[Ni(2,4-di-tert-butyl-6-(([bis(6-methyl-2-pyridyl)methyl]amino)methyl)phenolato)Cl] | 278606-64-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Ni(2,4-di-tert-butyl-6-(([bis(6-methyl-2-pyridyl)methyl]amino)methyl)phenolato)Cl]
• 英文别名: 2,4-di(tert-butyl)-6-(bis(6-methylpyridin-2-ylmethyl)aminomethyl)phenol；2,4-di(tert-butyl)-6-(bis[(6-methyl-2-pyridyl)methyl]aminomethyl)phenol；2,4-di(t-butyl)-6-[bis[(6-methyl-2-pyridyl)methyl]aminomethyl]phenol；2,4-di(t-butyl)-6-{bis[(6-methyl-2-pyridyl)methyl]aminomethyl}phenol；HtbuL(Mepy)2；2-[[Bis[(6-methylpyridin-2-yl)methyl]amino]methyl]-4,6-ditert-butylphenol；2-[[bis[(6-methylpyridin-2-yl)methyl]amino]methyl]-4,6-ditert-butylphenol
• CAS: 278606-64-7
• 化学式: C₂₉H₃₉N₃O
• 分子量: 445.648
• InChiKey: NGHPCBILBXLOIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  49.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  cobalt(II) chloride 、 [Ni(2,4-di-tert-butyl-6-(([bis(6-methyl-2-pyridyl)methyl]amino)methyl)phenolato)Cl] 在 N(C₂H₅)3 作用下， 以 乙腈 为溶剂， 生成 [Co(2,4-di(tert-butyl)-6-(bis(6-methylpyridin-2-ylmethyl)aminomethyl)phenolate)Cl]
  参考文献：
  名称：

  Formation and Characterization of Co(III)−Semiquinonate Phenoxyl Radical Species

  摘要：

  Co(III) complexes of N3O-donor tripodal ligands, 2,4-di(tert-butyl)-6-{[bis(2-pyridyl)methyl]aminomethyl}phenolate (tbuL), 2,4-di(tert-butyl)-6-{[bis(6-methyl-2-pyridyl)methyl]aminomethyl}phenolate (tbuL(Mepy)(2)), were prepared, and precursor Co(II) complexes, [Co(tbuL)Cl] (1) and [Co(tbuL(Mepy)(2))Cl] (2), and ternary Co(III) complexes, [Co(tbuL)(acac)]ClO4 (3), [Co(tbuL)(tbu-cat)] (4), and [Co(tbuL(Mepy)(2))(tbu-SQ)]ClO4 (5), where acac, tbu-cat, and tbu-SQ refer to pentane-2,4-dionate, 3,5-di(tert-butyl)catecholate, and 3,5-di(tert-butyl)semiquinonate, respectively, were structurally characterized by the X-ray diffraction method. Complexes 3 and 5 have a mononuclear structure with a fac-N3O3 donor set, while 4 has a mer-N3O3 structure. The cyclic voltammogram (CV) of complex 3 exhibited one reversible redox wave centered at 0.93 V (vs Ag/AgCl) in CH3CN. Complex 5 was converted to a phenoxyl radical species upon oxidation with Ce(IV), showing a characteristic pi-pi* transition band at 412 nm. The ESR spectrum at low temperature and the resonance Raman spectrum of 3 established that the radical species has a Co(III)-phenoxyl radical bond. On the other hand, the CVs showed two oxidation processes at E-1/2 = 0.01 and E-pa = 0.92 V for 4 and E-1/2a = 0.05 and E-1/2b = 0.69 V for 5. The rest potential of 4 (-0.11 V) was lower than the E-1/2 value, whereas that of 5 (0.18 V) was higher, indicating that the first redox wave of 4 and 5 is assigned to the tbu-cat and the tbu-SQ redox process, respectively. One-electron oxidized 4 showed absorption, resonance Raman, and ESR spectra which are similar to those of 5, suggesting formation of a stable Co(III)-semiquinonate species, which has the same oxidation level of 5. The resonance Raman spectrum of two-electron oxidized 4 showed the nu(8a) bands of the semiquinonate and phenoxyl radical, which were absent in the spectrum of one-electron oxidized 5. Since both oxidized species were ESR inactive at 5 K, the former was concluded to be a biradical species containing semiquinonate and phenoxyl radicals coupled antiferromagnetically and the latter to a species with a coordinated quinone.

  DOI：

  10.1021/ic700596g
• 作为产物：
  描述：

  3,5-二叔丁基水杨醛 、 bis(6-methyl-2-pyridylmethyl)amine 在 溶剂黄146 、 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 反应 72.0h， 以70.4%的产率得到[Ni(2,4-di-tert-butyl-6-(([bis(6-methyl-2-pyridyl)methyl]amino)methyl)phenolato)Cl]
  参考文献：
  名称：

  半乳糖氧化酶中 Cu(II)-苯氧基自由基位点的化学方法：自由基稳定性对 N-供体性质的依赖性

  摘要：

  几种新型 N3O 型三足配体的铜 (II) 配合物、2,4-二(叔丁基)-6-{[双(2-吡啶基)甲基]氨基甲基}苯酚 (HtbuL)、2,4-di( t-丁基)-6-{[(6-methyl-2-pyridyl)methyl](2-pyridylmethyl)aminomethyl}phenol (HtbuL(Mepy)), 2,4-di(t-butyl)-6-{bis [(6-甲基-2-吡啶基)甲基]氨基甲基}苯酚(HtbuL(Mepy)2)和2,4-二(叔丁基)-6-{[(1-甲基-2-咪唑基)甲基]制备[(6-甲基-2-吡啶基)甲基]氨基甲基}苯酚(HtbuL(im)(Mepy))。它们的结构特征是通过 X 射线晶体学方法具有方形锥体结构，在顶端位置具有弱配位基团。[CuCl(tbuL(Mepy))] (2)、[CuCl(tbuL(Mepy)2)] (3) 和 [CuCl(tbuL(im)(Mepy))]

  DOI：

  10.1246/bcsj.73.1187

文献信息

• Zinc Complex Chemistry of N,N,O Ligands Providing a Hydrophobic Cavity
  作者：Florian Gross、Heinrich Vahrenkamp

  DOI：10.1021/ic050042u

  日期：2005.5.1

  forms labile halide, p-nitrophenolate, and pyridine complexes. Triethylamine converts the aqua complexes to the labile hydroxides L2Zn-OH and L3Zn-OH, and in polar media [L3Zn-OH2]+ seems to be in equilibrium with L3Zn-OH. The hydroxides, but not the water complexes, effect the hydrolytic cleavage of tris(p-nitrophenyl) phosphate to bis(p-nitrophenyl) phosphate. The kinetic investigation of the cleavage

  合成了三个新的高度取代的双（2-吡啶甲基）（2-羟基苄基）胺配体，并探索了其仿生锌配合物的化学性质。它们在苯环的3和5位上具有叔丁基取代基，并且在其6位上带有一个苯基（HL2），两个甲基（HL3）或两个苯基（HL4）。吡啶环。他们与水合高氯酸锌的反应产生了三种截然不同的复杂类型。L2形成三角-双锥体水基络合物，L3形成正方形-锥体水基络合物。L4上的取代基没有留下水配体的空间，所得的锌络合物是具有空位配位点的三角-单锥体。L2Zn和L3Zn单元上的水配体可以被阴离子卤化物，硫氰酸盐，对硝基苯酚盐，苯甲酸盐取代，有机磷酸酯以及不带电荷的吡啶配体 L4Zn单元形成不稳定的卤化物，对硝基苯酚盐和吡啶配合物。三乙胺将水络合物转化为不稳定的氢氧化物L2Zn-OH和L3Zn-OH，在极性介质中[L3Zn-OH2] +似乎与L3Zn-OH处于平衡状态。氢氧化物而不是水络合物影响磷酸三（对硝基苯基）酯水解
• Zinc(II)–phenoxyl radical complexes: Dependence on complexation properties of Zn–phenolate species
  作者：Yuichi Shimazaki、Tatsuo Yajima、Tadashi Shiraiwa、Osamu Yamauchi

  DOI：10.1016/j.ica.2008.11.006

  日期：2009.5

  converted to the phenoxyl radicals upon oxidation with Ce(IV), giving a phenoxyl radical π–π∗ transition band at 394–407 nm. ESR and resonance Raman spectra established that the radical species had a Zn(II)–phenoxyl radical bond. The cyclic voltammograms showed similar quasi-reversible redox waves with E1/2 = 0.68, 0.67, and 0.63 V (versus Ag/AgCl) for 1, 2, and 3, respectively, corresponding to the formation

  摘要N3O供体三脚形配体，2,4-二（叔丁基）-6-[双（2-吡啶基）甲基]氨基甲基}苯酚（HtbuL），2,4-二（叔）的锌（II）配合物-丁基）-6-[（（6-甲基-2-吡啶基）甲基]-（2-吡啶基）甲基氨基甲基}苯酚（HtbuLMepy）和2,4-二（叔丁基）-6-[bis（ 6-甲基-2-吡啶基）甲基]氨基甲基}苯酚（HtbuL（Mepy）2），[Zn（tbuL）Cl]·CH3OH（1），[Zn（tbuLMepy）Cl]（2）和[Zn（tbuL）分别制备了（Mepy）2）Cl]（3），并通过X射线衍射法对其结构进行了表征。发现所有复合物均具有带有配位酚盐部分的单核结构，Zn（II）中心的几何形状为5配位三角双锥体。对于类似的配体，评估了有或没有6-甲基-2-吡啶基甲基部分的配体对Zn（II）的结合能力，通过在25°C（I = 0.1 M（KNO3））电位滴定确定的稳定性常数，
• Nickel(II)−Phenoxyl Radical Complexes:  Structure−Radical Stability Relationship
  作者：Yuichi Shimazaki、Stefan Huth、Satoru Karasawa、Shun Hirota、Yoshinori Naruta、Osamu Yamauchi

  DOI：10.1021/ic049040k

  日期：2004.11.1

  They were converted to the phenoxyl radicals upon oxidation with Ce(IV), giving a phenoxyl radical pi-pi transition band at 394-407 nm. ESR spectra at low temperature and resonance Raman spectra established that the radical species has a Ni(II)-phenoxyl radical bond. The cyclic voltammograms showed a quasi-reversible redox wave at E1/2=0.46-0.56 V (vs Ag/AgCl) corresponding to the formation of the phenoxyl

  N3O-供体三脚架配体，2,4-二叔丁基-6-[[[[（双（2-吡啶基）甲基]氨基）甲基]苯酚（HtbuL），2,4-二-叔丁基-6-[（[（（6-甲基-2-吡啶基）甲基]（2-吡啶基甲基）氨基）甲基] p苯酚（HtbuLMepy）和2,4-二叔丁基-6-[（制备[双（6-甲基-2-吡啶基）甲基]氨基）甲基]苯酚（HtbuL（Mepy）2），和[Ni（tbuL）Cl（H2O）]（1），[Ni（tbuLMepy）Cl用X射线衍射法对]（2）和[Ni（tbuL（Mepy）2）Cl]（3）进行结构表征。配合物1和3具有带配位酚酸酯部分的单核结构，而配合物2具有由两个氯离子桥接的双核结构。发现Ni（II）中心的几何形状对于1和2为八面体，对于3为5坐标三角双锥体。配合物1-3在CH3CN中表现出相似的吸收光谱，表明它们在溶液中都具有单核结构。它们在用Ce（IV）氧化后转化为苯氧基，在394-407