HIGH-OXIDATION STATE TRANSITION METAL CHEMISTRY

高氧化态过渡金属化学

• 批准号: 2176385
• 负责人: RICHARD R SCHROCK
• 金额: $ 17.9万
• 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/2176385
• 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 氮气在室温下可以催化还原为氨 采用过渡金属络合物以及质子和电子。 这 短期目标是研究配合物的化学性质 含有较高氧化态的钼或钨 与二氮相关的 (4+,5+,6+) 或铼 (5+,6+,7+) 还原，特别是含有 N2Hx 和 NHy 的单体配合物 配体。 下一个资助期的具体目标包括 (i) 深入研究含有 MCp*Me3 片段（M = Mo 或 W) 和酰肼基 (1-) 或酰肼基 (2-) 配体，或肼，或 氨; (ii) 相关配合物的合成和研究 ReCp*Me3 核心； (iii) 其他类型高活性物质的合成和研究 氧化态配合物，其中二氮、酰肼、肼或 氨配体将结合形成与催化相关的复合物 减少二氮。 除了合成之外，我们还将重点关注 电化学、15N 标记和机理研究、X 射线研究 N2 还原序列中经过验证的中间体，以及设计 催化均相二氮还原系统。