Density functional theory and ab initio calculations on carboxyphosphate (CP) have identified a single, unique dianionic pseudo-chair conformation (PC) stabilized by a strong intramolecular hydrogen bond. Natural bond orbital (NBO) and natural resonance theory (NRT) calculations on CP suggest the existence of resonance-assisted hydrogen bonding (RAHB) in PC. In order to understand RAHB in PC, NBO and NRT calculations have been carried out on structural analogues of carboxyphosphate, including donor and bridge subsitutions with sulfur, nitrogen groups, and methyl groups. Results suggest that the resonance effects of the carboxy moiety strengthen the hydrogen bond in the dianion, which was mimicked by the phosphate of the monoanion. Our evidence suggests that RAHB is a strong stabilizing force for the dianionic state, but is greater in the monoanion.

Comparison of resonance-assisted hydrogen bonding in carboxyphosphate and structural analogs

245th National Meeting (2013)

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