Ga & BULL;& BULL;& BULL;C Triel Bonds-Why They Are Not Strong Enough to Change Trigonal Configuration into Tetrahedral One: DFT Calculations on Dimers That Occur in Crystal Structures

Structures characterized by the trigonal coordination of the gallium center that interacts with electron rich carbon sites are described. These interactions may be classified as Ga & BULL;& BULL;& BULL;C triel bonds. Their properties are analyzed in this study since these interactions may be important in numerous chemical processes including catalytical activities; additionally, geometrical parameters of corresponding species are described. The Ga & BULL;& BULL;& BULL;C triel bonds discussed here, categorized also as the & pi;-hole bonds, do not change the trigonal configuration of the gallium center into the tetrahedral one despite total interactions in dimers being strong; however, the main contribution to the stabilization of corresponding structures comes from the electrostatic forces. The systems analyzed theoretically here come from crystal structures since the Cambridge Structural Database, CSD, search was performed to find structures where the gallium center linked to CC bonds of Lewis base units occurs. The majority structures found in CSD are characterized by parallel, stacking-like arrangements of species containing the Ga-centers. The theoretical results show that interactions within dimers are not classified as the three-centers links as in a case of typical hydrogen bonds and numerous other interactions. The total interactions in dimers analyzed here consist of several local intermolecular atom-atom interactions; these are mainly the Ga & BULL;& BULL;& BULL;C links. The DFT results are supported in this study by calculations with the use of the quantum theory of atoms in molecules, QTAIM, the natural bond orbital, NBO, and the energy decomposition analysis, EDA, approaches.

Automated summary

Structures with trigonal coordination of gallium center interacting with electron rich carbon sites are examined. These interactions, classified as Ga···C triel bonds, are scrutinized for their properties and potential importance in catalytic processes. Geometrical parameters of the corresponding species are also described. Despite the strong interactions in dimers, the Ga···C triel bonds discussed in this study, also known as π-hole bonds, do not alter the trigonal configuration of the gallium center into tetrahedral. Electrostatic forces are the main contributors to the stabilization of these structures. Crystal structures from the Cambridge Structural Database (CSD) were analyzed to find examples of gallium centers linked to CC bonds of Lewis base units. Majority of the structures found in CSD exhibit parallel stacking-like arrangements of species containing Ga-centers. Interactions within dimers analyzed consist of several local intermolecular atom-atom interactions, primarily Ga···C links, not classified as three-centered as in typical hydrogen bonds and other interactions. DFT results were supported by the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition analysis (EDA) approaches.