Many practically relevant inorganic solution systems have complex compositions with tens or hundreds of distinct species.Here,we present an approach to analyzing ESI-MS spectra combining a set of scripts for peak assi...Many practically relevant inorganic solution systems have complex compositions with tens or hundreds of distinct species.Here,we present an approach to analyzing ESI-MS spectra combining a set of scripts for peak assignment and a quantum chemical methodology for the determination of the structure of selected ions.We selected solutions of CuCl,PdCl_(2),and the CuCl–PdCl_(2) mixture as models of popular precatalysts in cross-coupling reactions and the Wacker process that can form“cocktail”-type systems.The spectra exhibited a great number of signals of mono-and bimetallic oligomeric chloride subnanoclusters.Few oligometallic ions had core–shell structures,according to the computations;the structure of most ions was completely unsymmetric,with bridging Cl−ligands supporting the oligomeric structures.Born-Oppenheimer molecular dynamics showed that some ions were structurally flexible under the selected conditions.Many considered ions exhibited rich configurational and conformational isomerism.The activation(polarization)of the N_(2) molecule(from the drying gas used during electrospray ionization)by some ions was determined by the analysis of electron density distributions.For the first time,we describe a flexible approach for semiautomatic analysis of highly complex mass-spectra of organometallic systems in solution with the possibility of revealing molecular structures.展开更多
基金Bondarenko and Valentine P.Ananikov thank SPbU for financial support(Pure ID:92285019).
文摘Many practically relevant inorganic solution systems have complex compositions with tens or hundreds of distinct species.Here,we present an approach to analyzing ESI-MS spectra combining a set of scripts for peak assignment and a quantum chemical methodology for the determination of the structure of selected ions.We selected solutions of CuCl,PdCl_(2),and the CuCl–PdCl_(2) mixture as models of popular precatalysts in cross-coupling reactions and the Wacker process that can form“cocktail”-type systems.The spectra exhibited a great number of signals of mono-and bimetallic oligomeric chloride subnanoclusters.Few oligometallic ions had core–shell structures,according to the computations;the structure of most ions was completely unsymmetric,with bridging Cl−ligands supporting the oligomeric structures.Born-Oppenheimer molecular dynamics showed that some ions were structurally flexible under the selected conditions.Many considered ions exhibited rich configurational and conformational isomerism.The activation(polarization)of the N_(2) molecule(from the drying gas used during electrospray ionization)by some ions was determined by the analysis of electron density distributions.For the first time,we describe a flexible approach for semiautomatic analysis of highly complex mass-spectra of organometallic systems in solution with the possibility of revealing molecular structures.
