Inspiration, Frustration, and Fascination: An Excursion into Low-Oxidation State Main Group Chemistry

本研究由化学系化学合成项目资助，由Gregory H.格鲁吉亚大学化学系的罗宾逊将开展一项雄心勃勃的计划，探索具有挑战性的低氧化态主族化学领域。这项工作将表明，N-杂环卡宾和它们的N-杂环二卡宾衍生物构成了一个独特的平台，从其中可以获得许多不寻常的低氧化态主族物种。主要目标包括：（a）合成含有单配位硼阳离子的不寻常物种;（B）合成双配位硼烯;（c）Si（0）原子和母体硅烯的卡宾稳定化;以及（d）制备与主族双原子同素异形体部分集成的扩展分子系统。这些目标的低氧化态物种可以进一步用于合成其他不寻常的主族分子，如羰基衍生物的NHC稳定的硼类似物。该项目利用一类有机碱在室温下稳定高反应性的双原子分子，如二硅，二磷和二砷。该提案描述了进一步研究这些碱稳定的化合物的合成、结构和反应性的努力。这些碱稳定的硅化物可能具有与在先进电子和计算机芯片的制造以及化学催化中存款元素硅或磷的新方法相关的应用。事实上，罗宾逊教授和同事最近获得了一项美国专利（编号：8278456），以表彰他们发现使用有机碱来稳定双原子分子。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Gregory H. Robinson of the Department of Chemistry at The University of Georgia will pursue an ambitious program to explore challenging areas of low-oxidation state main group chemistry. The work will demonstrate that N-heterocyclic carbenes and their N-heterocyclic dicarbene derivatives constitute a unique platform from which many unusual low-oxidation state main group species may be obtained. Major goals in the proposed work include: (a) the synthesis of unusual species containing one-coordinate borocations; (b) the synthesis of two-coordinate borylenes; (c) the carbene-stabilization of a Si(0) atom and a parent silylene; and (d) the preparation of extended molecular systems integrated with main group diatomic allotrope moieties. These targeted low-oxidation state species may further be utilized in the synthesis of other unusual main group molecules such as NHC-stabilized boron analogs of carbonyl derivatives.This project utilizes a class of organic bases to stabilize highly reactive diatomic molecules such as disilicon, diphosphorus, and diarsenic at room temperature. This proposal describes efforts to further study the synthesis, structure, and reactivity of these base-stabilized diatomics. It is possible that these base-stabilized diatomics may have applications related to new ways to deposit elemental silicon or phosphorus in the fabrication of advanced electronics and computer chips and chemical catalysis. Indeed, Professor Robinson and coworkers were recently granted a US patent (No.: 8278456) for their discovery of using organic bases to stabilize diatomic molecules.