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This review focuses on N<jats:sub>2<\/jats:sub> activation and addition to unsaturated substrates, including carbon monoxide, carbon dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, and allenes, mediated by transition metal complexes, which afforded a variety of N\u2212C bond formation products. Emphases are placed on the reaction modes and mechanisms. 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