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

Electrospray 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. This study investigates the soft ionization process of electrospray ionization mass spectrometry (ESI‐MS) and its implication for detecting thermally fragile inorganic species. It presents simple tests that reveal notable variations in instrument softness, highlighting the importance of instrument parameter optimization. These findings offer valuable guidance for selecting suitable instrument systems for a given analysis and ensuring dependable results.