Metal Influence on Cyaphide-Azide 1,3-Dipolar Cycloaddition Reactions: Aromaticity and Activation Strain

The factors governing 1,3-dipolar cycloaddition reactions involving C equivalent to P-containing compounds are computationally explored in detail using quantum chemical tools. To this end, the parent process involving tBuN3 and tBuCP is analyzed and compared to the analogous reaction involving organometallic cyaphide complexes (metal=Au, Pt, Ge, Mg), in order to understand the role of the metal fragment in such transformations. It is found that while the metal fragment does not significantly influence the aromaticity of the corresponding concerted transition states or the regioselectivity of the transformation, it may modify the reactivity of the cyaphide complexes (i. e. Ge and Mg cyaphide complexes are comparatively more reactive). The computed reactivity trends and the factors behind the regioselectivity of the cycloaddition reaction are quantitatively analyzed with the help of the activation strain model in combination with the energy decomposition analysis method. The influence of the metal fragment on the cyaphide-azide 1,3-dipolar cycloaddition reaction is computationally explored in detail. Whereas there is no impact on the aromaticity of the corresponding concerted transition states, a significant influence on the barrier of the cycloaddition, particularly for germanium and magnesium complexes, is found. image