通过[(bpy) 2 (((py) RuIVO]2+对C-H键的氧化发生在原子抽象过程中
Jasmine R Bryant1, James M Mayer
1Department of Chemistry, Campus Box 351700, University of Washington, Seattle, Washington 98195-1700, USA.
Journal of the American Chemical Society
|August 21, 2003
概括
((IV) 氧化物复合物通过原子抽象启动无氧氧化,形成导致各种产品的基. 这种机制在多个碳化合物基质中是一致的,与C-H键强度相关.
科学领域:
- 无机化学 无机化学
- 有机化学 有机化学
- 反应机制 反应机制
背景情况:
- 在氧化反应中研究高价值金属-氧合物复合物的反应性.
- 了解碳化合物的无氧氧氧化机制.
研究的目的:
- 为了阐明9,10-二甲 (DHA),桑和二氧化物的无氧氧化机制,由一个 (IV) 氧化物复合物.
- 探索其他碳化合物基质的拟议机制的普遍性.
- 为了将反应动力学与基质特性相关联,例如C-H键强度.
主要方法:
- 在乙尼中对无氧氧氧化反应的动力学研究.
- 产品分析以确定有氧和无氧化合物.
- 使用化基质 (DHA-d4) 的动态同位素效应测量.
主要成果:
- 氧化DHA,桑和产生复杂的产品混合物,包括二元化和氧原子转移产品.
- 对DHA氧化的显著动态同位素效应 (kH/kD ≥35) 支持初始的原子抽象.
- 原子抽象的机制,其次是激素反应,在各种基质中是一致的,包括和.
结论:
- ((IV) 氧化物复合体作为原子抽取器,启动涉及有机基的氧化途径.
- 反应速率与C-H键解离能相关,支持拟议的机制.
- 这些发现为金属介导氧化机制及其与马库斯理论的关系提供了洞察力.
相关概念视频
Covalent Bonding and Lewis Structures
Compared to ionic bonds, which results from the transfer of electrons between metallic and nonmetallic atoms, covalent bonds result from the mutual attraction of atoms for a “shared” pair of electrons.
Lewis Structures of Molecular Compounds and Polyatomic Ions
To draw Lewis structures for complicated molecules and molecular ions, it is helpful to follow a step-by-step procedure as outlined:
Hybridization of Atomic Orbitals II
sp3d and sp3d 2 Hybridization
Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Radical Formation: Homolysis
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
Radical Formation: Abstraction
The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...
Even though homolysis produces radicals, it is different from radical...


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