碳复合物作为一氧化碳在协调化学中的电子和固体调节类型
Andreas Krapp1, Gernot Frenking
1Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Strasse, D-35032 Marburg, Germany.
Journal of the American Chemical Society
|December 4, 2008
概括
过渡金属碳复合体表现出类似于一氧化碳 (CO) 的结合性和供体-接受体特性. 这些金属-碳复合物可以被认为是可调节的CO类似物,具有合成新型 adducts和同质复合物的潜力.
科学领域:
- 计算化学是一种计算化学.
- 有机金属化学 有机金属化学
- 协调化学 协调化学
背景情况:
- 过渡金属碳复合物由于其独特的结合,引起了人们的兴趣.
- 了解它们的配体特性对于设计新的催化剂和材料至关重要.
研究的目的:
- 为了研究过渡金属碳复合物的电子和粘合特性.
- 为了比较金属碳复合物的连接体行为与一氧化碳 (CO).
- 探索新型金属碳添加物和复合物的潜在合成.
主要方法:
- 密度函数理论 (DFT) 使用BP86函数的计算.
- 在初始合集群计算中,使用单,双和扰动三次激发 (CCSD(T)).
- 用于结合分析的电荷和能量分区方法.
主要成果:
- 金属碳复合物表现出与二氧化碳相比较的结合强度和供体-受体特性.
- 与其他金属碳复合物相比,基于氨酸的碳复合物 (10MC) 具有更强的结合能力和略有增强的pi受体能力.
- 金属碳复合物比CO的pi受体略弱,导致某些供体-受体复合物中的潜在的较弱键.
结论:
- 金属碳复合物作为一氧化碳的电子调类型.
- 这项研究表明,可以用多个碳联结体和同质金属碳复合体合成附加物.
- 计算的键能表明,碳复合物可能与d10过渡金属形成比CO更强的键.
相关概念视频
Structural Isomerism
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 be...
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 be...
Properties of Organometallic Compounds
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.
Metal-Ligand Bonds
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...
Stereoisomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Valence Bond Theory
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...
Coordination Compounds and Nomenclature
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...


