Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility

T. Rösener, A. Hoffmann, S. Herres-Pawlis, European Journal of Inorganic Chemistry 2018 (2018) 3164–3175.

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Abstract
Ligands DMEG6etqu, TMG6etqu, DMEG6buqu, and TMG6buqu were developed on the basis of guanidine quinoline (GUAqu) ligands 1,3-dimethyl-N-(quinolin-8-yl)imidazolidin-2-imine (DMEGqu) and 1,1,3,3-tetramethyl-2-(quinolin-8-yl)guanidine (TMGqu). These ligands feature an alkyl substituent at the C6 of the quinoline backbone. The synthetic strategy developed here enables inexpensive syntheses of any kind of C6-substituted GUAqu ligands. On one hand, the alkylation increases the solubility of corresponding copper complexes in apolar atom transfer radical polymerization (ATRP) monomers like styrene. On the other hand, it has a significant electronic influence and thus an effect on the donor properties of the new ligands. Seven CuI and CuII complexes of DMEG6etqu and TMG6etqu have been crystallized and were studied with regard to their structural and electrochemical properties. CuI and CuII complexes of DMEG6buqu and TMG6buqu turned out to be perfectly soluble in pure styrene even at room temperature, which makes them excellent catalysts in the ATRP of apolar monomers. The key characteristics of the ATRP equilibrium, KATRP and kact, were determined for the new complexes. In addition, we used our recently developed DFT methodology, NBO analysis, and isodesmic reactions to predict the influence of the introduced alkyl substituents. It turned out that high conformational freedom in the complex structures leads to a significant uncertainty in prediction of the thermodynamic properties.
Publishing Year
Journal Title
European Journal of Inorganic Chemistry
Volume
2018
Issue
27
Page
3164-3175
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Rösener T, Hoffmann A, Herres-Pawlis S. Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility. European Journal of Inorganic Chemistry. 2018;2018(27):3164-3175. doi:10.1002/ejic.201800511
Rösener, T., Hoffmann, A., & Herres-Pawlis, S. (2018). Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility. European Journal of Inorganic Chemistry, 2018(27), 3164–3175. https://doi.org/10.1002/ejic.201800511
@article{Rösener_Hoffmann_Herres-Pawlis_2018, title={Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility}, volume={2018}, DOI={10.1002/ejic.201800511}, number={27}, journal={European Journal of Inorganic Chemistry}, author={Rösener, Thomas and Hoffmann, Alexander and Herres-Pawlis, Sonja}, year={2018}, pages={3164–3175} }
Rösener, Thomas, Alexander Hoffmann, and Sonja Herres-Pawlis. “Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility.” European Journal of Inorganic Chemistry 2018, no. 27 (2018): 3164–75. https://doi.org/10.1002/ejic.201800511.
T. Rösener, A. Hoffmann, and S. Herres-Pawlis, “Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility,” European Journal of Inorganic Chemistry, vol. 2018, no. 27, pp. 3164–3175, 2018.
Rösener, Thomas, et al. “Next Generation of Guanidine Quinoline Copper Complexes for Highly Controlled ATRP: Influence of Backbone Substitution on Redox Chemistry and Solubility.” European Journal of Inorganic Chemistry, vol. 2018, no. 27, 2018, pp. 3164–75, doi:10.1002/ejic.201800511.

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