The Nature of Chalcogen‐Bonding‐Type Tellurium–Nitrogen Interactions: A First Experimental Structure from the Gas Phase

(C(6)F(5))Te(CH(2))(3)NMe(2) (1), a perfluorophenyltellurium derivative capable of forming intramolecular N⋅⋅⋅Te interactions, was prepared and characterized. The donor‐free reference substance (C(6)F(5))TeMe (2) and the unsupported adduct (C(6)F(5))(Me)Te⋅NMe(2)Et (2 b) were studied in parallel. Molecular structures of 1, 2 and 2 b were determined by single‐crystal X‐ray diffraction and for 1 and 2 by gas‐phase electron diffraction. The structure of 1 shows N⋅⋅⋅Te distances of 2.639(1) Å (solid) and 2.92(3) Å (gas). Ab initio plus NBO and QTAIM calculations show significant charge transfer effects within the N⋅⋅⋅Te interactions and indicate σ‐hole interactions.