Probing Cyanocuprates by Electrospray Ionization Mass Spectrometry

Putau, Aliaksei; Koszinowski, Konrad

doi:10.1021/om101038t

Cited by 15 publications

(6 citation statements)

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“…Before entering the ion trap, the ions passed a glass capillary (capillary exit: ±20 V), a skimmer (±20 V), and two transfer octopoles (±4.0 V/±1.7 V). As we have shown before, these very mild ESI conditions help to prevent labile organometallic species from unwanted decomposition reactions . The helium‐filled ion trap (estimated pressure p (He) ca.…”

Section: Methodsmentioning

confidence: 99%

Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions

Parchomyk

Koszinowski

2017

Chemistry A European J

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The cluster ion Me Fe is an unprecedented representative of organoiron species, which are of great interest because of their possible role as intermediates in iron-catalyzed cross-coupling reactions. To learn more about its behavior in solution, the possible formation of related cluster ions, and their reactivity, electrospray-ionization mass spectrometry and gas-phase experiments were performed. Me Fe adopts a highly dynamic behavior in solution and disappears in the presence of the chelating ligand N,N,N',N'-tetramethylethylenediamine. Besides homoleptic Me Fe , its heteroleptic analogues Me Fe Ph , n=1-5, are also accessible. Me Fe undergoes iron-halogen exchange reactions with aryl halides. These substrates, as well as their alkyl counterparts, mediate the formation of new homoleptic cluster ions up to Me Fe . In contrast, no evidence was found for oxidative additions or related reactions. Gas-phase fragmentation of the cluster ions results in numerous different reactions, ranging from the loss of single methyl radicals to the reductive elimination of MePh.

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Section: Methodsmentioning

confidence: 99%

Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions

Parchomyk

Koszinowski

2017

Chemistry A European J

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“…The ESI source was operated at a voltage of ±3000 V with N 2 as nebulizer gas (0.7 bar) and drying gas (5.0 L min −1 , 373 K). To transfer the generated ions into the quadrupole‐ion trap, very mild conditions were applied to prevent unwanted decomposition reactions . The helium‐filled trap [estimated pressure p (He)≈ 0.3 Pa] was typically operated at a trap drive of 40 to ensure efficient trapping and detection of ions of medium m / z ratios (typically recorded m / z range: 50–1000).…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl

Schnegelsberg

Bachmann

Kolter

et al. 2016

Chemistry A European J

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Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgCl⋅LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl⋅LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.

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“…Recently, also organometallic compounds sensitive to air and hydrolysis have been successfully studied via ESI-MS (e.g., cyanocuprates), and new sampling techniques for sensitive compounds were introduced, such that the scope of ESI-MS is likely to be extended to even more fragile metal organyls. Further, ESI can nowadays also be performed at low temperatures .…”

Section: Enthusiasmmentioning

confidence: 99%

Applications of Electrospray Ionization Mass Spectrometry in Mechanistic Studies and Catalysis Research

2012

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Mechanistic studies form the basis for a better understanding of chemical processes, helping researchers develop more sustainable reactions by increasing the yields of the desired products, reducing waste production, and lowering the consumption of resources and energy overall. Conventional methods for the investigation of reaction mechanisms in solution include kinetic studies, isotope labeling, trapping of reactive intermediates, and advanced spectroscopic techniques. Within the past decade, electrospray ionization mass spectrometry (ESI-MS) has provided an additional tool for mechanistic studies because researchers can directly probe liquid samples by mass spectrometry under gentle conditions. Specifically, ESI-MS allows researchers to identify the molecular entities present in solution over the course of a chemical transformation. ESI-MS is particularly useful for investigations of organic reactions or metal catalysis that involve ionic intermediates. Accordingly, researchers are increasingly using ESI-MS in mechanistic studies and catalyst development. However, a further understanding of the ESI process and how it can facilitate mechanistic studies has not accompanied this increased use of the technique. Therefore, at least in part the ESI-MS method not only has offered great promise for the elucidation of reaction mechanisms but also became a black box with the occasional risk of misinterpretation. In this Account, we summarize applications of ESI-MS for synthetic and mechanistic research. Recently researchers have established direct linkages between gas-phase data obtained via ESI-MS and processes occurring in solution, and these results reveal qualitative and quantitative correlations between ESI-MS measurements and solution properties. In this context, time dependences, concentration series, and counterion effects can serve as criteria that allow researchers assess if the gas-phase measurements correlate with the situation in the solution. Furthermore, we report developments that bridge the gap between gas-phase and solution-phase studies. We also describe predictions derived from ESI-MS that have been verified with solution-phase chemistry experiments.

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Probing Cyanocuprates by Electrospray Ionization Mass Spectrometry

Abstract: Supporting InformationTable of Contents 1.) Anion-mode ESI mass spectra recorded with the TSQ 7000 instrument (Figures S1 -S4) S2 2.) Characterization of the HCT ion trap (Figures S5 -S8) S4 3.) Comparison of measured and simulated isotope patterns (Figures S9 -S10) S6

Cited by 15 publications

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Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions

Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl

Applications of Electrospray Ionization Mass Spectrometry in Mechanistic Studies and Catalysis Research

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Probing Cyanocuprates by Electrospray Ionization Mass Spectrometry

Abstract: Supporting InformationTable of Contents 1.) Anion-mode ESI mass spectra recorded with the TSQ 7000 instrument (Figures S1 -S4) S2 2.) Characterization of the HCT ion trap (Figures S5 -S8) S4 3.) Comparison of measured and simulated isotope patterns (Figures S9 -S10) S6

Cited by 15 publications

References 0 publications

Solution and Gas‐Phase Reactivity of Me12Fe8− and Related Cluster Ions

Solution and Gas‐Phase Reactivity of Me12Fe8− and Related Cluster Ions

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl

Applications of Electrospray Ionization Mass Spectrometry in Mechanistic Studies and Catalysis Research

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Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions

Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions