光诱导的NO和HNO从单核{FeNO}⁶复合物中产生

相关实验视频

Updated: Dec 24, 2025

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions

Published on: October 5, 2019

Chuan-Kuei Chiang¹, Kai-Ti Chu², Chia-Chin Lin³

¹Department of Applied Science, National Taitung University, Taitung 950, Taiwan.

Journal of the American Chemical Society

|April 14, 2020

概括

铁-基复合物的光诱导反应产生氧化 (NO) 或其减少形式HNO. 铁复合体1上的一个悬挂醇组捕获NO,通过光促进的途径形成HNO,与酸反应不同.

科学领域:

协调化学
摄影化学
有机金属化学

背景情况:

金属-基复合物在各种化学和生物过程中至关重要.
对于开发新的催化和传感应用来说,了解这些复合物的光诱导变化至关重要.
悬挂组在调节反应性和产品选择性的作用仍然是一个活跃的研究领域.

研究的目的:

研究铁-基复合物的光化学与悬挂醇和乙烯配体.
在光照射下阐明氧化 (NO) 和氧化 (HNO) 的形成机制.
使用复合物作为捕获剂来区分光生成产品.

主要方法:

两个{FeNO}⁶复合体的合成和表征:[Fe(NO) }^TMSPS2) }^TMSPS2H) (1) 和[Fe(NO) }^TMSPS2) }^TMSPS2CH₃) (2).
光谱分析 (UV-Vis,IR) 和X射线晶体学
在可见光下进行光解研究,加上计算密度函数理论 (DFT) 的计算.
用于产品分化,光生成物种与复合物[Mn^III(^TMSPS3) 的反应.

主要成果:

复合物2在光解时经历NO分离,产生单核Fe (III) 复合物.
复合物1与悬挂醇在辐射时通过分子内[SH··ON-Fe]相互作用形成中间体.
在复合物1中中间体的光解导致HNO的产生,通过DFT计算和与复合物的反应得到证实.
复合物有效地区分来自复合物2的光生成NO和来自复合物1的HNO.

结论:

从铁-基复合物与悬挂醇生成HNO的新型光促进途径被证明.
悬挂醇在捕获NO和促进HNO形成方面发挥着至关重要的作用,与传统的酸路径不同.
该研究强调了悬挂组在控制光化学结果和复合物的有效性在区分NO和HNO.

更多相关视频

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F⁻

Published on: July 27, 2018

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

相关概念视频

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO₂ Overview

Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...

ortho–para-Directing Activators: –CH3, –OH, –&NoBreak;NH2, –OCH3

ortho–para-Directing Activators: –CH₃, –OH, –⁠NH₂, –OCH₃

All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...

2° Amines to N-Nitrosamines: Reaction with NaNO2

2° Amines to N-Nitrosamines: Reaction with NaNO₂

Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.

Nuclear Overhauser Enhancement (NOE)

Nuclear Overhauser Enhancement (NOE)

Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. This phenomenon, called the nuclear Overhauser enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring spin-active...

Preparation and Reactions of Thiols

Preparation and Reactions of Thiols

Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.

Nucleophilic Aromatic Substitution: Elimination–Addition

Nucleophilic Aromatic Substitution: Elimination–Addition

Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...