In‐Situ Analysis of Anionic Coordination Polymerizations by Electrospray‐Ionization Mass Spectrometry

Kreyenschmidt, Friedrich; Eisele, Niklas F.; Hevelke, Valentin; Rahrt, Rene; Kreyenschmidt, Anne-Kathrin; Koszinowski, Konrad

doi:10.1002/anie.202210211

Cited by 3 publications

(2 citation statements)

References 33 publications

(27 reference statements)

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“…This technique identifies charged species present in solution by measuring their m / z ratios, from which elemental compositions and molar mass distributions can be easily deduced [4] . Accordingly, it has been successfully applied to the in‐situ analysis of coordinative cationic [5] and coordinative anionic [6] polymerizations, in which the reactive center of the polymer chain is stabilized by binding to a transition metal [7] . Despite the great practical importance of simple transition‐metal‐free anionic polymerizations, these reactions have not been subjected to real‐time analysis by ESI‐MS.…”

Section: Introductionmentioning

confidence: 99%

Live Monitoring of Anionic Living Polymerizations by Electrospray‐Ionization Mass Spectrometry

Eisele

Peters

Koszinowski

2023

Chemistry A European J

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Anionic polymerizations are of exceptional practical importance, but difficult to analyze due to the high reactivity of the growing polymer chains. Here, we demonstrate that electrospray‐ionization mass spectrometry (ESI‐MS) permits direct observation of the active carbanionic intermediates formed in the anionic ring‐opening polymerization of 1‐cyanocyclopropanecarboxylate in tetrahydrofuran. This includes the identification of a side product, as well as real‐time analysis of the polymerization reaction. From the mass spectra obtained, we can derive not only the mean molar mass and the polydispersity, but also the rate constants for the initiation and the individual propagation steps. The initiation proceeds significantly faster than the propagation steps. Accordingly, the examined reaction corresponds to a living polymerization, as we also confirmed by additional control experiments. Besides giving detailed insight into the reaction system probed here, we also expect the presented methodology to make possible the in‐situ analysis of further anionic polymerizations.

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Section: Introductionmentioning

confidence: 99%

Live Monitoring of Anionic Living Polymerizations by Electrospray‐Ionization Mass Spectrometry

Eisele

Peters

Koszinowski

2023

Chemistry A European J

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“…Because it can provide highly-disciplined polymers, the anionic polymerization is one of the most important reactions mediated by reactive intermediates. Because of the importance, several efforts for direct analysis of the intermediate of the anionic polymerization have been studied, for example using mass spectroscopy, [16] focusing on its kinetic analysis in minute-scale. We hypothesized that, utilizing the flow inline system, highly reactive and unstable polymerized anionic intermediates, which must have the life time of second-or less scale, can be directly monitored.…”

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confidence: 99%

Flowmicro In‐Line Analysis‐Driven Design of Reactions Mediated by Unstable Intermediates: Flash Monitoring Approach

Ashikari,

Yoshioka,

Yonekura

et al. 2024

Chemistry A European J

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The direct observation of reactive intermediates is an important issue for organic synthesis. However, intermediates with an extreme instability are hard to be monitored by common spectroscopic methods such as FTIR. We have developed synthetic method utilizing flow microreactors, which enables a generation and reactions of unstable intermediates. Herein we report that, based on our flowmicro techniques, we developed an in‐line analysis method for reactive intermediates in increments of milliseconds. We demonstrated the direct observation of the living and dead species of the anionic polymerization of alkyl methacrylates. The direct information of the living species enabled the anionic polymerization and copolymerization of oligo(ethylene glycol) methyl ether methacrylates, which is the important but difficult reaction in the conventional method.

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In‐Situ Analysis of Anionic Coordination Polymerizations by Electrospray‐Ionization Mass Spectrometry

et al. 2022

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Anionic coordination polymerizations proceed via highly reactive intermediates, whose in situ analysis has remained difficult. Here, we show that electrosprayionization mass spectrometry is a promising method to obtain detailed information on the polymerization process. Focusing on polymerization reactions of 1,3dienes initiated by CoCl 2 /RLi (R = Me, nBu, tBu, Ph), we directly observe the growing polymer chains and characterize the active anionic cobalt centers by gasphase fragmentation experiments. On the basis of these results, we suggest a plausible mechanism for the polymerization reaction. Moreover, the ESI mass spectra permit the determination of molecular weight distributions, which are in good agreement with those derived from NMR-spectroscopic as well as MALDI mass-spectrometric measurements, and afford a wealth of kinetic data.

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In‐Situ Analysis of Anionic Coordination Polymerizations by Electrospray‐Ionization Mass Spectrometry

Cited by 3 publications

References 33 publications

Live Monitoring of Anionic Living Polymerizations by Electrospray‐Ionization Mass Spectrometry

Live Monitoring of Anionic Living Polymerizations by Electrospray‐Ionization Mass Spectrometry

Flowmicro In‐Line Analysis‐Driven Design of Reactions Mediated by Unstable Intermediates: Flash Monitoring Approach

In‐Situ Analysis of Anionic Coordination Polymerizations by Electrospray‐Ionization Mass Spectrometry

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