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Tetrel, Chalcogen, And Ch⋅⋅O Hydrogen Bonds In Complexes Pairing Carbonyl-Containing Molecules With 1, 2, And 3 Molecules Of Co2, L. M. Azofra, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The complexes formed by H2CO, CH3CHO, and (CH3)2CO with 1, 2, and 3 molecules of CO2 are studied by ab initio calculations. Three different types of heterodimers are observed, most containing a tetrel bond to the C atom of CO2, and some supplemented by a CH⋅⋅O H-bond. One type of heterodimer is stabilized by an anti-parallel arrangement of the C=O bonds of the two molecules. The binding energies are enhanced by methyl substitution on the carbonyl, and vary between 2.4 and 3.5 kcal/mol. Natural bond orbital analysis identifies a prime source of interaction as charge transfer into the π*(CO) antibonding …