Proton Transfers and Nucleophilic Reactions in Organic and Organometallic Systems

有机和有机金属体系中的质子转移和亲核反应

• 批准号: 9307659
• 负责人: Claude Bernasconi
• 金额: $ 60.82万
• 依托单位: University of California-Santa Cruz
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-06-15 至 1999-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9307659&HistoricalAwards=false
• 关键词: Proton; Transfers; Nucleophilic; Reactions; Organic

This grant from the Organic Dynamics Program supports the work of Professor Bernasconi at the University of California, Santa Cruz to study asynchronous transition states of proton transfer and nucleophilic addition and substitution reactions using the principle of nonperfect synchronization. The specific targets are: (a) to separate the polarizability and resonance effects in sulfur and phosphorus substituted anions, (b) to study proton transfer from carbon to carbon by experiment and theory, and (c) to study the influence of metallic substitution on proton transfer barriers as well as the more general area of nucleophilic additions to the C=M double bonds of Fischer carbene complexes. %%% In this project Professor Bernasconi will employ his empirical theory, the principle of nonperfect synchronization, to study asynchronous proton transfer reactions and additions to Fischer carbene complexes. The application of his physical organic methodology to the ubiquitous chemistry of metal carbenes will fill an important void.

来自有机动力学项目的这笔赠款支持加州大学圣克鲁斯分校的贝纳斯科尼教授利用非完全同步原理研究质子转移和亲核加成以及取代反应的异步过渡态的工作。具体目标是：(A)分离硫和磷取代阴离子中的极化和共振效应，(B)从实验和理论上研究质子从碳到碳的转移，以及(C)研究金属取代对质子转移势垒的影响，以及更一般的Fischer卡宾配合物C=M双键的亲核加成区域。在这个项目中，贝纳斯科尼教授将使用他的经验理论--非完全同步原理--来研究非同步质子转移反应和费希尔卡宾络合物的加成反应。将他的物理有机方法论应用于金属卡宾的无处不在的化学，将填补一个重要的空白。