Catalyticity of molybdenum-dinitrogen complexes in organic r

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IMAGE: (a) Typical Reactivity Modes of -N2 Units in Transition Metal-Dinitrogen Complexes; (b) This Work: Catalytic Reactivity of Mo-N2 Units in the Disproportionation of Cyclohexadienes and Isomerization of Terminal Alkenes...
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Credit: ©Science China Press
Dinitrogen (N2) fixation is considered as one of the most essential tasks in basic science, providing straightforward methods to produce ammonia and nitrogen-containing molecules. Exploring the reactivity of N2 units of transition metal-nitrogen complexes is of great significance and challenging in the chemistry. Since the first Ru-N2 complex was prepared in 1965, important progress has been made in the synthesis and reactivity of transition metal nitrogen complexes. In many cases, terminal end-on M-N2 complexes as the most prevalent bonding mode were proved to be effective to catalyze reductive reactions of N2 to afford ammonia or silylamines; moreover, due to the nucleophilicity of dinitrogen moiety, the activated dinitrogen ligands in M-N2 (M = Mo, W, Fe, Co) complexes were transformed into N-containing organic compounds with carbon-based electrophiles. On the other hand, late-transition metal-N2 complexes (M = Co, Ru, Ir, Fe) have also been reported as precatalysts for organometallic transformations including cycloaddition and hydrofunctionalization of olefins, semihydrogenation of alkynes, transfer hydrogenation of ketones and acceptorless dehydrogenation of alcohols. In these systems, dinitrogen (N2) as weakly π-accepting ligand to stabilize highly reactive and low valence-electron species, was proved not to be involved in the catalytic processes. The status quo urges exploration on the potential reactivity of coordinated N2 units in organometallic catalysis, which will inspire new strategies for catalytic conversions of N2.

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Zhang Jie Shi , National Science Review , Fudan University , Professor Zhang Jie Shi , Chemistry Physics Materials Sciences , ஜாங் ஜிே ஷி , தேசிய அறிவியல் விமர்சனம் , ப்ரொஃபெஸர் ஜாங் ஜிே ஷி , வேதியியல் இயற்பியல் பொருட்கள் அறிவியல் ,