US-France Cooperative Research: Structure/Reactivity Relationships in Transition Metal Chemistry

该奖项将支持印第安纳大学布卢明顿分校的Kenneth Caulton博士及其同事与巴黎第南大学理论化学实验室的Odile Eisenstein博士之间的合作研究。该项目将结合巴黎实验室的优势，该实验室在应用半经验量子化学方面有着悠久的传统，以及印第安纳小组在实验和严格量子化学方面的经验。开展正在进行的无机和有机金属化学实验理论分析联合项目。这个理论将在两个层面上：一是半经验的程序，它利用分子对称性和原子参数（性质），对实验化学家来说是直观透明的；第二是更严格和更普遍的。要研究的具体主题涵盖了无机和有机金属化学中广泛的基本重要主题：有机合成试剂，作为配体的分子氢，烯烃配体的氢化和偶联，以及桥接多金属化合物的结构和动力学。复杂的“从头算”计算将用于探测被怀疑受到细微影响的实验数据，以及测试半经验分子轨道方法的可靠性。

This award will support collaborative research between Dr. Kenneth Caulton and colleagues at Indiana University, Bloomington, and Dr. Odile Eisenstein, Laboratory for Theoretical Chemistry, University of Paris-Sud. The project will combine the strengths of the Paris laboratory, which has a long tradition in applied semi-empirical quantum chemistry, with the experience of the Indiana group in experimental and rigorous quantum chemistry. A joint program of theoretical analysis of on-going experimental inorganic and organometallic chemistry will be carried out. The theory will be on two levels: one, a semi-empirical procedure which employs molecular symmetry and atomic parameters (properties) of intuitive transparency to experimental chemists, and a second which is more rigorous and more general. The specific topics to be investigated cover a broad range of fundamentally significant themes in inorganic and organometallic chemistry: reagents for organic synthesis, molecular hydrogen as a ligand, hydrogenation and coupling of olefinic ligands, and the structure and dynamics of bridged multimetal compounds. Sophisticated "ab initio" calculations will be used to probe experimental data where subtle influences are suspected to be controlling, as well as to test the reliability of the semi-empirical molecular orbital methods.