Unusual Confinement-Induced Basicity and Proton-Mediated CH Activity of an Adipic Acid-Ammonium Cluster

07 November 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Organic acids play an important role in atmospheric chemistry, particularly in the formation of aerosol particles. Here we explore the reactivity of adipic acid, an analogue to the alpha-pinene oxidation product pinic acid, upon complexation with ammonium. Collision-induced dissociation mass spectra and mass-selective vibrational spectra show that relatively mild activation, consistent with breaking hydrogen bonds, yields (adipic acid)H+ and neutral ammonia. This is consistent with a higher proton affinity for adipic acid than ammonia that we trace to a specific structural motif in which both protonated carboxylic acid carbonyl groups combine to form a basic site that supports an additional bridging proton. Further mild collisional activation yields sequential loss of two water molecules, similar to the behavior of carboxylic acids in superacids, necessitating abstraction of at least one hydrogen from a CH group. Deuterium labeling experiments confirm that the second step indeed involves CH hydrogen atoms. Comparison of vibrational spectra and quantum chemical calculations allows us to assign structures for each step, identifying several ring structures but notably not forming the minimum energy structure upon the first loss of water. We propose a mechanism that explains this reactivity and discuss possible atmospheric implications of these observations.

Keywords

Vibrational Spectroscopy
Mass Spectrometry
Collision-Induced Dissociation

Supplementary materials

Title
Description
Actions
Title
Supporting Information
Description
Figures comparing anharmonic and harmonic calculations to the experimental spectrum of AAH+ - H2O, results of CID experiments on AAH+-d3, comparing computed spectra for different double bond locations in AAH+ - 2H2O, and coordinates for all computed structures.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.