Making and Breaking Bonds: Studying Intrinsic Chemistry in the Gas-Phase

Author

Luke MetzlerFollow

Defense Date

7-9-2024

Graduation Date

Summer 8-10-2024

Availability

Immediate Access

Submission Type

dissertation

Degree Name

PhD

Department

Chemistry and Biochemistry

School

School of Science and Engineering

Committee Chair

Michael van Stipdonk

Committee Member

Michael Cascio

Committee Member

Paul Lummis

Committee Member

Partha Basu

Keywords

Gas-phase, Chemistry, Mass Spectrometry, Copper, Uranium, Alkaline Earth Metal

Abstract

The nature of chemical interactions can be difficult to ascertain in the condensed phase; chemistry can be observed, but with the plethora of variables such as solvation, mixes of counter-ions, and complex equilibria, the true intrinsic chemical properties of a given chemical species may be obfuscated. By conducting research in the gas-phase, many of these variables can be reduced, if not eliminated entirely, which can allow for the careful observation of the true physical phenomena driving chemical reactivity.

The research presented herein focuses on the use of ion-trapping (specifically in a linear ion trap) as a method for unveiling the intrinsic chemistry of gaseous ions. The ion trap as a platform for this research provides a mechanism for inducing exergonic reactions by providing energy to the trapped species, and also a method of observing spontaneous (endergonic) reactions by allowing ions to interact with neutral molecules. A series of experiments are presented which highlight the methods available for the interrogation of gas-phase ions, showing how one may determine the composition, reactivity, and structure of both known and unknown species. These methods include isotopic substitution experiments, collection of high mass-accuracy measurements of the ions’ m/z, observation of reactions with adventitious neutral molecules, introduction of specific neutral molecules to observe reactivity, and the use of theoretical calculations such as density functional theory and natural bonding orbital theory. Data is presented on a range of metal-centered species is shown, specifically focusing on copper-, uranium-, calcium-, strontium-, and barium-centered complexes.

The development of a technique specific to the instrumentation discussed in this work for the measurement of kinetic data is also presented. Ideas for future work which can be based around the conclusions and methods of this work are also presented.

Language

English

Recommended Citation

Metzler, L. (2024). Making and Breaking Bonds: Studying Intrinsic Chemistry in the Gas-Phase (Doctoral dissertation, Duquesne University). Retrieved from https://dsc.duq.edu/etd/2241

Additional Citations

1. Metzler, L. J.; Koehler, S.; Somogyi, Á.; Van Stipdonk, M. J., Formation of [Cu (CO₂)(CH₃OH)]⁺ and [Cu (N₂)(CH₃OH)]⁺ by gas-phase dissociation and exchange reactions. International Journal of Mass Spectrometry 2019, 436, 1-6.

2. Van Stipdonk, M. J.; Tatosian, I. J.; Iacovino, A. C.; Bubas, A. R.; Metzler, L.; Sherman, M. C.; Somogyi, A., Gas-phase deconstruction of UO₂²⁺: Mass spectrometry evidence for generation of [OU^VICH]⁺ by collision-induced dissociation of [U^VIO₂(C≡CH)]⁺. J. Am. Soc. Mass Spectrom 2019, 30, 796-805.

3. Metzler, L. J.; Farmen, C. T.; Corcovilos, T. A.; Stipdonk, M. J., Intrinsic Chemistry of [OUCH]⁺: Reactions with H₂O, CH₃C≡N and O₂. Phys. Chem. Chem. Phys 2021, 23, 4475-4479.

4. Metzler, L. J.; Farmen, C. T.; Fry, A. N.; Seibert, M. P.; Massari, K. A.; Corcovilos, T. A.; Van Stipdonk, M. J., Intrinsic reactivity of [OUCH]⁺ : Apparent synthesis of [OUS]⁺ by reaction with CS². Rapid Commun Mass Spectrom 2022, 36 (8), e9260.