3D structural analysis of isomers of benzaldehydes and benzoic acids and their base catalysed C–C coupled derivatives under electrospray ionization conditions – mass spectrometric stochastic dynamic and quantum chemical approaches

Abstract

The paper draws on our stochastic dynamic approach providing exact analytical procedure to quantify experimental mass spectrometric outcome intensity “I” via the so–called mass spectrometric diffusion parameter “DSD.” A small–scale research, so far, has taken a closer look at the functional relation between DSD parameters and quantum chemical diffusion parameters “DQC” according to the Arrhenius's approximation, underlying an excellent linear correlation. Straightforward facts about the latter statement have shown excellent coefficients of linear correlations r = 0.95575–0.9956. This work continues the problematization of the issues relevant to this concept that affect the field of structural analytical chemistry, in particular, looking at experimental 3D molecular and electronic structures of analytes, and the catalysis. As a corollary, the application of the model equations, so far, only covers few examples of analysis of complexes of CuII– and AgI–ions with small organic molecules and oligopeptides. Herein, we move on to a thorny problematic dealing with 3D structural analysis of isomers and tautomers of benzaldehydes, benzoic acids and their products of homocoupling reactions of C–C bond formation leading to 6H-benzo-[c]-chromene[6]-one, chromeno[5,4,3-cde]chromene-5,10-dione, and 4,10-dioxa-pyrene-5,9-dione derivatives, amongst others. We account for the excellent capability of our method, studying quantitatively subtle electronic effects. The analysis encompasses one hundred thirty seven molecular species. Against the backdrop that mass spectrometry appears inapplicable to 3D structural analysis, we demonstrate persuasively its great applicability to exact multidimensional structural study of molecular objects by means of a highly selective quantification of DSD parameters and high accuracy ab initio and DFT DQC parameters of analytes and their fragment ions. A deeper experimental proof of dependence on DSD parameter with respect to experimental factor “temperature” is presented. In spite of, formulas are embedded within the general framework of stochastic dynamic the two equations provide different analytical information. Therefore, by means of our innovative functional relations we not only exactly determine 3D molecular structures by mass spectrometry, but also can quantitatively account for the effect of experimental factor temperature on them.