TY - JOUR

T1 - Towards Determining Molecular Structure with ESI-MS Backed by Computational Methods: Structures of Subnanoclusters of Pd and Cu Chlorides, Ion Dynamics in Vacuum, and Challenges to the Methodology

AU - Бондаренко, Антон Александрович

AU - Власова, Ю.С.

AU - Полынский, Михаил Вячеславович

AU - Ильюшенкова, В

AU - Анаников, Валентин Павлович

N1 - Publisher Copyright: © 2022 The Royal Society of Chemistry.

PY - 2022/8/22

Y1 - 2022/8/22

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85138991657&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/0a78cf93-2c06-39cb-9de0-96dca3bf21ba/

U2 - 10.1039/d2qi01098d

DO - 10.1039/d2qi01098d

M3 - Article

VL - 9

SP - 5279

EP - 5295

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 20

ER -