In an earlier post, I discussed[1] a phenomenon known as the “anomeric effect” exhibited by tetrahedral carbon compounds with four C-O bonds. Each oxygen itself bears two bonds and has two lone pairs, and either of these can align with one of three other C-O bonds to generate an anomeric effect. Here I change the central carbon to a boron to explore what happens, as indeed I promised earlier.
One can identify candidates for such molecules by a constrained search of the CSD or the Cambridge structural database, as shown below.
The four B-O distances for each compound matching the query are now subjected to further analysis, the greatest and least values are identified and the difference between them calculated.
The results are shown in the diagram below. Three outliers are identified for close inspection.
Each of the three candidates is also subjected to a Gaussian calculation (MD15L/Def2-TZVPP)[2] (See DOI: 10.14469/hpc/14092)
Intermolecular H-bonds | Intramolecular H-bonds |
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One lesson one always learns when comparing the lengths of bonds observed in crystal structures with those calculated using quantum mechanics is that they sometimes do not match well. These mis-matches can occur for various reasons; changes in hydrogen bonding, or the presence of unmodelled counterions or simply errors in the reported crystal structure. But we might suggest from this brief foray into B-O bonds that the anomeric effects found there may indeed be larger than those of their C-O counterparts.
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