Organosilver(I) and organozinc(II) catalysed synthesis of quaterphenyls – Experimental and theoretical treatment

3 years ago

Organosilver(I) and organozinc(II) catalysed synthesis of quaterphenyls – Experimental and theoretical treatment

An essential part of molecular scaffolds of organosilver(I) catalysing reactions of C–H bond activation and C–X (X = C or O) bond formation of polysubstituted benzoic acids in polar medium represent biphenyls, 6H-benzo-[c]-chromene[6]-one, chromeno[5,4,3-cde]chromene-5,10-dione, and 4,10-dioxa-pyrene-5,9-diones. A second strand of catalytic activity is in promoting synthesis of substituted quanterphenyls. This paper is a an extend of the systematic examining of catalytic activity of Ag^I–containing intermediates of substituted benzoic acids, gaining insights by synthesis of oligomers, studying benzene-1,2,4-tricarboxylic acid (124BA) and benzene-1,3,5-tricarboxylic acid (135BA). Arguably, the optimization of the latter reactions need further effort in order to achieve the standard characteristics allowing their effective implementation as routine routs in the field of organic synthesis. The purpose of this part of the research is mass spectrometric (MS) quantitative kinetic and thermodynamic treatment of collision induced dissociation (CID) reactions comparing experimental reaction kinetics and energetics with quantum chemical modelling of MS fragment processes. Analyses - experimental and theoretical - include deuterium labelled oligomers as the most useful technique studying MS reaction mechanisms. More specifically we treat eight substituted quaterphenyls both experimentally and theoretically along with a set of one hundred twenty 3D molecular models of MS fragment species. Importantly, the detail understanding of the molecular mechanistic aspects of the reactions causing for obtaining of high functionalized oligomers allows an efficient optimization of synthetic roads studying polyfunctional derivatives. This knowledge is the kay to understanding why the obtaining of the oligomer derivatives depends on the positional isomerism of the starting reagents as clearly evidenced in this study. In this context the study is relevant to the fields of organometallic synthesis and catalysis as well as the polymers' chemistry.

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DOI: S0022328X17305557