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  Not-so-innocent anions determine the mechanism of cationic alkylators

Taimoory, S. M., Cataldo, V. A., Schäfer, A., Trant, J. F., & Guterman, R. (2021). Not-so-innocent anions determine the mechanism of cationic alkylators. Chemistry – A European Journal, 27(10), 3440-3448. doi:10.1002/chem.202004208.

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Taimoory, S. Maryamdokht, Author
Cataldo, Vincenzo Alessandro1, Author              
Schäfer, Andreas, Author
Trant, John F., Author
Guterman, Ryan1, Author              
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1Ryan Guterman, Kolloidchemie, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_2411691              

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Free keywords: ionic liquids, alkylating agent, reaction mechanism, computational chemistry, ions
 Abstract: Alkylating reagents based on thioimidazolium ionic liquids were synthesized and the influence of the anion on the alkylation reaction mechanism explored in detail using both experimental and computational methods. Thioimidazolium cations transfer alkyl substituents to nucleophiles, however the reaction rate was highly dependent on anion identity, demonstrating that the anion is not innocent in the mechanism. Detailed analysis of the computationally-derived potential energy surfaces associated with possible mechanisms indicated that this dependence arises from a combination of anion induced electronic, steric and coordinating effects, with highly nucleophilic anions catalyzing a 2-step process while highly non-nucleophilic, delocalized anions favor a 1-step reaction. We also confirm the presence of ion-pairs and aggregates in solution thus supporting anion-induced control over the reaction rate and mechanism. These findings provide new insight into an old reaction allowing for better design of cationic alkylators in synthesis, gene expression, polymer science, and protein chemistry applications.

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Language(s): eng - English
 Dates: 2020-11-022021
 Publication Status: Published in print
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 Rev. Type: -
 Identifiers: DOI: 10.1002/chem.202004208
BibTex Citekey: doi:10.1002/chem.202004208
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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 27 (10) Sequence Number: - Start / End Page: 3440 - 3448 Identifier: ISSN: 0947-6539