Physical Organic Chemistry of Fischer Carbene Complexes

本研究的重点是阐明六基团三联体金属卡宾的水解和促进亲核加成的机制。配位碳的给电子和接受电子的性质会随着配位碳上的基团的系统修饰而改变，并与配合物的动力学和热力学酸度相关，从而形成结构-反应性关系。进行实验的研究生和博士后研究人员将被介绍有机金属碳配合物的合成以及用于阐明其化学反应性一般模式的程序。通过这个奖项，有机和大分子化学项目支持加州大学圣克鲁斯分校化学系克劳德·贝纳斯科尼博士的研究。贝纳斯科尼博士将重点研究铬、钼和钨碳络合物的反应活性与所附碳的结构之间的关系。这些配合物含有一种不寻常的碳反应形式，促进某些有机转化，并在合成有机化学中越来越多地使用。Bernasconi博士的教育活动包括培训研究生和博士后学生有机金属合成和用于阐明其化学过程的程序。

This research focuses on elucidating the mechanisms by which metallocarbenes of the group-six triad undergo hydrolysis and facilitate nucleophilic additions. Electron donating and accepting properties of the coordinated carbene will be varied through systematic modifications of the groups appendant to the carbene carbon and correlated with the kinetic and thermodynamic acidities of the complexes to develop structure-reactivity relationships. Graduate students and postdoctoral research associates carrying out the experiments will be introduced to the synthesis of organometallic carbene complexes and to the procedures used to elucidate the general patterns of their chemical reactivity. With this award, the Organic and Macromolecular Chemistry Program supports the research of Dr. Claude Bernasconi of the Department of Chemistry at the University of California at Santa Cruz. Dr. Bernasconi will focus his research on correlating the reactivity of chromium, molybdenum and tungsten carbene complexes with the structure of the attached carbene. These complexes, which contain an unusual, reactive form of carbon, facilitate certain organic transformations and are finding an increasing use in synthetic organic chemistry. Dr. Bernasconi's educational activities include the training of graduate and postdoctoral students in organometallic syntheses and the procedures used to elucidate their chemistry.