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

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 Full article

Journal

Inorganic chemistry frontiers
ISSN: 2052-1553 , E-ISSN: 2052-1545

Output data

Year: 2022, Volume: 9, Number: 20, Pages: 5279-5295 Pages count : 17 DOI: 10.1039/d2qi01098d

Authors

Bondarenko Anton A. ¹ , Vlasova Yulia S. ^2,3 , Polynski Mikhail V. ^2,1,3 , Ilyushenkova Valentina V. ² , Ananikov Valentine P. ^2,1,3

Affiliations

1	Saint Petersburg State University, Universitetsky Prospect 26, Saint Petersburg 198504, Russia
2	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russia
3	MSU, Faculty of Chemistry, Leninskiye Gory 1-3, Moscow 119991, Russia

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, PdCl2, and the CuCl–PdCl2 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 N2 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.

Bondarenko A.A. , Vlasova Y.S. , Polynski M.V. , Ilyushenkova V.V. , Ananikov V.P.
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
Inorganic chemistry frontiers. 2022. V.9. N20. P.5279-5295. DOI: 10.1039/d2qi01098d WOS Scopus OpenAlex

Web of science:	WOS:000849208000001
Scopus:	2-s2.0-85138991657
OpenAlex:	W4292656632

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