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Hexacoordinated Tetrel‐Bonded Complexes between TF 4 (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes
Author(s) -
Michalczyk Mariusz,
Zierkiewicz Wiktor,
Wysokiński Rafał,
Scheiner Steve
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201900072
Subject(s) - trimer , octahedron , crystallography , chemistry , molecule , tetrahedron , atom (system on chip) , binding energy , exothermic reaction , physics , atomic physics , dimer , crystal structure , organic chemistry , computer science , embedded system
Abstract In order to accommodate the approach of two NCH bases, a tetrahedral TF 4 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 TF 4 , 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.