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Determination and Gas-phase Stability Evaluation of Organometallic Complexes by Nanoelectrospray Ionization and Collision-induced Dissociation Tandem Mass Spectrometry
  • Xi Li,
  • Keisuke Sawada,
  • Hirotaka Shioji
Xi Li
Kabushiki Kaisha Toray Research Center Kenkyu Bumon Shiga

Corresponding Author:[email protected]

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Keisuke Sawada
Kabushiki Kaisha Toray Research Center Kenkyu Bumon Shiga
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Hirotaka Shioji
Kabushiki Kaisha Toray Research Center Kenkyu Bumon Shiga
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Rationale: The structures of organometallic complexes determine their stable functioning in product performance. Electrospray ionization-mass spectrometry (ESI-MS) is used in studying metal complexes, but it exhibits limitations in analyzing labile organometallics. Therefore, identifying a method of detecting unstable organometallics and evaluating their stabilities is necessary, providing a theoretical basis for material selection and performance evaluation. Methods: The standard complexes Zn(BTZ) 2, Fe(acac) 3, and Sn(Oct) 2 were analyzed using nanoelectrospray ionization-quadrupole orbitrap MS (nanoESI-MS) and compared with ESI-MS. Alkylamine-Ag + complexes were analyzed using nanoESI and collision-induced dissociation MS/MS (CID-MS/MS). Breakdown plots of the ion relative abundances against collision energies expressed in terms of the center-of-mass were constructed according to the obtained product ion spectra. Quantum chemical calculations based on density functional theory were performed to calculate the binding energies between the alkylamines and Ag +. Results: The molecular ions of the three standard complexes were only detected using nanoESI-MS, which confirmed the suitability of soft nanoESI for use in detecting unstable organometallics. The gas-phase stabilities of the amine-Ag + complexes, as estimated using the breakdown plots constructed by plotting the data obtained via nanoESI and CID-MS/MS, were consistent with the established theories, previous studies, and binding energies calculated using computational methods. Conclusions: NanoESI-MS is suitable for detecting labile organometallics and enables the structural analyses of unknown organometallic additives. A novel approach based on nanoESI and CID-MS/MS was developed to determine the gas-phase stabilities of organometallics, enabling their quantification and comparison and providing a technical basis for product improvement, which is essential in developing industrial materials.
22 May 2023Submitted to Rapid Communications in Mass Spectrometry
22 May 2023Assigned to Editor
22 May 2023Submission Checks Completed
22 May 2023Review(s) Completed, Editorial Evaluation Pending
22 May 2023Reviewer(s) Assigned
14 Jun 2023Editorial Decision: Revise Major