Synthesis of d- and p-Block Element Molecules, Reagents, and Precursors

在化学系化学合成计划的支持下，麻省理工学院化学系的克里斯托弗·康明斯教授正在合成可能与星际分子识别相关的含磷小分子。该项目位于合成化学和天体化学的交叉点上。化学合成将用于制备可能存在于星际空间的小分子。它们在实验室中的特征将为天体物理学家在太空中寻找它们铺平道路。以互惠的方式，已知的星际分子激发了新的、高活性的物种的发展，这些物种可以作为合成化学中的新试剂来开发。预计该项目还将对材料科学产生影响，因为一些新的小分子及其分子前驱体可能提供低温访问感兴趣的无机材料的电子性能。在该项目过程中开发的试剂可能会在有机合成和催化中得到应用。此外，该项目将教育和培训不同的本科生和研究生群体，以及博士后学者。更广泛的影响还包括通过麻省理工学院的Access计划，旨在将未被充分代表的基团的成员带入化学研究生学习，以及计划制作YouTube“无机合成视频”。该项目的主题是设计和合成基于蒽的试剂，以产生用于溶液中的基团转移反应的新型活性中间体，或者用于将小分子演化到气相，以便通过分子束质谱学和微波光谱分析进行研究。后一种形式的光谱学被用来收集射电天文学家所需的数据，以确定星际空间中的分子。要研究的具体体系包括三磷四面体、一氮化磷(PN)及其非爆炸性合成子、PNSO的分子前体、磷烷(C2H4PH的衍生物)的合成和化学，以及RBA和REA化合物(R=烷基；E=N或P；A=菲)。该项目还将涉及开发过渡金属催化反应，以将基团转移到有机底物，如烯烃。一条研究路线将探索应变能释放驱动的催化的分支，涉及到被称为磷酸四面体的应变分子。该项目涉及许多合作，可能最引人注目的是与对研究星际分子感兴趣的天体物理学家。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Synthesis Program of the Chemistry Division, Professor Christoper Cummins of the Chemistry Department at the Massachusetts Institute of Technology (MIT), is synthesizing phosphorus-containing small molecules that may have relevance to the identification of interstellar molecules. The project resides at the intersection of synthetic chemistry and astrochemistry. Chemical synthesis will be used to prepare small molecules that may exist in interstellar space. Their characterization in the laboratory will pave the way for astrophysicists to search for them in space. In reciprocal fashion, known interstellar molecules serve as inspiration for the development of new, highly reactive species that can be developed as new reagents in synthetic chemistry. The project also is expected to have impacts on materials science in that some of the new small molecules and their molecular precursors may provide low-temperature access to inorganic materials of interest for their electronic properties. Reagents developed in the course of the project may find application in organic synthesis and catalysis. Additionally, the project will educate and train a diverse group of undergraduate and graduate students, and postdoctoral scholars. Broader impacts also include outreach through the MIT Access program aimed at bringing members of underrepresented groups into graduate study in chemistry, and the planned production of YouTube “Inorganic Synthesis Videos.”The project has a theme of design and synthesis of anthracene-based reagents for generating novel reactive intermediates for group transfer reactions in solution, or for evolution of small molecules into the gas phase for study by molecular beam mass spectrometry and microwave spectroscopy. The latter form of spectroscopy is used to collect the data required by the radio astronomers to make a positive identification of the molecules in interstellar space. Specific systems to be investigated include triphosphatetrahedrane, phosphorus mononitride (PN) and non-explosive synthons to it, molecular precursors to PNSO, synthesis and chemistry of phosphiranes (derivatives of C2H4PH), and RBA and REA Compounds (R = alkyl; E = N or P; A = anthracene). The project also will involve the development of transition-metal catalyzed reactions for group transfer to organic substrates, such as olefins. One line of inquiry will explore the ramifications of strain energy release-driven catalysis involving strained molecules known as phosphatetrahedranes. The project involves a number of collaborations, perhaps most notably with astrophysicists interested in investigating interstellar molecules.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.