将自然界资源丰富但化学性质上极其惰性的氮气分子在温和条件下转化为氨及其他含氮化合物,具有非常重要的意义。过渡金属络合物引发氮分子的活化及官能化已成为现代工业固氮的一大研究热点。本文回顾了氮分子与双核过渡金属络合物结合的键型模式,总结了影响氮分子活化的诸多因素如配体调变效应、金属调变效应等,对双核过渡金属络合物引发的双氮裂解、双氮官能化及CO/CO2协助双氮活化官能化等反应的实验与理论研究现状和进展进行了简要综述,并对未来过渡金属络合物在氮分子固定的应用发展作了展望。
Dinitrogen fixation activated by organometallic complexes under mild conditions is one of hot fields in modern industry, which try to convert abound but quite inert dinitrogen into ammonia or other nitrogenous compounds. In this review, coordination modes of N2 molecule with transition-metal complexes are classified, and the main factors such as steric effect and electronic effect on the dinitrogen activation and functionalization promoted by dinuclear transition-metal complexes are surveyed. This review attempts to summarize recent experimental and theoretical studies concerning the reactivity patterns of dinitrogen with binuclear transition-metal complexes in the dinitrogen cleavage and functionalization as well as the CO/CO2 induced N2 activation. The prospects of dinitrogen fixation activated by transition-metal complexes is presented, which is hoped to assist chemists in guiding research in the future.