Alkyl Triarylstannanecarbodithioates: Synthesis, Crystal Structures, and Efficiency in RAFT Polymerization

Ihor Kulai; Nathalie Saffon-Merceron; Zoia Voitenko; Stéphane Mazières; Mathias Destarac

doi:10.1002/chem.201703412

Alkyl Triarylstannanecarbodithioates: Synthesis, Crystal Structures, and Efficiency in RAFT Polymerization

Chemistry. 2017 Nov 13;23(63):16066-16077. doi: 10.1002/chem.201703412. Epub 2017 Nov 8.

Authors

Ihor Kulai¹, Nathalie Saffon-Merceron², Zoia Voitenko³, Stéphane Mazières¹, Mathias Destarac¹

Affiliations

¹ Laboratoire des IMRCP, Université Paul Sabatier, CNRS UMR 5623, 118 route de Narbonne, 31062, Toulouse Cedex 9, France.
² Institut de Chimie de Toulouse, CNRS FR 2599, Université Paul Sabatier, 118 route de Narbonne, 31062, Toulouse Cedex 9, France.
³ Department of Chemistry, Taras Shevchenko National University of Kyiv, 12, Lva Tolstoho street, 01033, Kyiv, Ukraine.

PMID: 28853188
DOI: 10.1002/chem.201703412

Abstract

Eight alkyl triarylstannanecarbodithioates were synthesized starting from the corresponding triarylstannyl chlorides. They were fully characterized by IR and ¹ H, ¹³ C, and ¹¹⁹ Sn NMR spectroscopy and mass spectrometry. Their solid-state structures and geometric parameters were determined and compared to those of other classes of thiocarbonylthio compounds. These new organotin derivatives are efficient reversible chain-transfer agents for reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) and n-butyl acrylate (BA), with controlled number-average molecular weights and narrow dispersities (Ð<1.3). In some cases, loss of control of the polymerization was evidenced and supported by the observation of side products by ¹¹⁹ Sn NMR spectroscopy. This phenomenon was attributed to the thermal instability of the Sn-RAFT terminal group.

Keywords: NMR spectroscopy; polymerization; polymers; radical reactions; tin.