The paper highlighted Ag-I- and Zn-II-organometallic catalysing C-C 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 M-C 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. (C) 2013 Elsevier B.V. All rights reserved.