Enhancing Chemical Reactivity with Perfluorinated Oxyanions

在无机化学、生物无机化学和金属有机化学计划的支持下，Steven H.Strauss博士将合成负电荷离子(阴离子)，旨在与金属的正电荷离子(阳离子)形成极弱的键。这种阴离子的金属盐预计具有异常高的反应活性，因此它们可以用来制备其他任何路线都不能制得的金属加合物。该项目的目标是了解非常弱的供体溶剂，如氯碳和碳氢化合物对金属离子的溶剂化作用。将制备全氟含氧阴离子的金属盐，如氧五氟碲酸盐(VI)和二氧四氟碲酸盐(VI)，以及极大的全氟化阴离子，如四(氧五氟碲酸盐)硼酸盐。由于阴离子的电子和空间性质，金属离子将变得非常活跃，并有望与非常弱的碱性溶剂，如二氯甲烷、硝基甲烷、己烷和液体氙气配位。新的合成方法将被开发用于含有弱亲核、弱结合和挥发性溶剂配体的金属配合物的制备、分离和结构和光谱表征。将制备顺磁性过渡金属和稀土离子的络合物。用EXAFS光谱研究了溶剂分子与多种金属离子在纯净溶剂中的配位作用。这些反应络合物在金属化聚合物和新的金属盐亚稳定相中的潜在应用将被探索。

With support from the Inorganic, Bioinorganic and Organometallic Chemistry Program Dr. Steven H. Strauss will synthesize negatively charged ions (anions) designed to form extremely weak bonds with the positively charged ions (cations) of metals. The metal salts of such anions are expected to have unusually high reactivities, so that they can be used to prepare adducts of metals which cannot be made by any other route. The goal of the project is to understand the solvation of metal ions by very weak donor solvents such as chlorocarbons and hydrocarbons. Metal salts of perfluorinated oxyanions such as oxopentafluorotellurate(VI) and dioxotetrafluorotellurate(VI), and extremely large perfluorinated anions such as tetrakis- (oxopentafluorotellurato)borate will be prepared. By virtue of the electronic and steric properties of the anions, the metal ions will be rendered extremely reactive and are expected to coordinate to very weakly basic solvents such as methylene chloride, nitromethane, hexane and liquid xenon. New synthetic methodologies will be developed for the preparation, isolation and structural and spectroscopic characterization of metal complexes containing weakly nucleophilic, weakly bound, and volatile solvent ligands. Complexes of paramagnetic transition metals and lanthanide ions will be prepared. The coordination of solvent molecules to a variety of metal ions in neat solvent will be studied by EXAFS spectroscopy. Potential applications of the reactive complexes to metalized polymers and new metastable phases of metal salts will be explored.