HIGH OXIDATION STATE TRANSITION METAL CHEMISTRY

高氧化态过渡金属化学

• 批准号: 3280451
• 负责人: RICHARD R SCHROCK
• 金额: $ 16.98万
• 依托单位: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 1983
• 资助国家: 美国
• 起止时间: 1983-04-01 至 1994-11-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3280451
• 关键词: X ray spectrometry; ammonia; catalyst; chemical models; electrochemistry; electron spin resonance spectroscopy; heavy metals; hydrazines; ligands; metal complex; molybdenum; nitrogen; nitrogen fixation; organometallic compounds; oxidation; reduction; tungsten

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.

这项研究的长期目标是确定分子如何 氮可以在室温下催化至氨 采用过渡金属复合物以及质子和电子。 这 短期目标是研究复合物的化学 在相对较高的氧化态中含有钼或钨 （4+，5+，6+）或rhenium（5+，6+，7+） 还原，尤其是含有N2HX和NHY的单体复合物 配体。 下一个赠款期的具体目标包括（i） 在包含MCP*ME3片段的单体复合物的深度研究中（M = mo或w）和hildazido（1-）或hildazido（2-）配体，或 氨; （ii）合成和研究包含的相关复合物 RECP*ME3核心； （iii）合成和研究其他类型的高 氧化态复合物，二氮，hidyazido，hildazine或 氨配体将结合以形成与催化有关的复合物 减少二氮。 除了综合，我们还将重点放在 电化学，15N标记和机械研究，X射线研究 N2还原序列中已验证的中间体的设计 催化均质二氮还原系统。