene. Complex 1 (1 mu mol) in the presence of 35 equiv. of TIBA polymerizes ethylene with an activity of 7.02 x 10(6) g PE(molCr)(-1) h(-1) (75 degrees C). Published by Elsevier B.V.

  DOI：

  10.1016/j.jorganchem.2012.03.007
• 作为产物：
  描述：

  [CrCl2Me(tetrahydrofuran)3] 、 (Li2(N,N'-[1,3-phenylenebis(methylene)]bis-2,6-diisopropylaniline(-2H)))2 以 乙醚 为溶剂， 以10%的产率得到[chromium(IV)(methyl)(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)(THF)]
  参考文献：
  名称：

  Trianionic NCN^3– Pincer Complexes of Chromium in Four Oxidation States (Cr^II, Cr^III, Cr^IV, Cr^V): Determination of the Active Catalyst in Selective 1-Alkene to 2-Alkene Isomerization

  摘要：

  The synthesis and characterization of a series of four Cr complexes in the +2, +3, +4, and +5 oxidation states supported by an NCN trianionic pincer ligand are reported. Treating CrMeCl2(THF)(3) with the dilithio salt pincer ligand precursor {[2,6-(PrNCHN)-Pr-i]Li-2}(2) provides the Cr-III complex [2,6-(PrNCN)-Pr-i]Cr-III(THF)(3) (1), Cr-IV complex [2,6-(PrNCN)-Pr-i](CrMe)-Me-IV(THF) (2), and Cr-II complex [2,6-(PrNHCN)-Pr-i]Cr-II(THF)(2) (3). Complexes 2 and 3 are the result of disproportionation. Treating 1 with 1 equiv of styrene oxide in THF converts the Cr-III complex to the Cr-V(O) species [2,6-(PrNCN)-Pr-i]Cr-V(O)(THF) (4). Complex 2, characterized by single-crystal X-ray diffraction, is a rare Cr-IV methyl complex that is kinetically stable at 25 degrees C; at 85 degrees C, Cr-Me bond homolysis occurs. The homolytic cleavage results in CH4 formation and biphenyl via a radical mechanism. The metal-containing product from thermolysis is the same Cr-II species formed during metalation, except one of the protons is substituted for a deuterium from C6D6 (3-d). Complex 2 is a precatalyst for the selective isomerization of 1-hexene and 1-octene to the corresponding 2-alkenes. An induction period occurs during the catalytic isomerization, and the active catalyst was determined to be the Cr-II complex 3, not 2.

  DOI：

  10.1021/om200547u
• 作为试剂：
  描述：

  1-己烯 在 [chromium(IV)(methyl)(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)(THF)] 作用下， 以 氘代苯 为溶剂， 反应 60.0h， 以92%的产率得到2-己烯
  参考文献：
  名称：

  NCN TRIANIONIC PINCER COMPLEXES AS CATALYSTS FOR OLEFIN POLYMERIZATION AND ISOMERIZATION

  摘要：

  一种包含NCN夹夹持配体的六号族羰基复合物催化剂可用作烯烃聚合或异构化催化剂，无需昂贵的协同催化剂。该复合物具有NCN夹夹持配体，其处于三阴离子形式，羰基处于+3氧化态或+4氧化态，并与阴离子碳氢基团形成络合物，或者该复合物具有NCN夹夹持配体，其处于二阴离子形式，羰基处于+2氧化态。该复合物能够在无需添加活化剂的情况下启动烯烃的聚合反应。存在水清除剂和活化剂或协同催化剂，例如三异丁基铝，可增加催化活性。该复合物能够选择性地将1-烯烃异构化为顺式/反式2-烯烃。

  公开号：

  US20130289326A1