Physical Organic Chemistry of Fischer Carbene Complexes

本研究致力于阐明六族化合物中金属卡宾发生水解和促进亲核加成反应的机理。配位的卡宾的供电子和接受电子的性质将通过系统地修饰卡宾碳上的基团来改变，并与络合物的动力学和热力学酸度相关联，以建立结构-反应关系。进行实验的研究生和博士后研究助理将被介绍有机金属卡宾络合物的合成，以及用于阐明其化学反应的一般模式的程序。通过这一奖项，有机和高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。贝纳斯科尼博士将把他的研究重点放在铬、钼和钨的卡宾络合物的反应性与连接的卡宾的结构之间的关联上。这些络合物含有一种不寻常的活性碳，促进了某些有机转化，在合成有机化学中得到了越来越多的使用。贝纳斯科尼博士的教育活动包括对研究生和博士后进行有机金属合成方面的培训，以及用于阐明其化学组成的程序。

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.