通过N-C键裂变,从双价到五价铁化物复合物和Fe (V) 化物
Martin Keilwerth1, Weiqing Mao1, Sergio A V Jannuzzi2
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 1, 91058 Erlangen, Germany.
Journal of the American Chemical Society
|December 30, 2022
概括
研究人员使用新型联体合成和表征铁体复合物,揭示了多样化的电子结构和反应性. 这些研究提供了对中高价铁化学和转移反应的见解.
科学领域:
- 有机金属化学
- 无机化学
- 催化剂
背景情况:
- 终端铁复合物是金属催化转移反应中的关键中间体.
- 开发多功能模型化合物对于理解它们的反应性至关重要.
- 这种N-固的Tris-NHC合联体TIMMNMes为合成这种复合物提供了一个新的平台.
研究的目的:
- 合成和比较两系列中高价铁胺复合物.
- 研究这些复合物的电子结构和反应性.
- 探索Fe ((V) 胺介质的转化为Fe ((V) 化合物.
主要方法:
- 使用TIMMNMes连接体和1-阿达曼酸合成铁体复合物.
- 在氧化状态II到V的复合物中逐步进行化学还原和氧化.
- 通过单晶X射线衍射,SQUID磁化,电化学,Mössbauer,IR,UV/vis,NMR,EPR和X射线吸收光谱进行表征.
- 进行补充量子化学计算.
主要成果:
- 在氧化状态II到V中成功合成低旋铁亚达曼化物[TIMMNMes) ]0,1+,2+,3+ (2-5).
- 通过N-C键裂变转化为可分离的Fe(V) 化物复合物 (6) 的不稳定Fe(V) 化物中间体的观察.
- 通过导化化物合成类似的乙胺复合物,包括稳定的Fe(V) 乙胺.
- 详细描述与反应性相关的多种电子结构.
结论:
- TIMMNMes连接物促进了一系列铁和铁复合物的合成.
- 铁模复合物的电子结构显著影响它们的反应性.
- 这项工作提供了对高价值铁模复合物的基本化学和它们在转移反应中的潜力的宝贵见解.
相关概念视频
02:42Valence Bond Theory
9.0K
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...
9.0K
02:34Structural Isomerism
19.6K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
19.6K
02:58Properties of Transition Metals
26.8K
Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
26.8K
03:45Formation of Complex Ions
23.9K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
23.9K
01:19Complexation Equilibria: The Chelate Effect
590
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
590
02:51Metal-Ligand Bonds
21.3K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
21.3K