Abstract
Summary of main observation and conclusion1,3‐Dipolar cycloaddition reaction between organic azide and metal carbyne is a useful strategy to construct metallacycles. However, the electronic behavior of organic azide in 1,3‐dipolar cycloaddition reactions is less explored. This work revealed the unexpected role of organic azide as electrophiles in its cycloadditions with various metal carbynes. The feasibility and regioselectivity of a Fischer‐type osmium carbyne in its reaction with an organic azide are explained by the increased nucleophilicity of carbyne carbon upon bending.
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