Microwave and Computational Study of Pivalic Sulfuric Anhydride and the Pivalic Acid Monomer: Mechanistic Insights into the RCOOH + SO3 Reaction.

Abstract

The microwave spectrum of pivalic sulfuric anhydride, (CH3)3CCOOSO2OH (PivSA), has been observed by rotational spectroscopy. The compound was formed by the reaction of SO3 with (CH3)3CCOOH (pivalic acid) in a supersonic jet in a manner analogous to that previously observed with other carboxylic acids. Computational analysis indicates that the reaction is best described as a pericyclic process coupled with a 60° rotation of the t-butyl group. Product formation can occur through either a sequential (two-step) or a concerted (one-step) pathway. The former involves an internal rotation of the t-butyl group through a 0.11 kcal/mol barrier followed by the pericyclic reaction that joins the moieties. The latter passes through a second-order saddle point in which the internal rotation and pericyclic reaction occur simultaneously. This path is the most energetically favorable, as the zero-point corrected energy at the saddle point structure is 0.16 kcal/mol below that of a putative (CH3)3CCOOH-SO3 precursor complex. Additional computational work involving a series of carboxylic acids is reported, which explores the effects of gas-phase acidity and basicity of the RCOOH reactant on reaction energetics. These calculations, together with prior experimental and theoretical studies of the acetic and trifluoroacetic derivatives, demonstrate that the basicity of the carbonyl oxygen, not the acidity of the COOH proton, is the important driving factor for the reaction. As a precursor to the experimental work on the title molecule, microwave spectra of the parent and OD forms of the pivalic acid monomer were recorded and are reported here as well. A convenient synthesis of SO3 is also described.