含有新型皮拉衍生PCP钉连接体的普通金属复合物
Heiko Schratzberger1, Lorenzo A Liebminger1, Berthold Stöger2
1Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9, A-1060 Vienna, Austria. karl.kirchner@tuwien.ac.at.
Dalton transactions (Cambridge, England : 2003)
|August 18, 2023
概括
合成了一种新型的pyrazole衍生的链联结体 (PCP-iPr),并与金属碳基复合物反应. 这项研究详细介绍了这些新PCP具复合物的协调化学和后功能化.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 连接体设计 连接体设计
背景情况:
- 子连接体是协调化学中的多功能支架,提供独特的固体和电子特性.
- 基于皮拉的配体越来越多地被探索其可调节的协调模式和潜在的应用.
研究的目的:
- 为了合成和表征一种新的来自皮拉的PCP器连接体 (PCP-iPr).
- 调查PCP-iPr与六组和过渡金属碳化合物复合物的协调行为.
- 探索合成的金属-PCP复合物的后功能化.
主要方法:
- 合成来自皮拉的PCP器连接物 (PCP-iPr).
- PCP-iPr与各种金属碳烯基前体 ([M(CO) 6],[Mn2(CO) 10],[Fe2(CO) 9],[Co2(CO) 8],[Ni(COD) 2) 的反应.
- 使用NMR (1H, 13C, 31P),红外光谱,HR-MS和X射线晶体学对产生的复合体进行表征.
- 用密度函数理论 (DFT) 的计算来理解结合相互作用.
主要成果:
- 一种由皮拉衍生而来的新型PCP器连接体 (PCP-iPr) 已成功制备.
- 合成了六组金属 ([M(κ2PN-PCP-iPr) ((CO) 4)) 和过渡金属 ([Mn(κ3PCP-PCP-iPr) ((CO) 3),[Fe ((κ3PCP-PCP-iPr) ((H) ((CO) 2),[Co ((κ3PCP-PCP-iPr) ((CO) 2),[Ni ((κ3PCP-PCP-iPr) ((H)))) 的复合物,显示出不同的协调模式.
- 在较高温度下,复合体表现出 κ3PCP 协调与较弱的 Mo-C 键.
- 通过N-甲基化后功能化产生了阴离子PCP钉复合体.
结论:
- 来自皮拉的PCP钉连接体表现出与一系列金属中心的多功能协调能力.
- 根据金属和反应条件,联体可以采用不同的结合模式 (κ2PN和 κ3PCP).
- 后功能化提供了一条修改产生的金属复合物的电子性质和电荷的途径.
更多相关视频
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
9.7K
04:51Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
3.0K
相关概念视频
02:51Metal-Ligand Bonds
21.0K
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...
21.0K
02:42Valence Bond Theory
8.7K
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...
8.7K
01:19Complexation Equilibria: The Chelate Effect
551
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...
551
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
401
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
401
00:43Complexometric Titration: Ligands
989
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
989
00:56Extraction: Advanced Methods
483
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
483