Investigation of Molybdenum Metallocene Complexes for Hydrolyzing Phosphate Neurotoxins

刘易斯和克拉克学院化学系Louis Kuo博士由化学部无机、生物无机化学和有机金属化学支持，致力于水解磷酸酯的新型有机金属络合物的合成和研究。二氯钼(Cp2MoCl2)是目前已知的唯一一种在水溶液中进行有机磷酸解的有机金属体系。等电点分析表明，这个过程涉及钼络合物与磷酸盐中心之间的Lewis酸/碱相互作用。增加Mo(IV)的Lewis酸度可以加速酯的水解。因此，在这个项目中，Mo(IV)中心的Lewis酸性将通过在环戊二烯配体上附加小的电子吸/给基团来改变。将对其中的各种化合物进行研究，以发展将络合物的结构与其水解磷酸酯的能力联系起来的关系。利用这些关系，将设计新的过渡金属基材料来降解有机磷神经毒素。该项目的第二部分将研究钼杂多烯衍生物对硫代膦中的P-S键的水解能力。在整个项目中，将进行机械调查。许多化学战剂和杀虫剂是磷酸酯或类似硫代亚膦。这些物种的主要解毒策略是水解法和焚烧法。该项目寻求开发能够加速磷酸盐和硫代膦的水解的新试剂。目前重要的是开发更好的试剂来水解磷酸酯，因为在接下来的几年里必须销毁大量的化学战剂库存。在教育方面，该项目将对刘易斯和克拉克学院的本科生研究产生重大影响，该项目的环境影响将影响该学院蓬勃发展的环境研究项目以及其化学和生物化学项目。

Dr. Louis Kuo, Chemistry Department, Lewis and Clark College, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry of the Chemistry Division for research into the syntheses and investigation of new organometallic complexes that hydrolyze phosphate esters. Molybdocene dichloride (Cp2MoCl2) is the only known organometallic system that carries out the hydrolysis of organophosphates in aqueous solution. The PI has demonstrated that this process involves a Lewis Acid/Base interaction of the molybdenum complex with the phosphate center. Increasing the Lewis acidity of Mo(IV) should accelerate ester hydrolysis. Thus, in this project the Lewis acidity of Mo(IV) centers will be altered by attaching small electron withdrawing/donating groups to the cyclopentadienyl ligand. A variety of these will be investigated in order to develop relationships which relate the structures of the complexes with their ability to hydrolyze phosphate esters. Using these relationships, new transition metal-based materials will be designed for the degradation of organophosphate neurotoxins. The second part of the project will investigate the ability of the molybdocene derivatives to hydrolyze the P-S bond in phosphinothioates. Throughout the project, mechanistic investigations will be undertaken.Many chemical warfare agents and pesticides are phosphate esters or resemble phosphinothioates. The main detoxification strategies for these species are hydrolysis and incineration. This project seeks to develop new agents that can accelerate the hydrolysis of phosphates and phosphinothioates. There is current importance to developing better reagents that hydrolyze phosphate esters because substantial stockpiles of chemical warfare agents must be destroyed over the next few years. Educationally, this project will have a major impact on undergraduate research at Lewis and Clark College and the environmental implications of the project will impact the college's burgeoning Environmental Studies program as well as its chemistry and biochemistry programs.