Theoretical and Crystallographic Study of Lead(IV) Tetrel Bonding Interactions.

The ability of tetrahedral lead(IV) to establish noncovalent σ-hole tetrel bonding interactions with electron-rich atoms (ElRs; anions and Lewis bases) has been studied at the PBE0-D3/def2-TZVPD level of theory. An analysis of the Cambridge Crystallographic Database (CSD), which is a convenient storehouse of geometric information, has been performed to investigate the existence of tetrel bonding interactions involving tetrahedral lead(IV) derivatives. Several examples of tetrel bonding interactions that are crucial in crystal packing, ranging from 0D to 2D assemblies, have been found. In addition to the energetic and theoretical study of several XPb(CH3 )3 ⋅⋅⋅ElR complexes (X=F, CN, CF3 , and CH3 ), Bader's theory of atoms in molecules has also been used to further analyze and characterize the noncovalent interactions described herein.