Manipulating Ligand Fields: Can 1st Row Transition Elements Behave as Their 2nd Row Congeners?

化学系化学合成项目支持康奈尔大学化学系Peter T. Wolczanski教授对第2过渡元素到第1过渡系列元素的性质转化的研究。过渡金属的许多重要商业应用使用昂贵、较重的元素，这些元素往往构成重大的健康风险。该建议寻求含有丰富的、毒性较小的贱金属的替代化合物，因此第一行过渡金属配合物是一般的焦点。这项研究的一个重要成果是人的因素；能够适应充满挑战的市场，包括学术、工业、政府和企业家职业的独立、多才多艺的博士。这项工作将通过科学文献、专业会议、出现情况时的专利文献以及其他适当的公共论坛进行传播。铁是专门用于烯烃分解的，“氧化还原非纯真”（RNI）有机配体也具有特色，因为它们能够通过给予或从金属中获取电子来增强化学反应活性。特别强调化合物和转化，涉及到未来的催化和环境友好的应用。通过RNI的研究和过渡金属反应性的比较，对离子与共价性质的基本理解自然得到了解决。这项研究的科学成果是对第一行过渡金属电子结构及其反应性的一般知识的扩展。一种用于确定化学稳定性的桌面方法正在开发中，该方法可以深入了解第一行过渡金属与其较重同系物之间的差异，从而提供额外的教学产品。

The Chemical Synthesis Program of the Division of Chemistry supports Prof. Peter T. Wolczanski, Chemistry Department, Cornell University, for research into imparting properties associated 2nd transition elements to 1st transition series elements. Many important commercial applications of transition metals use expensive, heavier elements that often pose significant health risks. This proposal seeks replacement compounds that contain earth abundant, less toxic, base- metals, hence first row transition metal complexes are the general focus. A significant product of this research is the human element; the generation of independent, versatile PhDs capable of adapting to a challenging market, which encompasses academic, industrial, government, and entrepreneurial occupations. The work will be disseminated through the scientific literature, in professional meetings, in the patent literature should the situation arise, and via other appropriate public forums. Iron is targeted specifically for utilization in olefin metathesis, and "redox non-innocent" (RNI) organic ligands are also featured, due to their ability to enhance chemical reactivity by giving or taking electrons from the metal. Special emphasis is given to compounds and transformations that pertain to future catalytic and environmentally friendly applications. A fundamental understanding of ionic vs. covalent character is naturally addressed via the studies of RNI, and comparisons of transition metal reactivity. The scientific product of the research is the expansion of general knowledge regarding first row transition metal electronic structure, and concomitant reactivity. A desktop methodology for determining chemical stability, which provides insight into differences between first row transition metals and their heavier congeners, is under development, thus providing an additional pedagogical product.