Speciation Analysis in Iron-Mediated ATRP Studied via FT-Near-IR and Mössbauer Spectroscopy

Autor:	Franc Meyer, Serhiy Demeshko, Michael Buback, Hendrik Schroeder, Johannes Buback, Krzysztof Matyjaszewski
Rok vydání:	2015
Předmět:	Polymers and Plastics Chemistry media_common.quotation_subject Organic Chemistry Radical polymerization Photochemistry Redox Catalysis Inorganic Chemistry Solvent Speciation Mössbauer spectroscopy Materials Chemistry Physical chemistry Polar media_common
Zdroj:	Macromolecules. 48:1981-1990
ISSN:	1520-5835 0024-9297
DOI:	10.1021/acs.macromol.5b00023
Popis:	The structure of [FeIIBru(Solv)v] and [FeIIIBrw(Solv)x] complexes to be used as catalysts for atom-transfer radical polymerization (ATRP) was determined in several solvents via FT-near-IR in conjunction with Mossbauer spectroscopy. The relative amounts of these complexes are sensitive to both the type of solvent and pressure. The [FeIIBr3(Solv)]−/[FeIIIBr4]− redox pair essentially governs the ATRP equilibrium. The properties of these complexes are correlated with the measured ATRP activation rate coefficients, kact, for monomer-free model systems. In weakly polar solvents such as esters, ketones, and substituted benzenes, kact was found to be larger than in strongly polar solvents, such as NMP, MeCN, and DMF, due to stabilization of the [FeIIBr3(Solv)]− complex.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::656cdfc655f9cf66dd943e1d04582c59 https://doi.org/10.1021/acs.macromol.5b00023 Zobrazit plný text záznamu