Unusual Structure and Bonding in Strained Aromatic Molecules

分子的合成和性质，其中两个相对 非反应性官能团被迫靠近 互相学习。将特别强调 带有膦孤对电子的环蕃 与芳香环紧密相连。其他富含电子的群体， 例如烯烃、胺、氧化膦和甲硅烷基氟化物 也将被审查。通过平衡由于 这些化合物具有亲核性 或芳环的亲电性，可以 获得其中在所述材料之间存在部分键合的结构， 组的问题。这种结构可以作为模型， 一般芳香族反应中的过渡态结构。一 该项目的第二部分将涉及综合和研究 富勒烯碎片的物理性质。这一切成功都 片段将是巴克敏斯特富勒烯的不同片段 （球形C60）。 %%% 有机动力学计划的这笔赠款支持 普林斯顿大学的罗伯特·帕斯卡教授 大学该项目的主要重点是综合和 研究高度应变的有机分子，即，分子 一些原子被空间限制所占据 导致与其他原子发生非自然相互作用的位置 以及不寻常的键距和键角。特别感兴趣的 是分子的结构和反应性， 相对不反应的官能团被迫非常 靠得很近预计，强制接近将 导致相关群体的异常反应， 物理性能也是如此。在这个项目的另一部分， 最近发现的球形C60同素异形体的碎片， 碳（碳的其他同素异形体是金刚石和石墨）将 为了理解C60是如何从 碳碎片

The synthesis and properties of molecules in which two relatively unreactive functional groups are forced into close proximity to each other will be studied. Particular emphasis will be placed on in-cyclophanes bearing phosphine lone-pair electrons brought into close proximity with aromatic rings. Other electron-rich groups, such as olefins, amines, phosphine oxides, and silyl fluorides will also be examined. By balancing the forces due to intramolecular strain in these compounds with the nucleophilicity or electrophilicity of the aromatic ring, it may be possible to obtain structures in which there is partial bonding between the groups in question. Such structures may serve as models for transition state structures in ordinary aromatic reactions. A second part of the project will involve the synthesis and study of the physical properties of fullerene fragments. Each of these fragments will be a different segment of buckminsterfullerene (spherical C60). %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Robert Pascal at Princeton University. the main focus of the project is the synthesis and study of highly strained organic molecules, i.e., molecules in which some atoms are forced by steric constraints to occupy positions which lead to unnatural interactions with other atoms and to unusual bond distances and angles. Of particular interest are the structure and reactivity of molecules in which two relatively unreactive functional groups are forced to be very close together. It is expected that the enforced proximity will lead to unusual reactivity for the groups involved,and to unusual physical properties as well. In another part of this project, fragments of a recently discovered spherical C60 allotrope of carbon (other allotropes of carbon are diamond and graphite) will be prepared in order to understand how C60 may be formed from carbon fragments.