Chemically Triggered C–ON Bond Homolysis in Alkoxyamines. Part 2: DFT Investigation and Application of the pH Effect on NMP

Chemically Triggered C–ON Bond Homolysis in Alkoxyamines. Part 2: DFT Investigation and Application of the pH Effect on NMP Full article

Journal

Macromolecular Rapid Communications

Output data

Year: 2012, Volume: 33, Number: 2, Pages: 152-157 Pages count : 6 DOI: 10.1002/marc.201100590

Tags

C—ON bond homolysis, kinetics, nitroxide-mediated polymerization, pH effect polymerization

Authors

Bagryanskaya Elena ¹ , Brémond Paul ² , Edeleva Mariya ¹ , Marque Sylvain R.A. ² , Parkhomenko Dmitriy ¹ , Roubaud Valérie ² , Siri Didier ²

Affiliations

1	International Tomography Center SB RAS
2	Aix Marseille Univ, CNRS, ICR

In recent work, a 15-fold increase in the C–ON bond homolysis rate constant kd of 4-pyridylethyl-SG1-based alkoxyamine was observed upon protonation of the pyridyl moiety in organic solvent. In this report, the pH dependence of kd (pKa = 4.7) is investigated in D2O/CD3OD (v/v 1:1). A 64-fold increase in kd is observed at acidic pH. Calculations show that the increase in kd upon protonation is due to both an increase in the stabilization of the protonated 4-pyridylethyl radical and an increase of the destabilization of the starting materials through an increase in the polarity of the alkyl fragment. This new alkoxyamine is applied to NMP of styrene and sodium styrene sulfonate.

Bagryanskaya E. , Brémond P. , Edeleva M. , Marque S.R.A. , Parkhomenko D. , Roubaud V. , Siri D.
Chemically Triggered C–ON Bond Homolysis in Alkoxyamines. Part 2: DFT Investigation and Application of the pH Effect on NMP
Macromolecular Rapid Communications. 2012. V.33. N2. P.152-157. DOI: 10.1002/marc.201100590 WOS Scopus РИНЦ

Submitted:	Sep 7, 2011
Published online:	Nov 21, 2011

Web of science	WOS:000299102700008
Scopus	2-s2.0-84856022363
Elibrary	17974221
OpenAlex	W2100788317