High-Valent Metal Oxos to Model OEC in Photosystem II

描述(申请人提供)：拟议的研究旨在提供对光系统II中析氧复合体(OEC)中发生的水分解反应的机理的洞察。具体地说，提出了一项研究计划，描述了新型三阴离子、三(芳基苯氧基)配体的制备，以完成以下工作：(1)作为OEC模拟物的高价金属氧络合物的生成；(2)作为二次键合环境的函数研究金属氧合的生成和稳定性；(3)与OEC和其他功能模型相关的O-O键形成反应的机理；以及(4)朝着实现可持续裂水催化剂的最终目标取得进展。控制二次键环境对于稳定高价金属氧物种，使两个水分子靠近以进行偶联，以及调节氧亲核试剂的氧化还原电位和pKA是至关重要的。这里描述的模型是独特的，因为它们将促进酸碱和自由基偶联O-O键形成反应机理的研究。

DESCRIPTION (provided by applicant): The proposed research is designed to provide mechanistic insight into the water-splitting reaction that occurs at the oxygen-evolving complex (OEC) in photosystem II. Specifically, a research plan is presented that describes the preparation of novel trianionic, tris(arylphenoxide) ligands to accomplish the following: (1) the generation of high-valent metal oxo complexes to serve as OEC mimics, (2) investigate the metal oxo generation and stability as a function of secondary bonding environments; (3) probe the mechanism of O-O bond forming reactions relevant to the OEC and other functional models; and (4) make progress towards the ultimate goal of realizing a sustainable water-splitting catalyst. Controlling the secondary bonding environments will be critical for stabilizing high-valent metal oxo species, bringing two water molecules into a close proximity for coupling, and tuning the redox potential of the oxo and the pKa of incoming oxygen nucleophiles.The models described herein are unique in that they will facilitate both acid-base and radical- coupling O-O bond forming reaction mechanisms to be investigated.