(2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine)trichlorochromium(III) | 404866-60-0

• 英文名称: (2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine)trichlorochromium(III)
• CAS: 404866-60-0
• 化学式: C₃₃H₄₃Cl₃CrN₃
• 分子量: 640.08
• InChiKey: DHUHTBWYWGIAJP-VRCYMSAESA-K

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine)trichlorochromium(III) 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以22%的产率得到
  参考文献：
  名称：

  双（亚氨基）吡啶配体的铬配合物的反应活性：携带处于低氧化态的金属的高活性乙烯聚合催化剂

  摘要：

  A divalent chromium complex of bis(imino)pyridine, {2,6-[2,6-(i-Pr)(2)PhNC(CH3)](2)(C5H3N)}CrCl2 (1), was prepared with the aim of studying its reactivity with alkylating agents. Upon treatment with MeLi, the metal center was both reduced and alkylated, forming {2,6-[2,6-(i-Pr)(2)PhNC(CH3)](2)(C5H3N)}CrMe(mu-Me)Li(THF)(3) (2). Complex 1 is also conveniently reduced with either NaH or metallic sodium to give the new species {2,6-[2,6-(i-Pr)(2)PhNC(CH3)](2)(C5H3N)}CrCl (3). Despite the appearance of the metal center in a rare monovalent oxidation state, the square-planar geometry of the Cr atom suggests that the metal is most likely divalent, with the electron housed in the ligand pi* orbital. When it is activated with MAO, complex 3 is a very and even more active catalyst for the polymerization of ethylene than either the -CrCl2 or -CrCl3 derivative of this ligand system and yet produces polymers with similar properties. Subsequent reactivity studies of complex 3 have allowed the isolation of several products. Reaction with either LiCH2Si(CH3)(3) or MeLi resulted in deprotonation of one of the methyl groups on the ligand backbone, forming {2-[2,6-(i-Pr)(2)PhNC(CH3)]-6-[2,6-(i-Pr)(2)PhNCCH2](C5H3N)}Cr(THF) (4) and {2-[2,6-(i-Pr)(2)PhNC(CH3)]-6-[2,6-(i-Pr)(2)PhNCCH2](C5H3N)}Cr(mu-Me)Li(THF)(3) (5), respectively. On the other hand, alkylation with AlMe3 allowed the successful preparation of another organochromium species, {2,6-[2,6-(i-Pr)(2)PhNC(CH3)](2)(C5H3N)}CrCH3 (7), along with small amounts of the byproduct {2,6-[2,6-(i-Pr)(2)PhNC(CH3)](2)(C5H3N)}Cr(mu-Cl)(2)Al(CH3)(2) (6). Interestingly, complex 7, which also has the deceiving connectivity of a monovalent species, displays an even greater activity for ethylene polymerization than all of the other species reported herein, again producing a polymer with nearly identical characteristics. Activation with IBAO revealed a deactivation pathway similar to that observed with the FeCl2 system. In this case, the stronger reducing power of IBAO resulted in the usual reduction not only of the ligand backbone but also of the metal center. As a result of the metal reduction, partial transmetalation of the ligand system occurred, with formation of [eta(4)-{2,6-[2,6-(i-Pr)(2)PhNC(CH3)](2)(C5H3N)}Al-2(i-Bu)(3)(mu-Cl)]Cr-(eta(6)-C7H8) (8). By being catalytically inactive, the partly transmetalated 8 suggests that ligand demetalation is a possible catalyst deactivation pathway.

  DOI：

  10.1021/om0701423
• 作为产物：
  描述：

  trichlorotris(tetrahydrofuran)chromium(III) 、 2,6-双[1-(2,6-二异丙苯亚氨基)乙基]吡啶 以 丙酮 为溶剂， 以90%的产率得到(2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine)trichlorochromium(III)
  参考文献：
  名称：

  双（亚氨基）吡啶基铬（III）配合物的制备，结构和乙烯聚合行为

  摘要：

  报道了式[2,6-双（亚氨基）吡啶基] CrCl 3的一族铬（III）配合物的合成，表征和乙烯聚合行为。两个新的化合物的X射线衍射研究显示，围绕铬原子的几何形状是八面体，与在三个氯配体聚体布置。金属与一个转置的氯原子之间的距离明显长于其他两个Cr-Cl距离。复合物[2,6-双（亚氨基）吡啶基] CrCl 3的处理用甲基铝氧烷（MAO）与乙烯反应可制得非常活跃的乙烯聚合催化剂，可提供高度线性的聚乙烯。2，6-双（亚氨基）吡啶基配体的N-芳基邻位的取代基既调节催化活性，又调节所得聚乙烯的分子量。最活泼的催化剂是那些具有两个取代基在N-芳基（活动起来的邻位至4×10 7克的Cr（摩尔）- 1巴- 1个H ^ - 1实现）。关于取代基的大小，活性和分子量遵循相反的趋势。具有两个小的取代基的体系会产生非常活跃的体系，但聚乙烯的分子量低于存在较大取代基的体系。

  DOI：

  10.1021/om020561u

文献信息

• Participation of the α,α‘-Diiminopyridine Ligand System in Reduction of the Metal Center during Alkylation
  作者：Hiroyasu Sugiyama、Ghazar Aharonian、Sandro Gambarotta、Glenn P. A. Yap、Peter H. M. Budzelaar

  DOI：10.1021/ja020485m

  日期：2002.10.1

  The reaction of [2,6-(i-Pr)(2)PhN=C(Me)](2)(C5H3N)}MnCl2 with alkylating agents formed a dinuclear Mn(I) derivative via ligand reductive coupling. In the case of the trivalent Cr analogue, a similar reaction afforded reduction toward Cr(II) but also alkylation at the pyridine ring para position followed by an unprecedented cycloaddition that generated a tricyclic system.