Early Metal Mediated Chemistry of the Group 15 Elements

麻省理工学院化学系Christopher C.Cummins博士得到化学部无机、生物无机和有机金属计划的支持，以开发利用直接从元素中提取的氮、磷和砷原子的新反应。利用氮、磷或砷与Nb或Mo三键结合的络合物，将使用原子转移来合成有机氮、磷和砷化合物。将开发制备反应性双原子分子P2、Pn和Asp的路线。初步结果表明，P2分子可以通过与M(CO)5(M=Cr，Mo，或W)片段结合而暂时稳定，而简单的络合物(P2)W(CO)5可以被有机二烯(P？P键的双Diels-Alder反应)、金属络合物或金属-配体多键完全捕获。类似的反应将用PN和ASP进行探索。地球大气中最丰富的元素是氮。虽然大自然能够在生物系统中利用大气中的氮，但现代化学科学仍在寻找经济地利用元素氮的技术。该项目源于最近发现的钼和铌化合物，它们可以在温和的条件下裂解氮氮中的氮-氮键。为了利用这一化学，金属辅助二氮裂解得到的氮原子将被用于制备有机氮化合物。此外，还将设计相关工艺，分别使用从元素磷和砷中提取的磷和砷原子。这些结果将导致制备重要类别的有机和无机砷、磷和氮化合物的新方法。除了科学成果，该项目还将为不同的本科生、研究生、博士后和来访的高级科学家提供培训。

Dr. Christopher C. Cummins, Chemistry Department, Massachusetts Institute of Technology, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for the development of new reactions that utilize nitrogen, phosphorus, and arsenic atoms derived directly from the elements. Using complexes in which a nitrogen, phosphorus, or arsenic is triply bonded to a niobium or molybdenum, atom transfer will be used to synthesize organic nitrogen, phosphorus, and arsenic compounds. Routes will be developed for the preparation of reactive diatomic molecules P2, PN, and AsP. Preliminary results suggest that the P2 molecule can be stabilized transiently by binding to the M(CO)5 (M = Cr, Mo, or W) fragment, and that the simple complex (P2)W(CO)5 can be cleanly trapped by organic dienes (double Diels-Alder reactivity of the P?ßP bond), by metal complexes, or by metal-ligand multiple bonds. Similar reactions will be explored with PN and AsP. The most abundant element in the earth's atmosphere is nitrogen. While nature is able to utilize atmospheric nitrogen in biological systems, modern chemical science is still seeking technologies for the economical usage of elemental nitrogen. This project grows from the recent discovery of molybdenum and niobium compounds that can cleave the nitrogen-nitrogen bond in dinitrogen under mild conditions. In order to utilize this chemistry, the nitrogen atoms derived from metal assisted dinitrogen cleavage will be used to prepare organic nitrogen compounds. In addition, related processes will be devised to use phosphorus and arsenic atoms derived from elemental phosphorus and arsenic, respectively. These results will result in new ways to prepare important classes of organic and inorganic arsenic, phosphorus, and nitrogen compounds. In addition to the scientific results, this project will provide training to a diverse group of undergraduate, graduate, postdoctoral, and visiting senior scientists.