Ligand Enhancement of Transition Metal Reactivity

印第安纳大学化学系Kenneth G.Caulton博士得到化学系无机、生物无机和有机金属化学计划的支持，利用[(R2PCH2SiMe2)2N]-1(PNP)配体开发与其配位的金属之间的原子转移反应。建议的工作包括将原子转移到高度还原的(PNP)M或来自G可能是O或N的(PNP)MG的罕见例子。将研究配合物的性质，如自旋态、键序、化学键类型以及空轨道和孤对的位置，以了解它们对化学反应活性的影响。将对Fe-Ru-Os组和Fe-Co-Ni系进行比较研究，以确定周期性趋势。特别是，第一过渡系列金属配合物有望比重元素类似物反应更快，并具有使用1电子步骤的特殊自由。所研究的化学将发展对基础有机金属化学的基本理解。本科生、研究生和博士后的培养将是该项目的重要贡献。

Dr. Kenneth G. Caulton, Chemistry Department, Indiana University, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Divison to utilize the [(R2PCH2SiMe2)2N]-1 (PNP) ligand to develop atom transfer reactions to and from metals coordinated to it. Work proposed includes transfer of atoms to highly reduced (PNP)M or from rare examples of (PNP)MG where G may be O or N. Properties of the complexes, such as spin state, bond order, chemical bond-type and location of empty orbitals and of lone pairs, will be studied for their influence on chemical reactivity. Comparative studies down the Fe - Ru - Os group and across the Fe - Co - Ni series will be conducted to establish periodic trends. In particular, the first transition series metal complexes are expected to react more rapidly than heavier element analogs and possess special freedom to employ 1-electron steps.The chemistry to be studied will develop a basic understanding of fundamental organometallic chemistry. The education of undergraduate, graduate, and postdoctoral students will be an important contribution of this project.