The paper highlighted Ag I - and Zn II -organometallic catalysing CC coupling processes of polysubstituted benzoic acids in polar protic solutions. Six novel interaction products of substituted biphenyl, 6H-benzo-[c]-chromene[6]-one, chromeno[5,4,3-cde]chromene-5,10-dione, and 4,10-dioxa-pyrene-5,9-dione are isolated. The study, therefore impact the fields of inorganic, metal–organic and organometallic chemistry, catalysis, semi-synthetic natural products and materials research, polymer science, and more. The mechanistic aspects of the reactions with participation of nine MC bonded organometallic precursors (M=Zn II , Ag I /Ag II ) and four metal-organic coordination compounds are comprehensively discussed. The factors stabilizing the metal ion – containing systems in polar environment and gas–phase are elucidated, employing the method of quantum chemistry and variety of mass spectrometric approaches, utilizing the ESI-, APCI- and MALDI-methods. These latters provided experimental physical evidences for formation of Zn II and Ag I -containing organometallics species with closed d 10 shell electronic configuration of the metal ions. The data reported are of methodological importance for the field of the mass spectrometry as well. Due to the matrix-analyte sample preparation techniques in UV–MALDI–MS method widely utilize polysubstituted benzoic acids as organic matrixes. The study contributed as well to the fundamentals of CT- and MLCT-effects in coordination compounds of metal ions with closed d 10 -electronic configuration. Electronic absorption spectroscopy, single crystal X-ray diffraction and nuclear magnetic resonance methods are also utilized.