铁基复合物:电子结构对Fe-C键同解和迁移反应的贡献,这些反应从N2形成N-C键
Samuel M Bhutto1, Reagan X Hooper1, Sean F McWilliams1
1Department of Chemistry, Yale University New Haven Connecticut 06520 USA patrick.holland@yale.edu.
Chemical science
|March 8, 2024
概括
研究人员用一种新的双化方法合成了罕见的高价值铁基复合物. 这些铁(IV) 复合体具有独特的反应性,通过碳酸迁移形成新的N-C键,取决于基组.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学
- 计算化学的计算化学
背景情况:
- 高价值的铁基复合物由于Fe-C键同解而难以合成.
- 以前对铁复合物的研究往往集中在类类似物上.
- 了解铁复合体中高氧化状态的稳定至关重要.
研究的目的:
- 开发一种新型合成路径,以正式化铁 (IV) 基复合物.
- 为了研究这些不寻常的铁复合物的电子结构和稳定性.
- 探索铁 (IV) 基复合物的反应性,特别是碳化合物迁移.
主要方法:
- 铁的合成 (I) 基二化合物.
- 通过双重化,形成NNSi2连接体.
- 用光谱验证的计算研究 (DFT) 来分析电子结构和结合.
- 用不同的基组 (三甲基甲基,甲基,基) 进行反应性研究.
主要成果:
- 通过一个disiyllehydrazido{2-) 连接物稳定形式铁{IV) 基复合物的成功合成.
- 计算分析显示了强烈的共价Fe-N π相互作用和显著的铁 (II) 共振贡献.
- 基复合物表现出S = 2的基态,与基相似物 (S = 1) 不同,导致较弱的Fe-N键.
- 反应性因基组而异:重的三甲基甲基是稳定的,甲基经历N-C键的形成,基导致Fe-C同解.
结论:
- 一种新的方法可以获得罕见的高价值铁基复合物.
- 基化2-) 连接物有效地稳定了铁4-) 氧化状态.
- 在正式的铁 (IV) 中心的碳化合物迁移是可行的,形成新的N-C键,其选择性取决于基组的特性.
更多相关视频
07:56Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyltroponeiron
Published on: August 12, 2019
8.0K
09:45Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
10.4K
相关概念视频
01:23Properties of Organometallic Compounds
994
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
994
02:10Carbocations
11.2K
Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
11.2K
02:24Introduction to Electrophilic Addition Reactions of Alkenes
7.9K
The double bond in a simple, unconjugated alkene is a region of high electron density that can act as a weak base or a nucleophile. The filled π orbital (HOMO) of the double bond can interact with the empty LUMO of an electrophile. A bonding interaction occurs when the electrophile attacks between the two carbons; the electrophile then accepts a pair of electrons from the π bond and undergoes addition across the double bond, yielding a single product.
Addition and elimination...
Addition and elimination...
7.9K
02:38Electrophilic Addition to Alkynes: Halogenation
8.2K
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
8.2K
02:58Crystal Field Theory - Octahedral Complexes
26.5K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
26.5K
02:42Valence Bond Theory
8.5K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.5K