四價鎳、錳錯合物之合成及鑑定與其質子還原反應之探討

Abstract

此研究延續先前本實驗室許育禎學姊之論文，以兩分子H2PS2三牙配位基製備出Ni(PS2)2 (1)，空氣穩定之四價鎳錯合物，並且藉由取代基的修飾以及錳金屬置換，進而合成出一系列鎳及錳四價錯合物，Ni(PS2TMS)2 (2)、Ni(PDMAS2)2 (3)、Mn(PS2)2 (4)、Mn(PS2TMS)2 (5)及Mn(PDMAS2)2 (6)。六個錯合物依據不同電子組態，分別進行NMR及EPR的鑑定，同時，利用紫外光/可見光光譜及X光吸收光譜進行光譜的分析。電化學方面利用循環伏安法鑑定錯合物之氧化還原性質以及探討其應用於質子還原反應性的可能性。To extend the research of our previously developed six-coordinated Ni(IV) complex supported by two R-PS22- ligand, Ni(PS2)2 (1). The Ni(IV) complex was modified with trimethylsilane and dimethylamino as substituent group. Besides, Mn(IV) complex was also synthesized with the same ligands. Here we present a series of nickel(IV) and manganese(IV) complexes (Ni(PS2TMS)2 (2), Ni(PDMAS2)2 (3), Mn(PS2)2 (4), Mn(PS2TMS)2 (5) and Mn(PDMAS2)2 (6). These complexes was characterized by X-ray crystallography, NMR, EPR, UV-vis spectra, X-ray absorption spectroscopy, and cyclic voltammetry. Cyclic voltammogram revealed two redox waves, which could provide the possibility of two electron reduction to Ni(II) or Mn(II) species. To examine these complexes as potential electrocatalysts for proton reduction, TFA was added to each complex solution and the system was examined by cyclic voltammetry.