([2,6-([2,6-(i-Pr)2C6H3]N-C(=CH2))2(C5H3N)]Li(tetrahydrofuran))[Li(tetrahydrofuran)4] | 749223-17-4

• 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: ([2,6-([2,6-(i-Pr)2C6H3]N-C(=CH2))2(C5H3N)]Li(tetrahydrofuran))[Li(tetrahydrofuran)4]
• 英文别名: [((2,6-(i-Pr)2PhNC=(CH2))(C5H3N)(2,6-(i-Pr)2PhN=C(CH2)))Li(THF)][Li(THF)4]；([2,6-([2,6(i-Pr)2C6H3]N-C=(CH2))2(C5H3N)]Li(THF))(Li(THF)4)
• CAS: 749223-17-4
• 化学式: C₁₆H₃₂LiO₄*C₃₇H₄₉LiN₃O
• 分子量: 854.125
• InChiKey: KZCAMBKKSQMWBD-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：

  iron(dichloride)*1.5(tetrahydrofuran) 、 ([2,6-([2,6-(i-Pr)2C6H3]N-C(=CH2))2(C5H3N)]Li(tetrahydrofuran))[Li(tetrahydrofuran)4] 以 四氢呋喃 为溶剂， 以56%的产率得到(2,6-[2,6(i-Pr)2PhN-C=(CH2)]2(C5H3N))Fe(μ-Cl)Li(THF)3
  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

• Preparation, Characterization, and Magnetic Behavior of the Ln Derivatives (Ln = Nd, La) of a 2,6-Diiminepyridine Ligand and Corresponding Dianion
  作者：Hiroyasu Sugiyama、Ilia Korobkov、Sandro Gambarotta、Angela Möller、Peter H. M. Budzelaar

  DOI：10.1021/ic049820t

  日期：2004.9.1

  Nd atom antiferromagnetically coupled to a radical anion. By using the doubly deprotonated form of the diimino pyridine ligand [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)](2-) (2) the corresponding trivalent complexes [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)]Ln (THF)](mu-Cl)(2)[Li(THF)(2)].0.5 (hexane) [Ln = Nd (3), La (4)] were obtained and characterized. Reduction of these

  空前的Nd [2,6-[[2,6-（i-Pr）（2）C（6）H（5）] N = C（CH（3））]（2）（C（5）H （3）N）] NdI（2）（THF）（1）配合物的制备方法是：在2,6-[[2,6-（i-Pr）]存在下，用I（2）在THF中氧化金属Nd （2）C（6）H（5）] N ＝ C（CH（3））]（2）（C（5）H（3）N）。变量T处的磁行为清楚地表明，该络合物应视为反铁磁耦合至自由基阴离子的三价Nd原子。通过使用二亚氨基吡啶配体[[2,6-[[2,6-（i-Pr）（2）C（6）H（5）] NC = CH（2）]（2）的双去质子化形式（C（5）H（3）N）]（2-）（2）相应的三价络合物[[2,6-[[2,6-（i-Pr）（2）C（6）H（5 ）] NC = CH（2）]（2）（C（5）H（3）N）] Ln（THF）]（mu-Cl）（2）[Li（THF）（2）]。0.5（己烷）[Ln
• Ligand-assisted reduction of Co(II) to Co(I) and subsequent coordination of dinitrogen
  作者：Jennifer Scott、Sandro Gambarotta、Ilia Korobkov

  DOI：10.1139/v05-010

  日期：2005.4.1

  Reaction of the bis-aminopyridine dianion [2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)]Li(THF)}Li(THF)4} with CoCl2(THF)1.5 under Ar afforded the dinuclear complex [2,6-(i-Pr)2PhN-C=(CH2)](C5H3N)[2,6-(i-Pr)2PhN=C(CH2)]}2[Co(µ-Cl)Li(THF)3]2·4(THF) (1) in which the ligand is coupled to a second identical unit at a terminal methylene carbon. In turn, the C—C bond formation caused reduction of the Co(II) center

  双氨基吡啶二价阴离子 [2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)]Li(THF)}Li(THF)4} 与 CoCl2 的反应(THF)1.5 在 Ar 下得到双核络合物 [2,6-(i-Pr)2PhN-C=( )]( )[2,6-(i-Pr)2PhN=C( )]} 2[Co(μ-Cl)Li(THF)3]2·4(THF) (1) 其中配体在末端亚甲基碳上与第二个相同单元偶联。反过来，C 2 C 键的形成导致Co（II）中心还原为单价状态。在氮气氛下进行相同的反应得到双二氮络合物 [2,6-(i-Pr)2PhN-C=( )]( )[2,6-(i-Pr)2PhN=C( )]}2[Co(N2)]2·2(甲苯) (2)。关键词：低价钴，二亚氨基吡啶，二氮固定。
• Preparation of an Active Neodymium Catalyst for Regioselective Butadiene <i>cis</i>-Polymerization Supported by a Dianionic Modification of the 2,6-Diiminopyridine Ligand
  作者：Hiroyasu Sugiyama、Sandro Gambarotta、Glenn P. A. Yap、David R. Wilson、Sven K.-H. Thiele

  DOI：10.1021/om0496434

  日期：2004.10.1

  Treatment of the 2,6-diiminopyridine ligand 2,6-[2,6-(i-Pr)(2)C6H3]N=C(CH3)}(2)(C5H3N) with 2 equiv of Me3SiCH2Li afforded the corresponding [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)](2-) (1) dianion via deprotonation of the two methyl groups attached to the two imine functions. Reaction of 1 with NdCl3(THF)(3) yielded [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd(THF)}(mu-Cl)(2)[Li(THF)(2)](.)0.5(hexane) (2a), whose recrystallization from DME gave the corresponding ionic [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]NdCl2(DME)}Li(DME)(3)] (2b). With the exception of the reaction with (allyl)MgBr, which proceeded readily with 2b to form the allyl derivative [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd(eta(3)-C3H5)Br}Li(DME)(3)} (3), compounds 2a,b are not suitable starting substrates for further alkylation reactions. A viable synthetic strategy for the preparation of alkyl derivatives of 2 consisted instead of the pretreatment of NdCl3(THF)(3) with RLi [R = Me3SiCH2, CH3] at low T followed by treatment with either the diimine ligand or 1. According to this procedure, the terminally bound alkyl derivative [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd[CH2Si(CH3)(3)](THF) (4) was prepared and subsequently crystallographically characterized. The same synthetic procedure with MeLi afforded [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd}(mu-CH3)(2)[Li(THF)(2)] (5) and [2,6-[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd}(mu-Cl)(mu-X)[Li(THF)(2)] (6) [X = Cl 53%, Me 47%] depending on the MeLi/Nd ratio. Both 5 and 6 as well as 2a are potent catalysts for the cis-polymerization of butadiene.