A Computational Study of Chalcogen‐containing H 2 X…YF and (CH 3 ) 2 X…YF (X=O, S, Se; Y=F, Cl, H) and Pnicogen‐containing H 3 X′…YF and (CH 3 ) 3 X′…YF (X′=N, P, As) Complexes

A computational study was undertaken for the model complexes H 2 X…YF and (CH 3 ) 2 X…YF (X=O, S, Se; Y=F, Cl, H), and H 3 X′…YF and (CH 3 ) 3 X′…YF (X′=N, P, As), at the MP2/6‐311++G(d,p) level of theory. For H 2 X…YF and H 3 X′…YF, noncovalent interactions dominate the binding in order of increasing YF dipole moment, except for H 3 As…F 2 , and possibly H 3 As…ClF. However, for the methyl‐substituted complexes (CH 3 ) 2 X…YF and (CH 3 ) 3 X′…YF the binding is especially strong for the complexes containing F 2 , implying significant chemical bonding between the interacting molecules. The relative stability of these complexes can be rationalized by the difference in the electronegativity of the X or X′ and Y atoms.