通过使用酸常数方程发现过渡金属化物复合物的电化学特性

相关实验视频

Updated: Dec 8, 2025

Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

Published on: September 7, 2019

Benjamin E Rennie¹, Renée G Eleftheriades¹, Robert H Morris¹

¹Department of Chemistry, University of Toronto, 80 Saint George St., Toronto, Ontario M5S3H6, Canada.

Journal of the American Chemical Society

|September 17, 2020

概括

这项研究引入了一种新方法来估计对磁性过渡金属化合物的酸度. 这项工作通过预测化物稳定性和氧化可逆性,为催化剂设计提供了洞察力.

科学领域:

协调化学
有机金属化学
催化剂

背景情况:

在设计电催化剂和有机金属催化剂时,偏磁过渡金属化物的热力学是至关重要的.
现有的化物复合热力学测定方法有限,特别是丰富的三维金属.

研究的目的:

首次使用连体酸度常数 (LAC) 方程估计在乙酸 (MeCN) 中的偏磁化物的pKa.
揭示氧化还原配对的系统趋势,并估计未氧化化物的键解离自由能 (BDFE(MH)).
预测氧化物的电化学潜力并评估其可逆性.

主要方法:

开发并应用了连体酸度常数 (LAC) 方程来估计200多个化物复合物的pKa值.
使用热化学循环与文学电化学潜力来分析氧化还原趋势.
使用密度函数理论 (DFT) 计算来验证选定的化物pKa值.

主要成果:

成功估计了200多个偏磁化物复合物的pKa.
揭示了M (III/II),M (V/IV),M (II/I),Re (VI/V),Re (IV/III),M (IV/III) 和M (II/I) 氧化还原对的系统趋势.
已确定pKa值与化物氧化的可逆性之间的相关性,pKa<0表示不可逆的氧化,pKa>0表示可逆的氧化.

结论:

LAC方程式提供了一种可靠的方法来估计偏磁过渡金属化物的热力学.
估计的pKa值和BDFE (MH) 对于预测催化剂性能和稳定性是有价值的.
了解pKa和氧化还原行为的关系是设计高效的电催化剂和有机金属催化剂的关键.

更多相关视频

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Published on: June 9, 2023

Analysis of AtHIRD11 Intrinsic Disorder and Binding Towards Metal Ions by Capillary Gel Electrophoresis and Affinity Capillary Electrophoresis

Analysis of AtHIRD11 Intrinsic Disorder and Binding Towards Metal Ions by Capillary Gel Electrophoresis and Affinity Capillary Electrophoresis

Published on: August 22, 2018

相关概念视频

Ladder Diagrams: Complexation Equilibria

Ladder Diagrams: Complexation Equilibria

Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

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...

Metal-Ligand Bonds

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...

Complexation Equilibria: Factors Influencing Stability of Complexes

Complexation Equilibria: Factors Influencing Stability of Complexes

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...

Valence Bond Theory

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

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...