通过铜 (II) 复合体将酸盐减少为NO的机制研究:不同协同的酸盐和酸盐复合体之间的质子电子转移反应性
Yohei Kametani1, Kei Ikeda1, Kazunari Yoshizawa1
1Institute for Materials Chemistry and Engineering and IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.
Inorganic chemistry
|August 17, 2023
概括
这项研究揭示了铜复合体对化物减少的机制. 计算表明Cu-ONO路径是受欢迎的,涉及协调的质子电子转移以释放氧化.
科学领域:
- 无机化学 无机化学
- 计算化学计算化学
- 反应机制 反应机制
背景情况:
- 铜复合物已被广泛研究以减少化物,但反应机制尚不清楚.
- 讨论了亚酸盐和质子/电子转移通路的协调模式.
- 之前的研究提出了铜催化化还原过程中的质子合电子转移.
研究的目的:
- 通过使用计算方法阐明铜 (II) 复合物的化物减少的详细机制.
- 研究酸盐协调模式 (Cu-ONO与Cu-NO2) 对反应途径的影响.
- 了解氧化释放过程中质子和电子转移的性质.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 几何优化确定了两个初始的铜-酸盐复合结构 (Cu-ONO和Cu-NO2).
- 对反应路径,电子结构,内在反应坐标和键轨道的分析.
主要成果:
- 发现Cu-ONO路径在能量方面比Cu-NO2路径更有利.
- 这两种途径都涉及协同质子电子转移 (CPET).
- 对于这两种途径,已确定了不同的CPET机制,Cu-ONO表现出协调一致的异步事件.
结论:
- Cu-ONO协调模式为化物减少提供了有利的途径.
- 在这种复杂的铜系统中,协同的质子电子转移对于氧化释放至关重要.
- 计算分析为复杂的反应动态和电子/质子转移事件提供了关键的见解.
相关概念视频
Rate-Determining Steps
32.7K
Relating Reaction Mechanisms
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
32.7K
Preparation of Amines: Reduction of Oximes and Nitro Compounds
3.7K
Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
3.7K
Multi-Step Reactions
7.4K
Chemical reactions often occur in a stepwise fashion involving two or more distinct reactions taking place in a sequence. A balanced equation indicates the reacting species and the product species, but it reveals no details about how the reaction occurs at the molecular level. The reaction mechanism (or reaction path) provides details regarding the precise, step-by-step process by which a reaction occurs. Each of the steps in a reaction mechanism is called an elementary reaction. These...
7.4K
Nitriles to Amines: LiAlH4 Reduction
3.6K
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
3.6K
Reaction Mechanisms
26.0K
Chemical reactions often occur in a stepwise fashion, involving two or more distinct reactions taking place in a sequence. A balanced equation indicates the reacting species and the product species, but it reveals no details about how the reaction occurs at the molecular level. The reaction mechanism (or reaction path) provides details regarding the precise, step-by-step process by which a reaction occurs.
For instance, the decomposition of ozone appears to follow a mechanism with two steps:
For instance, the decomposition of ozone appears to follow a mechanism with two steps:
26.0K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
3.8K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
3.8K


