A quintessential approach to activate and functionalize the exceptionally stable diatomic nitrogen(N_(2))consists of its coordination to transition metal complexes.Accordingly,coordinated N_(2) can undergo reduction s...A quintessential approach to activate and functionalize the exceptionally stable diatomic nitrogen(N_(2))consists of its coordination to transition metal complexes.Accordingly,coordinated N_(2) can undergo reduction steps to deliver a variety of anionic species such as(N_(2))^(1-),(N_(2))^(2-),(N_(2))^(3-)and(N_(2))^(4-).In this context,trianionic hydrazido radicals(N_(2))^(3-)seem to possess atypical reactivity which can be harnessed to forge unprecedented nitrogen-element functionalities(N-E)(E=element).In spite of these promising characteristics,the reaction chemistry of metal-coordinated(N_(2))^(3-)ligands remains considerably scarce in the literature.In this article,we have surveyed the limited reports related to(N_(2))^(3-)species and performed preliminary DFT calculations on the known scandium-(N_(2))^(3-)complex[(η^(5)-C_(5)Me_(5)){^(n)BuC(NiPr)_(2)}Sc]_(2)(μ^(2)-η^(2):η^(2)-N_(2))[{K(2.2.2)cryptand}](1).We have emphasized the future study of the coordinated trianionic hydrazido radical(N_(2))^(3-)by proposing reaction intermediates and possible reaction pathways as well as radical coupling strategies.These ideas represent an effort to stimulate alternative perspectives on the activation and transformation of N_(2) into N-containing compounds.展开更多
基金supported by the National Natural Science Foundation of China(No.21988101 and 22201013)the Beijing Natural Science Foundation(No.2222008).
文摘A quintessential approach to activate and functionalize the exceptionally stable diatomic nitrogen(N_(2))consists of its coordination to transition metal complexes.Accordingly,coordinated N_(2) can undergo reduction steps to deliver a variety of anionic species such as(N_(2))^(1-),(N_(2))^(2-),(N_(2))^(3-)and(N_(2))^(4-).In this context,trianionic hydrazido radicals(N_(2))^(3-)seem to possess atypical reactivity which can be harnessed to forge unprecedented nitrogen-element functionalities(N-E)(E=element).In spite of these promising characteristics,the reaction chemistry of metal-coordinated(N_(2))^(3-)ligands remains considerably scarce in the literature.In this article,we have surveyed the limited reports related to(N_(2))^(3-)species and performed preliminary DFT calculations on the known scandium-(N_(2))^(3-)complex[(η^(5)-C_(5)Me_(5)){^(n)BuC(NiPr)_(2)}Sc]_(2)(μ^(2)-η^(2):η^(2)-N_(2))[{K(2.2.2)cryptand}](1).We have emphasized the future study of the coordinated trianionic hydrazido radical(N_(2))^(3-)by proposing reaction intermediates and possible reaction pathways as well as radical coupling strategies.These ideas represent an effort to stimulate alternative perspectives on the activation and transformation of N_(2) into N-containing compounds.
