(Li2(N,N'-[1,3-phenylenebis(methylene)]bis-2,6-diisopropylaniline(-2H)))2 | 500876-61-9

• 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: (Li2(N,N'-[1,3-phenylenebis(methylene)]bis-2,6-diisopropylaniline(-2H)))2
• 英文别名: [(2,6-bis(([2,6-bis(1-methylethyl)phenyl]azanidyl)methyl)phenyl)Li2]2；tetralithium;[2,6-di(propan-2-yl)phenyl]-[[3-[[2,6-di(propan-2-yl)phenyl]azanidylmethyl]phenyl]methyl]azanide
• CAS: 500876-61-9
• 化学式: C₆₄H₈₄Li₄N₄
• 分子量: 937.162
• InChiKey: ZFMVGGXAHYKHRU-UHFFFAOYSA-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：

  [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

文献信息

• NCN TRIANIONIC PINCER COMPLEXES AS CATALYSTS FOR OLEFIN POLYMERIZATION AND ISOMERIZATION
  申请人：UNIVERSITY OF FLORIDA RESEARCH FOUNDATION, INC.

  公开号：US20130289326A1

  公开（公告）日：2013-10-31

  A catalyst comprising a NCN pincer ligand group VI complex is capable of being used as an olefin polymerization or isomerization catalyst that does not require an expensive cocatalyst. The complex has the NCN pincer ligand in a trianionic form with the group VI in the +3 oxidation state or the +4 oxidation state and complexed to an anionic hydrocarbon group, or the complex has the NCN pincer ligand in a dianionic form with the group VI in the +2 oxidation state. The complex is capable of initiating the polymerization of alkenes without an added activator. The presence of a water scavenger and activator or cocatalyst, such as triisobutylaluminum, increases the catalytic activity. The complex is capable of selectively isomerizing 1-alkenes to cis/trans 2-alkenes.

  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。
• NCN Trianionic Pincer Ligand Precursors: Synthesis of Bimetallic, Chelating Diamide, and Pincer Group IV Complexes
  作者：Soumya Sarkar、Kevin P. McGowan、Jeffrey A. Culver、Adam R. Carlson、Jürgen Koller、Andrew J. Peloquin、Melanie K. Veige、Khalil A. Abboud、Adam S. Veige

  DOI：10.1021/ic100232s

  日期：2010.6.7

  explain the apparent low symmetry of 13 in solution. Extension of the aliphatic arm of the NCN ligand provides the new NCCCN pincer ligand precursors N,N′-(2,2′-(1,3-phenylene)bis(ethane-2,1-diyl))bis(3,5-bis(trifluoromethyl)aniline) [3,5-CF3NCCCN]H3 (16) and [3,5-CF3NCCHCN](SiMe3)2 (17). A more rigid ligand architecture was accessed by synthesis of the anthracene derived pincer ligand anthracene-1

  该报告详细介绍了新的NCN三阴离子钳形配体前体的合成和金属化反应，以形成基团（IV）配合物。Ñ，Ñ ' - [1,3-亚苯基双（亚甲基）]双- 2,6-二异丙基[2,6-我PrNCN 1 H 3（8）转化成Ñ，Ñ '取代的Si（IV）， Sn（IV），Mg（II）和Zn（II）衍生物。[2,6- i PrNCHN]（SiMe 3）2（9-Si）和[2,6- i PrNCHN]（SnMe 3）2（9-Sn）形式，首先用MeLi处理8，然后用Me 3处理MCl，其中M = Si或Sn。单晶X射线实验表明8，9-硅，和9-Sn系具有在固态相似的结构特征。[ 2,6- i PrNCHN]（μ-MgCl·THF）2（12）通过用MeMgCl处理8形成，其固态结构显示双-μ-MgCl桥联单元。12的1 H NMR光谱表明溶液中发生了动态过程。可变温度1 H NMR实验未能消除动力学过程。2,6- i