Therrien Jeffrey A, Wolf Michael O
Department of Chemistry, University of British Columbia , 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
Inorg Chem. 2017 Feb 6;56(3):1161-1172. doi: 10.1021/acs.inorgchem.6b02213. Epub 2017 Jan 10.
The effect of modifying the pyridyl para position of lutidine-linked bis(N-heterocyclic carbene) Pd pincer complexes is studied both experimentally (R = OMe, H, Br, and COOR) and computationally, showing a strong effect on the first reduction potential of the complex and allowing the reduction potential to be tuned over a wide range in relation to the Hammett σ constant of the para substituent. The effect of the pyridyl para substituent on electron density of the metal center, frontier orbital energies, and dissociation energy of the trans ligand are also investigated in the context of reactivity with CO through electrochemical characterization of the complexes under N and CO and controlled potential electrolysis experiments where CO is reduced to CO.
研究了修饰联吡啶双（N-杂环卡宾）钯钳形配合物吡啶基对位的效果，通过实验（R = OMe、H、Br和COOR）和计算进行研究，结果表明其对配合物的首次还原电位有强烈影响，并能使还原电位相对于对位取代基的哈米特σ常数在很宽的范围内进行调节。还通过在N和CO气氛下对配合物进行电化学表征以及将CO还原为CO的控制电位电解实验，在与CO反应的背景下研究了吡啶基对位取代基对金属中心电子密度、前沿轨道能量和反式配体解离能的影响。
