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

Autor: Kreyenschmidt F; Institut für Organische und Biomolekulare Chemie, Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany., Eisele NF; Institut für Organische und Biomolekulare Chemie, Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany., Hevelke V; Institut für Organische und Biomolekulare Chemie, Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany., Rahrt R; Institut für Organische und Biomolekulare Chemie, Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany., Kreyenschmidt AK; Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany., Koszinowski K; Institut für Organische und Biomolekulare Chemie, Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Oct 24; Vol. 61 (43), pp. e202210211. Date of Electronic Publication: 2022 Sep 26.
DOI: 10.1002/anie.202210211
Abstrakt: Anionic coordination polymerizations proceed via highly reactive intermediates, whose in situ analysis has remained difficult. Here, we show that electrospray-ionization mass spectrometry is a promising method to obtain detailed information on the polymerization process. Focusing on polymerization reactions of 1,3-dienes 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 gas-phase 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.
(© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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