6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(2,4-di-tert-butylphen-3,5-d2-ol) | 1186078-52-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(2,4-di-tert-butylphen-3,5-d2-ol)
• CAS: 1186078-52-3
• 化学式: C₃₆H₅₄N₂O₂
• 分子量: 550.805
• InChiKey: FYNXDGNCEBQLGC-GQCAQXIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.14
• 重原子数：
  40.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  65.18
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(2,4-di-tert-butylphen-3,5-d2-ol) 、 cobalt(II) diacetate tetrahydrate 以 乙醇 、 甲苯 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  Unique Ligand-Radical Character of an Activated Cobalt Salen Catalyst That Is Generated by Aerobic Oxidation of a Cobalt(II) Salen Complex

  摘要：

  The Co(salen)(X) complex, where salen is chiral N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine and X is an external axial ligand, has been widely utilized as a versatile catalyst. The Co(salen)(X) complex is a stable solid that has been conventionally described as a Co-III(salen)(X) complex. Recent theoretical calculations raised a new proposal that the Co(salen)(H2O)(SbF6) complex contains appreciable contribution from a Co-II(salen(circle+)) electronic structure (Kochem, A.; Kanso, H.; Baptiste, B.; Arora, H.; Philouze, C.; Jarjayes, O.; Vezin, H.; Luneau, D.; Orb, M.; Thomas, F. Inorg. Chem. 2012, 51, 10557-10571), while other theoretical calculations for Co(salen)(Cl) indicated a triplet Co-III(salen) electronic structure (Kemper, S.; Hrobarik, P.; Kaupp, M.; Schlorer, N. E. J. Am. Chem. Soc. 2009, 131, 4172-4173). However, there have been no experimental data to evaluate these theoretical proposals. We herein report key experimental data on the electronic structure of the Co(salen)(X) complex (X = CF3SO3-, SbF6-, and p-MeC6H4SO3-). The X-ray crystallography shows that Co(salen)(OTf) has a square-planar N2O2 equatorial coordination sphere with OTf as an elongated external axial ligand. Magnetic susceptibility data indicate that Co(salen)(OTf) complexes belong to the S = 1 spin system. H-1 NMR measurements provide convincing evidence for the Co-II(salen(circle+))(X) character, which is estimated to be about 40% in addition to 60% Co-III(salen)(X) character. The CH2Cl2 solution of Co(salen)(X) shows an intense near-IR absorption, which is assigned as overlapped transitions from a ligand-to-metal charge transfer in Co-III(salen)(X) and a ligand-to-ligand charge transfer in Co-II(salen(circle+))(X). The present experimental study establishes that the electronic structure of Co(salen)(X) contains both Co-II(salen(circle+))(X) and Co-III(salen)(X) character.

  DOI：

  10.1021/ic302677f
• 作为产物：
  描述：

  3,5-di-tert-butyl-2-hydroxybenzaldehyde-4,6-d2 、 (1R,2R)-1,2-diaminocyclohexane 在 硫酸 作用下， 以 乙醇 、 水 为溶剂， 反应 2.0h， 以89%的产率得到6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(2,4-di-tert-butylphen-3,5-d2-ol)
  参考文献：
  名称：

  外轴配体在反式环己烷-1,2-二胺在Salen配合物中手性扩增中的关键作用

  摘要：

  一系列带有不同外部轴向配体（L = Cl、NO(3)、N(3) 和 OCH(2)CF(3)）的 Mn(IV)(salen)(L)(2) 复合物来自手性 salen合成了具有反式环己烷-1,2-二胺作为手性支架的配体，以深入了解金属salen配合物的构象特性。X 射线晶体结构表明，Mn(IV)(salen)(OCH(2)CF(3))(2) 和 Mn(IV)(salen)(N(3))(2) 采用阶梯构象，其中一个由于来自反式环己烷-1,2-二胺部分的偏向，两个水杨叉环指向上方而另一个指向下方，这与Mn(IV)(salen)的相对平面的固态构象形成鲜明对比（ Cl)(2)。Mn(IV)(salen)(L)(2) 的 CH(2)Cl(2) 溶液显示出强度增加的圆二色性，顺序为 L = Cl < NO(3) << N(3) < OCH( 2)CF(3), 这表明Mn（IV）（salen）（L）（2）

  DOI：

  10.1021/ja904635n

文献信息

• Comparative Spectroscopic Studies of Iron(III) and Manganese(III) Salen Complexes Having a Weakly Coordinating Triflate Axial Ligand
  作者：Takuya Kurahashi、Hiroshi Fujii

  DOI：10.1246/bcsj.20120146

  日期：2012.9.15

  We thoroughly compared spectroscopic and magnetic properties of mononuclear iron(III) and manganese(III) complexes with symmetric and nonsymmetrical salen ligands, in order to investigate the relation between spectroscopic properties and electronic structures. Magnetic susceptibility and dual-mode electron paramagnetic resonance data show the assignment of [FeIII(salen)(OTf)] and [MnIII(salen)(OTf)] as high-spin S = 5/2 and S = 2 electronic configurations, respectively, irrespective of the electron-donating properties and symmetry of the salen ligand. Further insights into electronic structures of central metal are obtained from 2H NMR spectra of selectively deuterated complexes, in which [FeIII(salen)(OTf)] and [MnIII(salen)(OTf)] exhibit well-resolved paramagnetic NMR signals of quite different shift patterns, due to the presence or absence of the unpaired electron in the dx2 - y2 orbital expected for S = 5/2 iron(III) or S = 2 manganese(III) centers.

  我们深入比较了具有对称和非对称沙林配体的单核铁(III)和锰(III)配合物的光谱和磁学性质，以研究光谱性质与电子结构之间的关系。磁感应强度和双模电子顺磁共振数据表明，[FeIII(salen)(OTf)]和[MnIII(salen)(OTf)]分别具有高自旋 S = 5/2 和 S = 2 电子构型，与沙仑配体的电子供能特性和对称性无关。选择性氚化配合物的 2H NMR 光谱进一步揭示了中心金属的电子结构，其中[FeIII(salen)(OTf)]和[MnIII(salen)(OTf)]由于 S = 5/2 铁(III)或 S = 2 锰(III)中心预期的 dx2 - y2 轨道中未配对电子的存在或缺失，显示出移位模式迥异的分辨良好的顺磁 NMR 信号。