Comparative Assessment of ESI‐MS Softness for Inorganic Complexes: How Soft Is Your ESI‐MS?

Author:

Chagunda Ian C.1ORCID,Williams Peter J. H.1ORCID,Fisher Tiago1,Stock Naomi L.2ORCID,Beach Daniel G.3ORCID,Thomas Gilian T.4ORCID,Zhu Jane5,McIndoe J. Scott1ORCID

Affiliation:

1. Department of Chemistry University of Victoria PO Box 1700 STN CSC Victoria BC V8W 2Y2 Canada

2. Water Quality Centre Trent University 1600 West Bank Drive Peterborough ON K9L 0G2 Canada

3. Biotoxin Metrology National Research Council Canada 1411 Oxford St. Halifax NS B3H 3Z1 Canada

4. Centre for Catalysis Research and Innovation Department of Chemistry and Biomolecular Sciences University of Ottawa 10 Marie Curie Ottawa ON K1N 6 N5 Canada

5. Department of Chemistry University of British Columbia 2036 Main Mall Vancouver BC V6T 1Z1 Canada

Abstract

AbstractElectrospray ionization mass spectrometry (ESI‐MS) is a powerful tool for identifying and characterizing organometallic and coordination compounds. However, detection of fragile structures bound by weaker intermolecular forces can be significantly limited in ESI‐MS owing to the use of relatively harsh instrument conditions and configurations. In this study, a set of tests was developed to assess the softness of ESI‐MS systems. Two variants are presented: positive ion mode, utilizing a mixture of sodium ions and triphenylphosphine oxide producing [Na(OPPh3)n]+ ions (n=1–4), and negative ion mode utilizing Pd(PPh3)4 and sulfonated triphenylphosphine producing [Pd(L)(PPh3)n] ions (n=0–2), where softer instrument conditions preserve a higher proportion of the high‐coordinate ions and harsher conditions will result in increased detection of products of ion fragmentation. The results revealed notable variations in instrument softness, which were influenced by a combination of instrument design and experimental parameters. Meticulously optimizing experimental conditions and ESI‐MS parameters is essential to achieving the softest ionization possible, ensuring reliable analysis where applicable. This study offers valuable insight through straightforward tests that can be employed to assess the suitability of an instrument for specific research needs.

Funder

Institute of Coal Chemistry, Chinese Academy of Sciences

Natural Sciences and Engineering Research Council of Canada

Universities Space Research Association

University of Victoria

Trent University

Publisher

Wiley

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