New Reactions for Utilizing N and P Atoms Derived Directly from the 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和磷原子的新反应。使用其中氮或磷与铌或钼三重键合的络合物，三键复分解将被开发为有机氮和磷化合物的合成路线。目标包括磷炔、腈和酰亚胺化合物。金属络合物也将被探索作为碳烯捕获试剂，可以进行β-消除，以产生包括腈的物种。基于这些结果，将制备与元素氮和/或磷反应以形成金属-氮化物或金属-磷化物络合物的催化和化学计量体系，所述金属-氮化物或金属-磷化物络合物将经历合成上有价值的反应。这种化学将扩展到金属-碳三键的催化和化学计量反应。其中一个目标是探索碳-碳三键化学在合成含有烯二炔官能团的分子中的应用。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，将设计相关工艺以使用衍生自元素磷的磷原子。这些结果将导致新的方法来制备重要类别的有机磷和氮化合物。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 and phosphorus atoms derived directly from the elements. Using complexes in which a nitrogen or phosphorus is triply bonded to a niobium or molybdenum, triple-bond metathesis will be developed as a synthetic route to organic nitrogen and phosphorus compounds. Targets include phosphaalkynes, nitriles, and acylimido compounds. The metal complexes also will be explored as carbene trapping reagents that can undergo beta-elimination to produce species including nitriles. Based on these results, catalytic and stoichiometric systems that react with elemental nitrogen and/or phosphorus to form metal-nitrido or -phosphido complexes that will undergo synthetically valuable reactions will be prepared. This chemistry will be extended to catalytic and stoichiometric reactions of metal-carbon triple bonds. One objective is to explore molybdenum-carbon triple bond chemistry as applied to the synthesis of molecules containing the enediyne functionality.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 atoms derived from elemental phosphorus. These results will result in new ways to prepare important classes of organic 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.