Synthesis and Study of Non-Kekule Molecules

非凯库勒分子的合成与研究

基本信息

批准号：
9321241
负责人：
Joseph Grabowski
金额：
$ 30.5万
依托单位：
University of Pittsburgh
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1994
资助国家：
美国
起止时间：
1994-01-01 至 1997-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=9321241&HistoricalAwards=false
关键词：
Synthesis Study Non Kekule Molecules

项目摘要

This proposal requests funds to examine a series of disjoint biradicals by chemical and spectroscopic methods. Molecular orbital calculations have predicted that disjoint biradicals will possess a singlet ground state. Previous work from this laboratory has resulted in finding a triplet ground state disjoint biradical. This contradiction of theory will be pursued further with new examples which have rigidly defined structures for comparison to theoretical calculations. Non-alternant biradicals will be explored, which contain in some fashion, cyclopentadiene rings. The interplay between structure and multiplicity of these biradicals will be explored, where lower membered systems are expected to be singlets and higher membered systems triplets. This grant from the Organic Dynamics Program supports the continuing work of Professor Paul Dowd at the University of Pittsburgh. The chemical and spectroscopic properties of a novel series of reactive intermediates known as biradicals will be examined. Biradicals are molecules where there are an odd number of electron at two sites. For example, in a hydrocarbon biradical, two carbon atoms will each be bonded to three other carbon atoms and have one unbonded electron. The two odd electrons may have spins paired (a singlet) or unpaired (a triplet). The lowest energy states (singlet or triplet) of the biradicals will be determined experimentally as a function of structure. These results will be compared to theoretical calculations.

该提案要求资金通过化学和光谱方法检查一系列脱节的Biradicals。分子轨道计算预测，脱节的Biradicals将具有单线基态。该实验室的先前工作导致发现了三胞胎基态脱节的分娩。理论的这种矛盾将通过新的示例进行进一步追求，这些新示例已确定了与理论计算进行比较的结构。将探索非替代的Biradicals，其中包含某些方式环境环。将探索这些Biradicals的结构与多样性之间的相互作用，其中预计较低的成员系统将是单元和较高的成员系统三重态。有机动力学计划的这项赠款支持匹兹堡大学保罗·道德（Paul Dowd）教授的持续工作。将检查一系列新型反应性中间体的化学和光谱特性，称为Biradicals。 Biradicals是分子，其中两个位点有奇数的电子。例如，在碳氢化合物Biradical中，两个碳原子将分别粘合到其他三个碳原子，并具有一个无粘性电子。这两个奇数电子可能配对旋转（单线）或未配对（三胞胎）。 Biradicals的最低能量状态（单线或三重态）将根据结构的函数进行实验确定。这些结果将与理论计算进行比较。