Unsaturated, Multifunctional Transition Metal Complexes

该奖项属于无机、生物无机和有机金属化学项目，为印第安纳大学化学系的 Kenneth G. Caulton 博士进行不饱和有机金属化合物的合成和反应研究提供持续支持。 理论工作将与法国蒙彼利埃大学的 Odile Eisenstein 博士合作进行。 该研究的目的是确定具有连接到同一金属原子的几种不同功能配体的化合物的反应模式。 合成的化合物将包含配体的混合物，例如氢化物、卤化物、烷基和卡宾。 将直接测定各种配体的相对反应性，并监测同一分子中的烷基迁移和分子内还原消除等复杂反应。 多官能金属络合物还可以将多于一个的官能团传递至另一分子。 选择目标化合物是因为它们能够在低温下进行亲核或氧化反应。 研究这些条件下的反应性可以提高识别初级反应产物的可能性并最大限度地提高反应的选择性。 将确定热力学参数。 待研究的具体反应包括从羰基锇中还原消除苯、从16电子物质中除去卤化物以形成14电子化合物以及三氟甲基配体反应形成二氟甲基配体。 将研究各种有机金属化合物的异常反应，包括 C-H 和 C-F 键活化以及配位不饱和化合物的反应性。 此类反应对于基本了解均相催化剂的行为非常重要。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides continued support to Dr. Kenneth G. Caulton of the Chemistry Department, Indiana University, for synthesis and reaction studies of unsaturated organometallic compounds. Theoretical work will be carried out in collaboration with Dr. Odile Eisenstein of the Universite de Montpellier, France. The goal of the research is to determine reactivity patterns for compounds having several different functional ligands attached to the same metal atom. The compounds synthesized will contain a mixture of ligands such as hydride, halide, alkyl, and carbene. Relative reactivity of various ligands will be determined directly and complex reactions such as alkyl migration and intramolecular reduction elimination in the same molecule will be monitored. Multifunctional metal complexes may also deliver more than one functional group to another molecule. The target compounds will be selected because of their ability to undergo nucleophilic or oxidation reactions at low temperature. Studying reactivity under these conditions improves the possibility of identifying primary reaction products and maximizes the selectivity of reactions. Thermodynamic parameters will be determined. Specific reactions to be investigated include reductive elimination of benzene from osmium carbonyls, removal of halide from 16-electron species to form 14-electron compounds, and reaction of trifluoromethyl ligands to form difluoromethyl ligands. Unusual reactions of a wide range of organometallic compounds will be studied, including C-H and C-F bond activation and reactivity of coordinatively unsaturated compounds. Reactions of this kind are important to obtaining a basic understanding the behavior of homogeneous catalysts.