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Computational Investigation of the Aminolysis of RAFT Macromolecules

Gilles Desmet (UGent) , Dagmar D'hooge (UGent) , Maarten Sabbe (UGent) , Marie-Françoise Reyniers (UGent) and Guy Marin (UGent)
(2016) JOURNAL OF ORGANIC CHEMISTRY. 81(23). p.11626-11634
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Abstract
This work presents a detailed computational study and kinetic analysis of the aminolysis of dithioates, dithiobenzoates, trithiocarbonates, xanthates, and thiocarbamates, which are frequently used as chain-transfer agents for reversible addition fragmentation chain-transfer (RAFT) polymerization. Rate coefficients were obtained from ab initio calculations, taking into account a diffusional contribution according to the encounter pair model. A kinetic model was constructed and reveals a reaction mechanism of four elementary steps: (i) formation of a zwitterionic intermediate, (ii) formation of a complex intermediate in which an assisting amine molecule takes over the proton from the zwitterionic intermediate, (iii) breakdown of the complex into a neutral tetrahedral intermediate with release of the assisting amine molecule, and (iv) amine-assisted breakdown of the neutral intermediate to the products. Furthermore, a comparative analysis indicates that the alkanedithioates and dithiobenzoates react the fastest, followed, respectively, by xanthates and trithiocarbonates, which react almost equally fast, and dithiocarbamates, which are not reactive at typical experimentally used conditions.
Keywords
ZWITTERIONIC TETRAHEDRAL INTERMEDIATE, FRAGMENTATION CHAIN TRANSFER, FREE-RADICAL POLYMERIZATION, ADDITION-FRAGMENTATION, CLICK CHEMISTRY, FUNCTIONAL POLYMERS, END-GROUPS, THIOL, KINETICS, STABILITY

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Chicago
Desmet, Gilles, Dagmar D’hooge, Maarten Sabbe, Marie-Françoise Reyniers, and Guy Marin. 2016. “Computational Investigation of the Aminolysis of RAFT Macromolecules.” Journal of Organic Chemistry 81 (23): 11626–11634.
APA
Desmet, G., D’hooge, D., Sabbe, M., Reyniers, M.-F., & Marin, G. (2016). Computational Investigation of the Aminolysis of RAFT Macromolecules. JOURNAL OF ORGANIC CHEMISTRY, 81(23), 11626–11634.
Vancouver
1.
Desmet G, D’hooge D, Sabbe M, Reyniers M-F, Marin G. Computational Investigation of the Aminolysis of RAFT Macromolecules. JOURNAL OF ORGANIC CHEMISTRY. American Chemical Society (ACS); 2016;81(23):11626–34.
MLA
Desmet, Gilles et al. “Computational Investigation of the Aminolysis of RAFT Macromolecules.” JOURNAL OF ORGANIC CHEMISTRY 81.23 (2016): 11626–11634. Print.
@article{8507481,
  abstract     = {This work presents a detailed computational study and kinetic analysis of the aminolysis of dithioates, dithiobenzoates, trithiocarbonates, xanthates, and thiocarbamates, which are frequently used as chain-transfer agents for reversible addition fragmentation chain-transfer (RAFT) polymerization. Rate coefficients were obtained from ab initio calculations, taking into account a diffusional contribution according to the encounter pair model. A kinetic model was constructed and reveals a reaction mechanism of four elementary steps: (i) formation of a zwitterionic intermediate, (ii) formation of a complex intermediate in which an assisting amine molecule takes over the proton from the zwitterionic intermediate, (iii) breakdown of the complex into a neutral tetrahedral intermediate with release of the assisting amine molecule, and (iv) amine-assisted breakdown of the neutral intermediate to the products. Furthermore, a comparative analysis indicates that the alkanedithioates and dithiobenzoates react the fastest, followed, respectively, by xanthates and trithiocarbonates, which react almost equally fast, and dithiocarbamates, which are not reactive at typical experimentally used conditions.},
  author       = {Desmet, Gilles and D'hooge, Dagmar and Sabbe, Maarten and Reyniers, Marie-Françoise and Marin, Guy},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  keywords     = {ZWITTERIONIC TETRAHEDRAL INTERMEDIATE,FRAGMENTATION CHAIN TRANSFER,FREE-RADICAL POLYMERIZATION,ADDITION-FRAGMENTATION,CLICK CHEMISTRY,FUNCTIONAL POLYMERS,END-GROUPS,THIOL,KINETICS,STABILITY},
  language     = {eng},
  number       = {23},
  pages        = {11626--11634},
  publisher    = {American Chemical Society (ACS)},
  title        = {Computational Investigation of the Aminolysis of RAFT Macromolecules},
  url          = {http://dx.doi.org/10.1021/acs.joc.6b01844},
  volume       = {81},
  year         = {2016},
}

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