Early Metal Mediated Chemistry of the Group 15 Elements

Christopher C.博士马萨诸塞州理工学院化学系的康明斯得到了化学系无机、生物无机和有机物项目的支持，用于开发利用直接来自元素的氮、磷和砷原子的新反应。使用其中氮、磷或砷三重键合到铌或钼上的络合物，原子转移将用于合成有机氮、磷和砷化合物。路线将被开发用于制备反应性双原子分子P2，PN和AsP。 初步结果表明，P2分子可以通过与M（CO）5（M = Cr，Mo或W）片段结合而瞬时稳定，并且简单的络合物（P2）W（CO）5可以被有机二烯干净地捕获（P？β P键）、金属络合物或金属-配体多重键。将对PN和Asp的类似反应进行探索。地球大气中最丰富的元素是氮。虽然自然界能够在生物系统中利用大气氮，但现代化学科学仍在寻求经济利用元素氮的技术。这个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双氮中的氮-氮键。为了利用这种化学，将使用来自金属辅助的二氮裂解的氮原子来制备有机氮化合物。此外，还将设计相关工艺，以分别使用来自元素磷和砷的磷和砷原子。这些结果将导致新的方法来制备重要类别的有机和无机砷，磷和氮化合物。除了科学成果外，该项目还将为本科生、研究生、博士后和访问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.