Hexacoordinated Tetrel‐Bonded Complexes between TF4 (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes. Issue 7 (7th March 2019)

• Record Type: Journal Article
• Authors: Michalczyk, Mariusz; Zierkiewicz, Wiktor; Wysokiński, Rafał; Scheiner, Steve
• Is Part Of: Chemphyschem. Volume 20:Issue 7(2019)
• Page Start: 959
• Page End: 966
• Publication Date: 2019-03-07
• Subjects: density functional calculations -- donor−acceptor systems -- σ-hole -- π-hole, molecular modelling; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201900072
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: In order to accommodate the approach of two NCH bases, a tetrahedral TF4 molecule (T=Si, Ge, Sn, Pb) distorts into an octahedral structure in which the two bases can be situated either cis or trans to one another. The square planar geometry of TF4, associated with the trans arrangement of the bases, is higher in energy than its see‐saw structure that corresponds to the cis trimer. On the other hand, the square geometry offers an unobstructed path of the bases to the π‐holes above and below the tetrel atom and hence enjoys a higher interaction energy than is the case for the σ‐holes approached by the bases in the cis arrangement. When these two effects are combined, the total binding energies are more exothermic for the cis than for the trans complexes. This preference amounts to some 3 kcal mol −1 for Sn and Pb, but is amplified for the smaller tetrel atoms. Abstract : σ‐ or π‐hole bond ? Isolated TF4 molecule (T=Si, Ge, Sn, Pb) has tetrahedral configuration. In complexes with two HCN ligands this entity is able to adopt either see‐saw or planar geometry, which makes possible creation of σ‐hole or π‐hole bonded trimers, respectively.