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Fortuitous Ion-Molecule Reaction Enables Enumeration of Metal-Hydrogen Bonds Present in Gaseous Ions.

ABSTRACT: Upon mass selection and ion activation under mass spectrometric conditions, gaseous formate adducts of many metal formates undergo decarboxylation and form product ions that bear metal-hydrogen bonds. Fortuitously, we noted that negative-ion spectra of several such formate adducts showed many peaks that could not be rationalized by the conventional fragmentation pathways attributed to the precursor ion. Subsequent experimentation proved that these enigmatic peaks are due to an ion-molecule reaction that takes place between traces of adventitious water vapor in the collision gas and the in situ formed product anions bearing metal-hydrogen bonds, generated by the fragmentation of the formate adducts. Results show that metal-hydrogen bonds of the group 2 elements are particularly susceptible to this reaction. For example, in the product-ion spectrum of [Sr(?²-O₂CH)₃]^-, the peak at m/z 91 for SrH₃ ^- was accompanied by three peaks at higher m/z ratios. These peaks, at m/z 107, 123, and 139, represented SrH₂(OH)₁ ^-, SrH₁(OH)₂ ^-, and Sr(OH)₃ ^-, respectively. These satellite peaks, which were separated by 16 m/z units, were attributed to adducts formed due to the high affinity of gas-phase anions bearing metal-hydrogen bonds to water. Although undesired, these peaks are diagnostically useful to determine the number of metal-hydrogen bonds present in a precursor ion. Even though the peaks were less pronounced, analogous reactions were noted from the adducts of the group 1 elements as well. Moreover, Gibbs free energy values computed for the interaction of [H-Mg(?²-O₂CH)₂]^- with water to form [HO-Mg(?²-OCOH)₂]^- and H₂ indicated that this is an exergonic reaction.

SUBMITTER: Zheng Z

PROVIDER: S-EPMC6648366 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Fortuitous Ion-Molecule Reaction Enables Enumeration of Metal-Hydrogen Bonds Present in Gaseous Ions.

Zheng Zhaoyu Z Pavlov Julius J Attygalle Athula B AB

ACS omega 20190222 2

Upon mass selection and ion activation under mass spectrometric conditions, gaseous formate adducts of many metal formates undergo decarboxylation and form product ions that bear metal-hydrogen bonds. Fortuitously, we noted that negative-ion spectra of several such formate adducts showed many peaks that could not be rationalized by the conventional fragmentation pathways attributed to the precursor ion. Subsequent experimentation proved that these enigmatic peaks are due to an ion-molecule react ...[more]

PMID: 31459605

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Project description:Our intention is to provide easy methods for estimating entropy and chemical potentials for gas phase reactions. Clausius' virial theorem set a basis for relating kinetic energy in a body of independent material particles to its potential energy, pointing to their complementary role with respect to the second law of maximum entropy. Based on this partitioning of thermal energy as sensible heat and also as a latent heat or field potential energy, in action mechanics we express the entropy of ideal gases as a capacity factor for enthalpy plus the configurational work to sustain the relative translational, rotational, and vibrational action. This yields algorithms for estimating chemical reaction rates and positions of equilibrium. All properties of state including entropy, work potential as Helmholtz and Gibbs energies, and activated transition state reaction rates can be estimated, using easily accessible molecular properties, such as atomic weights, bond lengths, moments of inertia, and vibrational frequencies. We conclude that the large molecular size of many enzymes may catalyze reaction rates because of their large radial inertia as colloidal particles, maximising action states by impulsive collisions. Understanding how Clausius' virial theorem justifies partitioning between thermal and statistical properties of entropy, yielding a more complete view of the second law's evolutionary nature and the principle of maximum entropy. The ease of performing these operations is illustrated with three important chemical gas phase reactions: the reversible dissociation of hydrogen molecules, lysis of water to hydrogen and oxygen, and the reversible formation of ammonia from nitrogen and hydrogen. Employing the ergal also introduced by Clausius to define the reversible internal work overcoming molecular interactions plus the configurational work of change in Gibbs energy, often neglected; this may provide a practical guide for managing industrial processes and risk in climate change at the global scale. The concepts developed should also have value as novel methods for the instruction of senior students.

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Fortuitous Ion-Molecule Reaction Enables Enumeration of Metal-Hydrogen Bonds Present in Gaseous Ions.

Publications

Fortuitous Ion-Molecule Reaction Enables Enumeration of Metal-Hydrogen Bonds Present in Gaseous Ions.

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