tert-butyl-2-pyridyl nitroxide | 42166-55-2

• 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: tert-butyl-2-pyridyl nitroxide
• 英文别名: N-^tBu-N-2-pyridylhydroxylamine；2pyNO
• CAS: 42166-55-2
• 化学式: C₉H₁₃N₂O
• 分子量: 165.215
• InChiKey: BZPUJWJPEDXORM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [Ce^III(μ-(N-tert-butyl-N-2-pyridylnitroxide))(N-tert-butyl-N-2-pyridylnitroxide)₂]₂ 、 tert-butyl-2-pyridyl nitroxide 以 乙醚 为溶剂， 反应 14.0h， 生成 Ce[N-tert-butyl-N-2-pyridylnitroxide]₄
  参考文献：
  名称：

  实验和DFT计算的Ce（IV / III）电化学势对4f嵌段的配体场级数

  摘要：

  铈（IV）阳离子的还原电势对配体场强的敏感性的了解尚未受益于配体环境的系统变化。详细分析了一系列七种铈（IV）四（吡啶基-硝基氧）化合物及其铈（III）类似物在不同配体场强下的分布。电化学，光谱和计算结果表明，电子性质与配体取代基密切相关。结合已报道的八配位化合物的电化学数据，DFT计算揭示了与配体场强相关的大量铈（IV / III）氧化还原电势，建立了用于调节铈氧化还原热力学和配体场强的半经验预测模型。各种科学领域的应用都利用了铈的基本氧化还原热力学。这样的应用将从评估铈化合物的氧化还原循环的实验和理论相结合的方法中受益。

  DOI：

  10.1021/ic503000z
• 作为产物：
  描述：

  N-tert-butyl-N-(2-pyridyl)hydroxylamine 在 air 作用下， 生成 tert-butyl-2-pyridyl nitroxide
  参考文献：
  名称：

  Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines

  摘要：

  N-tert-Butyl-N-2-pyridylhydroxylamines were synthesized from 2-halopyridines and 2-methyl-2-nitrosopropane using magnesium halogen exchange. The use of Turbo Grignard generated the metallo-2-pyridyl intermediate more reliably than alkyllithium reagents. The hydroxylamines were characterized using NMR, electrochemistry, and density functional theory. Substitution of the pyridyl ring in the 3-, 4-, and 5-positions was used to vary the potential of the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations of the electrochemical properties agree with experiment and provide a toolset for the predictive design of pyridyl nitroxides.

  DOI：

  10.1021/jo400944r

文献信息

• Homoleptic Cerium(III) and Cerium(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State
  作者：Justin A. Bogart、Andrew J. Lewis、Scott A. Medling、Nicholas A. Piro、Patrick J. Carroll、Corwin H. Booth、Eric J. Schelter

  DOI：10.1021/ic401974t

  日期：2013.10.7

  [2-(tBuNO)py]− = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [nBu4N]2[Ce(NO3)6] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework

  电化学实验在复杂的Ce进行IV [2-（吨BUNO）吡啶] 4，其中[2-（吨BUNO）吡啶] - = ñ -叔丁基- ñ -2- pyridylnitroxide，表示的一个2.51 V稳定与[ n Bu 4 N] 2 [Ce（NO 3）6与乙腈在水溶液中的离子电势相比，具有2.95 V的稳定度（与离子的标准电势相比）。密度泛函理论计算表明，这种对较高氧化态的偏爱是由于Ce阳离子上的四（硝基氧）配体骨架的结果，该骨架允许将有效的电子捐赠给具有δ对称性的空的4f轨道，并与之部分共价重叠。结果证明了CeO 2和相关固溶体在氧气吸收和运输应用中的行为，特别是稳定4+氧化态的键的固有局部特征。结果表明，铈（IV）配合物已通过调整其配体场环境而被稳定到了前所未有的程度。
• Ferro- and Antiferromagnetic Coupling Switch Accompanied by Twist Deformation around the Copper(II) and Nitroxide Coordination Bond
  作者：Atsushi Okazawa、Daisuke Hashizume、Takayuki Ishida

  DOI：10.1021/ja102163d

  日期：2010.8.25

  Two novel copper(II) complexes with tert-butyl 2-pyridyl nitroxide (2pyNO(*)), [Cu(2+)(2pyNO(-))(2pyNO(*))](2)(BF(4)(-))(2) (1 x BF(4)) and [Cu(2+)(2pyNO(-))(2pyNO(*))](2)(ClO(4)(-))(2) (1 x ClO(4)), were prepared and structurally characterized. They contained mixed-valent ligands from 2pyNO, whose oxygen atoms were located at equatorial positions of the copper ion. The [Cu(2+)(2pyNO(-))(2pyNO(*))]

  两种新型铜 (II) 与叔丁基 2-吡啶基氮氧化物 (2pyNO(*))、[Cu(2+)(2pyNO(-))(2pyNO(*))](2)(BF(4)( -))(2) (1 x BF(4)) 和 [Cu(2+)(2pyNO(-))(2pyNO(*))](2)(ClO(4)(-))(2) ( 1 x ClO(4))，进行了制备和结构表征。它们包含来自 2pyNO 的混合价配体，其氧原子位于铜离子的赤道位置。[Cu(2+)(2pyNO(-))(2pyNO(*))] 单元通过阴离子配体的 mu-oxo 桥进行二聚化，给出了一个涉及四个顺磁性 S = 1/2 中心的锯齿形线性自旋系统。这两种化合物在正交 Pbca 空间群中是同晶的。磁性研究表明 1 x ClO(4) 显示在这里调查的所有温度范围内的铁磁铜自由基耦合。另一方面，1 x BF(4) 在 64 K 表现出结构相变，其中磁化率在冷却时急剧下
• Magnetic study on radical-gadolinium(III) complexes. Relationship between the exchange coupling and coordination structure
  作者：Takayuki Ishida、Rina Murakami、Takuya Kanetomo、Hiroyuki Nojiri

  DOI：10.1016/j.poly.2013.04.004

  日期：2013.12

  Antiferro- and ferromagnetic couplings were observed in [Gd(hfac)(3)(2pyNO)(H2O)] and [Gd(hfac)(3)(-HNN)(2)], respectively, where 2pyNO stands for tert-butyl 2-pyridyl nitroxide and HNN for 4,4,5,5-tetramethylimidazolin-1-oxyl 3-oxide. The magnitude of the former is the largest in Gd-nitroxide complexes (2J/k(B) = -13.8(3) K). An empirical relation between the exchange coupling and torsion angle Gd-O-N-C is drawn, where large torsion (>36 degrees) favors ferromagnetic coupling. (C) 2013 Elsevier Ltd. All rights reserved.
• Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines
  作者：Justin A. Bogart、Heui Beom Lee、Michael A. Boreen、Minsik Jun、Eric J. Schelter

  DOI：10.1021/jo400944r

  日期：2013.6.21

  N-tert-Butyl-N-2-pyridylhydroxylamines were synthesized from 2-halopyridines and 2-methyl-2-nitrosopropane using magnesium halogen exchange. The use of Turbo Grignard generated the metallo-2-pyridyl intermediate more reliably than alkyllithium reagents. The hydroxylamines were characterized using NMR, electrochemistry, and density functional theory. Substitution of the pyridyl ring in the 3-, 4-, and 5-positions was used to vary the potential of the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations of the electrochemical properties agree with experiment and provide a toolset for the predictive design of pyridyl nitroxides.
• A Ligand Field Series for the 4f-Block from Experimental and DFT Computed Ce(IV/III) Electrochemical Potentials
  作者：Justin A. Bogart、Andrew J. Lewis、Michael A. Boreen、Heui Beom Lee、Scott A. Medling、Patrick J. Carroll、Corwin H. Booth、Eric J. Schelter

  DOI：10.1021/ic503000z

  日期：2015.3.16

  Understanding of the sensitivity of the reduction potential of cerium(IV) cations to ligand field strength has yet to benefit from systematic variation of the ligand environment. Detailed analyses for a series of seven cerium(IV) tetrakis(pyridyl-nitroxide) compounds and their cerium(III) analogues in varying ligand field strengths are presented. Electrochemical, spectroscopic, and computational results

  铈（IV）阳离子的还原电势对配体场强的敏感性的了解尚未受益于配体环境的系统变化。详细分析了一系列七种铈（IV）四（吡啶基-硝基氧）化合物及其铈（III）类似物在不同配体场强下的分布。电化学，光谱和计算结果表明，电子性质与配体取代基密切相关。结合已报道的八配位化合物的电化学数据，DFT计算揭示了与配体场强相关的大量铈（IV / III）氧化还原电势，建立了用于调节铈氧化还原热力学和配体场强的半经验预测模型。各种科学领域的应用都利用了铈的基本氧化还原热力学。这样的应用将从评估铈化合物的氧化还原循环的实验和理论相结合的方法中受益。