Relating Bond Strength and Nature to the Thermodynamic Stability of Hypervalent Togni‐Type Iodine Compounds

The bond strength and nature of a set of 32 Togni‐like reagents have been investigated at the M062X/def2‐TZVP(D) level of theory in acetonitrile described with the SMD continuum solvent model, to rationalize the main factors responsible for their thermodynamic stability in different conformations, and trifluoromethylation capabilities. For the assessment of bond strength, we utilized local stretching force constants and associated bond strength orders, complemented with local features of the electron density to access the nature of the bonds. Bond dissociation energies varied from 31.6 to 79.9 kcal/mol depending on the polarizing power of the ligand trans to CF3. Based on the analysis of the Laplacian of the density, we propose that the charge‐shift bond character plays an important role in the stability of the molecules studied, especially for those containing I−O bonds. New insights on the trans influence and on possible ways to fine‐tune the stability of these reagents are provided. The stability of Togni‐like hypervalent iodine reagents depends on the strength and nature of the bonds that participate in the 3c–4e bond. An increase in charge‐shift bond character tends to stabilize I−O bonds but destabilizes the I−C bond. New insights on the trans influence and on possible ways to fine‐tune the stability and reactivity of Togni‐like reagents are provided.