Two Sterically Encumbered 1,3,2‐Dioxaphospholanes – Reactions,Comparison of Crystal Structures and Computational Explanations

3,4,5,6‐Tetrachlorobenzo‐3‐(2,4,6‐tri‐tert‐butylphenyl)‐1,3,2‐dioxaphospholane ( 2 ) and benzo‐3‐(2,4,6‐tri‐tert‐butylphenyl)‐1,3,2‐dioxaphospholane ( 4 ), in which the reactive P^III‐center lies close to the sterically demanding Mes* group (Mes* = 2,4,6‐tri‐tert‐butylphenyl), were prepared from Mes*–Br and the corresponding P‐chloro‐phospholane. Compounds 2 and 4 reacted with various oxidants, azides, MeSO₃CF₃ or (tht)AuCl] (tht = tetrahydrothiophene) to give the expected products. All crystal structures of the products display a strongly distorted Mes* system with a boat conformation of the phenyl ring and appreciable out‐of‐plane deviations of phosphorus and the ortho‐tert‐butyl groups to opposite sides of the ring. Quantum chemical calculations at the DFT (density functional theory) level of theory were used in order to discriminate between intra‐ and intermolecular forces, which are responsible for these distortions.