Controlled Reduction of N2 at a Transition Metal Center

超出所提供的空间。本研究的长期目标是确定如何在相对温和的条件下（<100°C和<10°atm），利用明确定义的过渡金属配合物、质子和电子，将分子氮催化还原为氨，或还原为一些含有氮的有机分子。近期目标是制备含有三氨基/供体配体的Mo、W、V、Fe和Ru的新配合物，其中氨基氮上的取代基是一个非常大的间三苯基，并探索与二氮还原相关的化学反应，特别是含有N2Rx （x = 0-4）或NRv （y = 0-3）配体（R = H或c基或si基）的配合物的化学反应。含有这些多齿状三胺胺配体的配合物被稳定的大体积间terphenyl取代，可以抵抗双分子分解反应，并且对质子和电子也相对稳定，因此在二氮还原过程中必需的十几种中间体可以在催化循环中成为稳定的中间体。如果能开发出一种能在氮气作用下催化将氮气还原为氨的系统，那么它就有可能节省大量用于高能耗（200- 400 atm, 350-650℃）、多相、铁催化、Haber-Bosch工艺的能源。对质子和电子活化和还原二氮具有基本和普遍意义的原理，也可能被证明与涉及许多易于发生双分子分解反应的中间体的其他催化反应有关。网站性能 ======================================== 节结束 ===========================================

EXCEED THE SPACE PROVIDED. The long-term objectives of this research are to determine how molecular nitrogen can be reduced to ammonia catalytically under relatively mild conditions (<100 ¿C and <10 atm) employing a well-defined transition metal complex, protons, and electrons, or to some organic molecule that contains nitrogen. The near-term objective is to prepare new complexes of Mo, W, V, Fe, and Ru that contain triamido/donor ligands in which the substituent on the amido nitrogens is an extremely bulky m-terphenyl group, and to explore chemistry that is relevant to the reduction of dinitrogen, especially the chemistry of complexes that contain N2Rx (x = 0-4) or NRv (y = 0-3) ligands (R = H or a C-based or Si-based group). Complexes that contain these multidentate triamidoamine ligands substituted by stable, bulky m-terphenyl groups are resistant to bimolecular decomposition reactions, and also are relatively stable to protons and electrons, so that the dozen or so intermediates that are necessary intermediates in dinitrogen reduction can be stable intermediates in a catalytic cycle. If a system that will catalytically reduce dinitrogen to ammonia under dinitrogen can be developed, it has the potential of saving huge quantities of energy that are used in the energy-intensive (200- 400 atm, 350-650 ¿C), heterogeneous, iron-catalyzed, Haber-Bosch process. Principles that are of fundamental and general significance to the activation and reduction of dinitrogen with protons and electrons may also prove to be relevant to other catalytic reactions that involve many intermediates prone to bimolecular decomposition reactions. PERFORMANCE SITE ========================================Section End===========================================