Rhodium(III) azide half-sandwich complexes of general formula [Rh(Cp*)(N 3 )(bpy R,R )]CF 3 SO 3 with R = H, OCH 3 were prepared in three steps in an overall yield of 55-65 %. Their stability strongly depends on the 4,4′-substituent on the 2,2′-bipyridine (bpy) ligand and increases in the order COOCH 3 < H < OCH 3 . Consequently, no stable product could be isolated for the complex with the methyl ester substituent. The title compounds easily underwent cycloaddition reactions with ethyl 4,4,4-trifluoro-2-butynoate in acetonitrile at room temperature in the absence of catalyst. The resulting triazolate products

This cover feature shows the iClick reaction of a rhodium(III) azide complex with an electron‐poor alkyne. Like pieces in a jigsaw puzzle, the two reactants just “fit together” to form the triazolate complex in good yield. This catalyst‐free room‐temperature cycloaddition reaction can easily be followed by solution IR spectroscopy, and some spectral traces are shown in the background. Details are discussed in the article by U. Schatzschneider et al. on page 3024 ff (https://doi.org/10.1002/ejic.201700199).