Apparent activation of H<sub>2</sub>O and elimination of H<sub>2</sub> from gas‐phase mixed‐metal complexes containing silver, calcium and deprotonated glycine

Osburn, Sandra; Plaviak, Alexandra; Pestok, Jordan; Stipdonk, Michael J. Van

doi:10.1002/rcm.7418

Cited by 3 publications

(6 citation statements)

References 56 publications

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“…Apparently, the H 2 elimination reported here is analogous to the CH 4 loss reported in the formation of metal–hydrogen bonds from organometallic ions such as [(CH 3 M(O 2 CCH 3 )) n ] − upon interaction with water . Moreover, an analogous water addition reaction followed by a subsequent H 2 loss has been observed previously by Osburn et al during their studies under positive-ion-generating conditions with mixed-metal complexes containing silver, calcium, and deprotonated glycine. Interestingly, when silver was the only metal present, then only the addition of water took place without the loss of H 2 .…”

Section: Resultssupporting

confidence: 69%

“…Since a direct addition of an oxygen atom by itself is unlikely, we envisaged that the fragment ion is reacting with traces of water in a manner similar to the known behavior of metal hydrides in aqueous solutions. Metal–hydrogen bonds are known to be highly susceptible to moisture, forming products with metal–hydroxide bonds. ,, If this indeed were the case, the hydrogen atom in the OH groups of the enigmatic ions should also be from an external source, and not from the original hydrogens in the M–H bonds. To verify this, a sample of Sr(O 2 CD) 2 was synthesized.…”

Section: Resultsmentioning

confidence: 99%

“…Metal− hydrogen bonds are known to be highly susceptible to moisture, forming products with metal−hydroxide bonds. 12,13,32 If this indeed were the case, the hydrogen atom in the OH groups of the enigmatic ions should also be from an external source, and not from the original hydrogens in the M−H bonds. To verify this, a sample of Sr(O 2 CD) 2 was synthesized.…”

Section: Acs Omegamentioning

confidence: 99%

“…Unwarranted ion–molecule reactions that occur under tandem mass-spectrometric conditions are often a nuisance because they complicate spectral interpretations . Occasionally, such reactions take place in the ion source under electrospray ionization (ESI) conditions. − Ion–molecule reactions are more common in mass spectrometric investigations conducted in tandem-in-time devices, such as ion traps, because the ions are stored in a confined space for a relatively longer period of time prior to ion activation. − Although less common, ion-neutral adduct peaks have also been observed in the spectra recorded on tandem-in-space instruments when reactants such as water, − methanol, ethanol, nitrogen, , oxygen, and carbon dioxide are either present as impurities, or added intentionally as reagents to the collision gas. , …”

Section: Introductionmentioning

confidence: 99%

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

2019

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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( η 2 - O 2 CH) 3 ] − , the peak at m / z 91 for SrH 3 – was accompanied by three peaks at higher m / z ratios. These peaks, at m / z 107, 123, and 139, represented SrH 2 (OH) 1 – , SrH 1 (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(η 2 -O 2 CH) 2 ] − with water to form [HO-Mg(η 2 -OCOH) 2 ] − and H 2 indicated that this is an exergonic reaction.

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Section: Resultssupporting

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Acs Omegamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

2019

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“…The group also studied this type of H 2 O activation in mixed metal complexes of the formula [Ag 2 XxXx(Gly‐H) 3 ] + where Xx = Ca, Mg, Sr, and Ag (Osburn et al, 2016). The [AgHXx(Gly‐H)] + product ion was generated after multiple rounds of CID and allowed to react with water in the ion trap.…”

Section: Reactions Of Uranyl Complexesmentioning

confidence: 99%

Ion‐molecule reactions of mass‐selected ions

Parker

Bollis

Ryzhov

2022

Mass Spectrometry Reviews

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Gas‐phase reactions of mass‐selected ions with neutrals covers a very broad area of fundamental and applied mass spectrometry (MS). Oftentimes, ion‐molecule reactions (IMR) can serve as a viable alternative to collision‐induced dissociation and other ion dissociation techniques when using tandem MS. This review focuses on the literature pertaining applications of IMR since 2013. During the past decade considerable efforts have been made in analytical applications of IMR, including advances in one of the major techniques for characterization of unsaturated fatty acids and lipids, ozone‐induced dissociation, and the development of a new technique for sequencing of large ions, hydrogen atom attachment/abstraction dissociation. Many advances have also been made in identifying gas‐phase chemistry specific to a functional group in organic and biological compounds, which are useful in structure elucidation of analytes and differentiation of isomers/isobars. With “soft” ionization techniques like electrospray ionization having become mainstream for quite some time now, the efforts in the area of metal ion catalysis have firmly moved into exploring chemistry of ligated metal complexes in their “natural” oxidation states allowing to model individual steps of mechanisms in homogeneous catalysis, especially in combination with high‐level DFT calculations. Finally, IMR continue to contribute to the body of knowledge in the area of chemistry of interstellar processes.

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Computed Mass-Fragmentation Energy Profiles of Some Acetalized Monosaccharides for Identification in Mass Spectrometry

et al. 2022

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Our study found that quantum calculations can differentiate fragmentation energies into isomeric structures with asymmetric carbon atoms, such as those of acetalized monosaccharides. It was justified by the good results that have been published in recent years on the discrimination of structural isomers and diastereomers by correlating the calculated mass energy fragmentation profiles with their mass spectra. Based on the quantitative structure–fragmentation relationship (QSFR), this technique compares the intensities of primary ions from the experimental spectrum using the mass energy profiles calculated for the candidate structures. Maximum fit is obtained for the true structure. For a preliminary assessment of the accuracy of the identification of some di-O-isopropylidene monosaccharide diastereomers, we used fragmentation enthalpies (ΔfH) and Gibbs energies (ΔfG) as the energetic descriptors of fragmentation. Four quantum chemical methods were used: RM1, PM7, DFT ΔfH and DFT ΔfG. The mass energy database shows that the differences between the profiles of the isomeric candidate structures could be large enough to be distinguished from each other. This database allows the optimization of energy descriptors and quantum computing methods that can ensure the correct identification of these isomers.

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Apparent activation of H₂O and elimination of H₂ from gas‐phase mixed‐metal complexes containing silver, calcium and deprotonated glycine

Cited by 3 publications

References 56 publications

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

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

Ion‐molecule reactions of mass‐selected ions

Computed Mass-Fragmentation Energy Profiles of Some Acetalized Monosaccharides for Identification in Mass Spectrometry

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Apparent activation of H2O and elimination of H2 from gas‐phase mixed‐metal complexes containing silver, calcium and deprotonated glycine

Cited by 3 publications

References 56 publications

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

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

Ion‐molecule reactions of mass‐selected ions

Computed Mass-Fragmentation Energy Profiles of Some Acetalized Monosaccharides for Identification in Mass Spectrometry

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Product

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Apparent activation of H₂O and elimination of H₂ from gas‐phase mixed‐metal complexes containing silver, calcium and deprotonated glycine