Reactions of doubly deprotonated 2,6-naphthalenedicarboxylic acid with alcohols: Proton transfer versus solvation

- A dicarboxylate dianion clusters with alcohols.
- Sequential solvation is observed.
- Surprisingly, the weakest base undergoes proton transfer.
- Solvation of the conjugate acid results in a kinetically enhanced process.
- Coulomb barriers can be mitigated by cluster formation.

Electrospray ionization of 2,6-naphthalenedicarboxylic acid readily affords its doubly deprotonated dicarboxylate dianion (12−). This species clusters with background water and added alcohols in an ion trap at ∼10−3 Torr. Sequential solvation is observed to afford mono and dicoordinated ions. Surprisingly, the latter cluster (12−
- 2TFE) is protonated by 2,2,2-trifluoroethanol (TFE) whereas 12−and 12−
- TFE are not even though ΔH°acid(TFE) = 361.7 ± 2.5 kcal mol−1 (as given in the NIST website at http://webbook.nist.gov) and the B3LYP/6-31+G(d,p) proton affinities are 384.7 (12−), 377.6 (12−
- TFE), and 362.7 (12−
- 2TFE) kcal mol−1. That is, only the weakest base in this series, and the dianion with an equal number of solvent molecules and charged sites, undergoes proton transfer. In a FTMS instrument at lower pressures (∼10−8 Torr) inefficient proton abstraction is observed with the monosolvated dianion. This difference, and the observed reactivities of 12−, 12−
- TFE and 12−
- 2TFE are rationalized with the aid of computed potential energy surfaces. The chemical structures of these cluster ions were also probed via collision-induced dissociations, infrared photodissociation from 2700 to 3200 cm−1, and extensive calculations. All of the TFE species are found to be solvated dianions, but incipient proton transfer to afford electrostatically defying anion-anion clusters is noted in two cases. In proton transfer reactions, formation of the conjugate acid as a solvated ion lowers the energy of the system and reduces the Coulomb repulsion barrier facilitating the overall process.

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