(15)N-二氧化氮 | 14184-22-6

• 物质功能分类: 化学试剂 - 氘代试剂
• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属有机物
• 中文名称: (15)N-二氧化氮
• 英文名称: (15)N-nitrogen dioxide
• 英文别名: nitrogen dioxide
• CAS: 14184-22-6；137496-65-2
• 化学式: NO₂
• 分子量: 46.9988
• InChiKey: JCXJVPUVTGWSNB-OUBTZVSYSA-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：

  (15)N-二氧化氮 、 2,3,5,7-四苯基-21H,23H-卟吩锰(2+)盐(1:1) 以 neat (no solvent) 为溶剂， 生成 Mn(meso-tetraphenylporphyrinatodianion)(η¹-O¹⁵NO)
  参考文献：
  名称：

  Six-Coordinate Nitrito and Nitrato Complexes of Manganese Porphyrin

  摘要：

  Reaction of small increments of NO2 gas with sublimed amorphous layers of Mn-II(TPP) (TPP = meso-tetra-phenylporphyrinato dianion) in a vacuum cryostat leads to formation of the 5-coordinate monodentate nitrato complex Mn-III(TPP)(eta(1)-ONO2) (II). This transformation proceeds through the two distinct steps with initial formation of the five coordinate O-nitrito complex Mn-III(TPP)(eta(1)-ONO) (I) as demonstrated by the electronic absorption spectra and by FTIR spectra using differently labeled nitrogen dioxide. A plausible mechanism for the second stage of reaction is offered based on the spectral changes observed upon subsequent interaction of (NO2)-N-15 and NO2 with the layered Mn(TPP). Low-temperature interaction of I and II with the vapors of various ligands L (L = O-, S-, and N-donors) leads to formation of the 6-coordinate O-nitrito Mn-III(TPP)(L)(eta(1)-ONO) and monodentate nitrato Mn-III(TPP)(L)(eta(1)-ONO2) complexes, respectively. Formation of the 6-coordinate O-nitrito complex is accompanied by the shifts of the nu(N=O) band to lower frequency and of the nu(N=O) band to higher frequency. The frequency difference between these bands triangle nu = nu(N=-O) - nu(N=O) is a function of L and is smaller for the stronger bases. Reaction of excess NH3 with I leads to formation of Mn(TPP)(NH3)(eta(1)-ONO) and of the cation [Mn(TPP)(NH3)(2)](+) plus ionic nitrite. The nitrito complexes are relatively unstable, but several of the nitrato species can be observed in the solid state at room temperature. For example, the tetrahydrofuran complex Mn(TPP)(THF)(eta(1)-ONO2) is stable in the presence of THF vapors (similar to 5 mm), but it loses this ligand upon high vacuum pumping at RT. When L = dimethylsulfide (DMS), the nitrato complex is stable only to similar to 30 degrees C. Reactions of II with the N-donor ligands NH3, pyridine, or 1-methylimidazole are more complex. With these ligands, the nitrato complexes Mn-III(TPP)(L)(eta(1)-ONO2) and the cationic complexes [Mn(TPP)(L)(2)](+) coexist in the layer at room temperature, the latter formed as a result of NO3- displacement when L is in excess.

  DOI：

  10.1021/ic5014329
• 作为产物：
  描述：

  lead (15)N-nitrate 以 not given 为溶剂， 以83%的产率得到(15)N-二氧化氮
  参考文献：
  名称：

  ¹⁵N nuclear polarization in the reactions of diallyl ether with nitrogen dioxide

  摘要：

  DOI：

  10.1139/cjc-77-5-6-647
• 作为试剂：
  描述：

  2,4,6-三叔丁基苯酚 在 (15)N-二氧化氮 作用下， 以 全氘代环己烷 为溶剂， 反应 80.0h， 生成 2,4,6-tritert-butyl-4-[oxido(oxo)(15N)(15N)azaniumyl]cyclohexa-2,5-dien-1-one
  参考文献：
  名称：

  位阻硝基环己二烯酮的缓慢重排和一氧化氮不氧化苯酚

  摘要：

  将溶液中的 2,4,6-三叔丁基苯酚 (1) 暴露于 NO2· 导致 2,4,6-三叔丁基-4-硝基-2,5-环己二烯酮快速形成（ 2），然后在没有空气的情况下经历缓慢（约 3 d）重排。描述这种重排的机制首次被理解，它涉及 2 的初始异构化以形成 (-ONO)-取代的环己二烯酮 (6)。亚硝酸盐部分经历键均裂释放NO·同时形成氧基自由基中间体。在 6 和该氧自由基之间进行的分子间协同夺氢导致所有稳定产物的同时形成，其中一些先前未观察到。此外，当 1 在厌氧条件下暴露于 NO· 时，没有观察到反应。(© Wiley-VCH Verlag GmbH & Co. KGaA,

  DOI：

  10.1002/ejoc.200901074

文献信息

• Structure, harmonic force field and hyperfine coupling constants of nitrosyl chloride
  作者：Bethany Gatehouse、Holger S. P. Müller、Nils Heineking、Michael C. L. Gerry

  DOI：10.1039/ft9959103347

  日期：——

  of nitrosyl chloride were measured using a cavity pulsed microwave Fourier-transform spectrometer. Some a-type transitions of all five isotopomers, and some weak b-type transitions of four of these isotopomers were measured in the 4–26 GHz frequency range. Precise values for the rotational constants and the quartic centrifugal distortion constants were obtained. The rotational constants were used in

  使用腔脉冲微波傅里叶变换光谱仪测量了亚硝酰氯的五个同位素物种的纯旋转光谱。在4–26 GHz频率范围内测量了所有五个同位素异构体的一些a型跃迁，以及其中四个同位素异构体的一些弱b型跃迁。获得了旋转常数和四次离心畸变常数的精确值。旋转常数用于结构确定，离心变形常数用于改进谐波总价力场。还计算了一个谐波中心价价场。
• Six-Coordinate Nitrosyl and Nitro Complexes of <i>meso</i>-Tetratolylporphyrinatocobalt with Trans Sulfur-Donor Ligands
  作者：Tigran S. Kurtikyan、Gurgen M. Gulyan、Arina M. Dalaloyan、Bryce E. Kidd、John A. Goodwin

  DOI：10.1021/ic1007846

  日期：2010.9.6

  and optical spectroscopy, it has been observed that interactions of dimethyl sulfide and tetrahydrothiophene with nitrosyl and nitro complexes of meso-tetra-p-tolylporphyrinatocobalt [Co(TTP)] lead to the formation of previously unknown six-coordinate species. Nitrosyl complexes of the general formula (S-donor)Co(TTP)(NO) are thermally unstable and can be seen only at low temperatures both in the solid

  通过傅立叶变换红外光谱和光谱学，已经观察到二甲基硫醚和四氢噻吩与内消旋-四-对-甲苯基卟啉钴[Co（TTP）]的亚硝酰基和硝基配合物的相互作用导致形成了以前未知的六配位物质。通式（S-给体）Co（TTP）（NO）的亚硝酰基配合物是热不稳定的，只能在低温下以固态和溶液形式看到。硝基络合物（S-给体）Co（TTP）（NO 2）在室温下在固态下相当稳定，但在溶解时会部分分解。确定这些络合反应的结合常数。与固态亚硝化卟啉铁配合物相反，Co（TTP）（NO 2）的配位硝基基团向S供体的羰基转移反应导致这些硫化物的氧化并形成Co（TTP）（NO） ），未观察到。
• Interaction of Nitrogen Bases with Iron−Porphyrin Nitrito Complexes Fe(Por)(ONO) in Sublimed Solids
  作者：Tigran S. Kurtikyan、Astghik A. Hovhannisyan、Gurgen M. Gulyan、Peter C. Ford

  DOI：10.1021/ic700846x

  日期：2007.8.1

  6-coordinate amino-nitro complexes with sterically unprotected iron-porphyrins. The interaction of ammonia with Fe(Por)(ONO) at 140 K initially led to the nitrito species Fe(Por)(NH3)(eta1-ONO), and this species isomerized to the nitro complexes Fe(Por)(NH3)(eta1-NO2) upon warming to 180 K. When the latter were warmed to room temperature under intense pumping, the initial nitrito complexes Fe(Por)(eta1-ONO)

  氮路易斯碱（B）1-甲基咪唑（1-MeIm），吡啶（Py）和NH3作为气体与升华层中含有5配位亚硝基铁（III）-卟啉配合物Fe（Por）（eta1）的反应-ONO）（1）被描述（Por =中-四苯基-卟啉基或中-四-对甲苯基-卟啉基二价阴离子）。原位FTIR和光谱用于表征由1与B = 1-MeIm，Py或NH3反应形成的6-配位硝基络合物的形成。这些代表了具有空间上未保护的铁卟啉的6-配位的氨基-硝基配合物的第一个实例。氨在140 K下与Fe（Por）（ONO）的相互作用最初导致亚硝基物种Fe（Por）（NH3）（eta1-ONO），并且该物种异构化为硝基络合物Fe（Por）（NH3）（ η1-NO2）加热至180K。当后者在强力泵送下加热到室温时，初始的亚硝基络合物Fe（Por）（eta1-ONO）被还原。给出了6-配位的铁-卟啉配合物中配位的硝基振动频率的分配，并使用15N标记的二氧
• Remarkable oxygen promotion of the selective reduction of nitric oxide by hydrogen over Au/NaY and Au/ZSM-5 zeolite catalysts
  作者：Tarek M. Salama、Ryuichiro Ohnishi、Masaru Ichikawa

  DOI：10.1039/a606761a

  日期：——

  A significant enhancement of the selective reduction of nitrogen oxide by H 2 is produced in the presence of oxygen over Au/NaY and Au/ZSM-5 catalysts by forming NO 2 and N 2 O 4 intermediates, which are eventually reduced to N 2 .

  在Au/NaY和Au/ZSM-5催化剂存在下，通过形成NO₂和N₂O₄中间体，氧气促进了H₂选择性还原氮氧化物的能力显著提升，并最终转化为N₂。
• Reactions of Nitrogen Oxides with the Five-Coordinate Fe^III(porphyrin) Nitrito Intermediate Fe(Por)(ONO) in Sublimed Solids
  作者：Tigran S. Kurtikyan、Astghik A. Hovhannisyan、Manya E. Hakobyan、James C. Patterson、Alexei Iretskii、Peter C. Ford

  DOI：10.1021/ja067245h

  日期：2007.3.1

  Detailed experimental studies are described for reactions of several nitrogen oxides with iron porphyrin models for heme/NxOy systems. It is shown by FTIR and optical spectroscopy and by isotope labeling experiments that reaction of small increments of NO2 with sublimed thin layers of the iron(II) complex Fe(Por) (Por = meso-tetraphenylporphyrinato dianion, TPP, or meso-tetra-p-tolylporphyrinato dianion

  详细的实验研究描述了几种氮氧化物与血红素/NxOy 系统的铁卟啉模型的反应。FTIR 和光学光谱以及同位素标记实验表明，少量的 NO2 与升华的铁 (II) 配合物 Fe(Por) 薄层发生反应（Por = 内消旋四苯基卟啉二价阴离子、TPP 或内消旋四对甲苯基卟啉二价阴离子 (TTP) 导致形成 5 配位亚硝基配合物 Fe(Por)(eta1-ONO) (1)，它们相当稳定，但在真空下分解非常缓慢，主要生成相应的亚硝酰基配合物 Fe(Por) （不）。1 与新的 NO2 增量的进一步反应导致形成硝基复合物 Fe(Por)(eta2-O2NO) (2)。NO 与 1 在低温下的相互作用涉及配体加成，得到亚硝基-亚硝酰基配合物 Fe(Por)(eta1-ONO)(NO) (3)；然而，它们在加热时异构化为硝基亚硝酰基类似物 Fe(Por)(eta1-NO2)(NO) (4)。用标记的氮氧化物