HIGH OXIDATION STATE TRANSITION METAL CHEMISTRY

这项研究的长期目标是确定分子 在室温下，氮可以被催化还原成氨 使用过渡金属络合物和质子和电子。 的 短期目标是研究络合物的化学性质 含有较高氧化态的钼或钨的 （4+，5+，6+）或（5+，6+，7+）与二氮有关 还原，特别是含有N2 Hx和NHy的单体络合物 配体。 下一个资助期的具体目标包括（i） 深入研究了含有MCp* Me 3片段的单体复合物（M = Mo或W）和肼基（1-）或肼基（2-）配体，或肼，或 氨;（ii）合成和研究含有氨的相关络合物; ReCp* Me 3核;和（iii）其他类型的高分子的合成和研究 氧化态络合物，其中二氮、肼基、肼或 氨配体将结合以形成与催化剂相关的络合物。 还原二氮。 除了综合，我们将重点放在 电化学、15 N标记和机理研究、X射线研究 证明中间体在N2还原序列，和设计的一个 催化均相二氮还原系统。

The long-term objective of this research is to determine how molecular nitrogen can be reduced to ammonia catalytically at room temperature employing a transition metal complex and protons and electrons. The short-term objective is to investigate the chemistry of complexes containing molybdenum or tungsten in a relatively high oxidation state (4+,5+,6+) or rhenium (5+,6+,7+) that are relevant to dinitrogen reduction, especially monomeric complexes containing N2Hx and NHy ligands. Specific objectives for the next grant period include (i) an in depth study of monomeric complexes containing the MCp*Me3 fragment (M = Mo or W) and hydrazido(1-) or hydrazido(2-) ligands, or hydrazine, or ammonia; (ii) synthesis and study of related complexes containing the ReCp*Me3 core; and (iii) synthesis and study of other types of high oxidation state complexes to which dinitrogen, hydrazido, hydrazine, or ammonia ligands will bind to form complexes relevant to catalytic reduction of dinitrogen. In addition to synthesis we will focus on electrochemistry, 15N labelling and mechanistic studies, x-ray studies of proven intermediates in N2 reduction sequences, and the design of a catalytic homogeneous dinitrogen reduction system.