McKinnon Meaghan, Belkina Veronika, Ngo Ken T, Ertem Mehmed Z, Grills David C, Rochford Jonathan
Department of Chemistry, University of Massachusetts Boston, Boston, MA, United States.
Chemistry Division, Brookhaven National Laboratory, Upton, NY, United States.
Front Chem. 2019 Sep 24;7:628. doi: 10.3389/fchem.2019.00628. eCollection 2019.
The subject of this study [-Mn(bqn)(CO)(CHCN)] (bqn = 2,2'-biquinoline), is of particular interest because the bqn ligand exhibits both steric and electronic influence over the fundamental redox properties of the complex and, consequently, its related catalytic properties with respect to the activation of CO. While not a particularly efficient catalyst for CO to CO conversion, generation and activity measurements of the [-Mn(bqn)(CO)] active catalyst allows for a better understanding of ligand design at the Mn center. By making direct comparisons to the related 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen), and 2,9-dimethyl-1,10-phenanthroline (dmphen) ligands via a combination of voltammetry, infrared spectroelectrochemistry, controlled potential electrolysis and computational analysis, the role of steric vs. electronic influences on the nucleophilicity of Mn-based CO reduction electrocatalysts is discussed.
本研究的对象[-Mn(bqn)(CO)(CHCN)]（bqn = 2,2'-联喹啉）特别引人关注，因为bqn配体对该配合物的基本氧化还原性质同时表现出空间和电子影响，因此，其与CO活化相关的催化性质也是如此。虽然[-Mn(bqn)(CO)]活性催化剂对于CO到CO的转化并非特别高效的催化剂，但对其生成和活性的测量有助于更好地理解锰中心的配体设计。通过结合伏安法、红外光谱电化学、控制电位电解和计算分析，与相关的2,2'-联吡啶（bpy）、1,10-菲咯啉（phen）和2,9-二甲基-1,10-菲咯啉（dmphen）配体进行直接比较，讨论了空间和电子影响对基于锰的CO还原电催化剂亲核性的作用。
