6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene-d))bis(2,4-di-tert-butylphenol) | 1300738-47-9

• 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: 6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene-d))bis(2,4-di-tert-butylphenol)
• CAS: 1300738-47-9
• 化学式: C₃₆H₅₄N₂O₂
• 分子量: 548.821
• InChiKey: FYNXDGNCEBQLGC-AVGGIDPOSA-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-d))bis(2,4-di-tert-butylphenol) 、 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：

  2,4-di-tert-butyl-1-(methoxymethoxy)benzene 在 盐酸 、 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 正己烷 、 水 为溶剂， 反应 10.0h， 生成 6,6'-((((1R,2R)-cyclohexane-1,2-diyl)bis(azaneylylidene))bis(methaneylylidene-d))bis(2,4-di-tert-butylphenol)
  参考文献：
  名称：

  电子多样化锰（III）和镍（II）Salen配合物的单电子氧化：从定域到离域混合价配体自由基的转变

  摘要：

  来自salen配合物的配体自由基是独特的混合价化合物，其中苯氧基自由基通过相邻的氧化还原活性金属离子与远程酚盐电子连接，为研究从酚盐到由氧化还原介导的苯氧基自由基的电子转移提供了机会- 活性金属离子作为桥梁。我们在此从电子多样化的锰 (III) salen 络合物合成单电子氧化产物，其中氧化位点以配体为中心，而不是以金属为中心，提供锰 (III)-苯氧基自由基物种。本研究的关键点是通过使用非对称 salen 配合物明确分配间隔电荷转移带，这使我们能够获得对混合价属性的其他无法访问的见解。d(4) 高自旋锰 (III) 离子形成 Robin-Day II 类混合价系统，其中电子转移发生在局部苯氧基自由基和酚盐之间。这与具有相同 salen 配体的 ad(8) 低自旋镍 (II) 离子形成鲜明对比，后者在两个酚盐环上诱导离域自由基（Robin-Day III 级），正如其他人先前报道的那样。目

  DOI：

  10.1021/ja2016813

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。