A1 Journal article (refereed)
Shedding light on the interaction of hydrocarbon ester substituents upon formation of dimeric titanium(IV) triscatecholates in DMSO solution (2020)
Kwamen, C., Schlottmann, M., VanCraen, D., Isaak, E., Baums, J., Shen, L., Massomi, A., Räuber, C., Joseph, B., Raabe, G., Göb, C., Oppel, I., Puttreddy, R., Ward, J., Rissanen, K., Fröhlich, R., & Albrecht, M. (2020). Shedding light on the interaction of hydrocarbon ester substituents upon formation of dimeric titanium(IV) triscatecholates in DMSO solution. Chemistry : A European Journal, 26(6), 1396-1405. https://doi.org/10.1002/chem.201904639
JYU authors or editors
Publication details
All authors or editors: Kwamen, Carel; Schlottmann, Marcel; VanCraen, David; Isaak, Elisabeth; Baums, Julia; Shen, Li; Massomi, Ali; Räuber, Christoph; Joseph, Benjamin; Raabe, Gerhard; et al.
Journal or series: Chemistry : A European Journal
ISSN: 0947-6539
eISSN: 1521-3765
Publication year: 2020
Volume: 26
Issue number: 6
Pages range: 1396-1405
Publisher: Wiley
Publication country: Germany
Publication language: English
DOI: https://doi.org/10.1002/chem.201904639
Publication open access: Openly available
Publication channel open access: Partially open access channel
Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/66470
Abstract
The dissociation of hierarchically formed dimeric triple‐lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The 1H NMR dimerization constants for the monomer/dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. E.g., the dimer is destabilized by internal double or triple bonds due to π−π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n‐alkyls, n‐Ω‐alkenyls or n‐Ω‐alkynyls. This corresponds to the interaction of the parent hydrocarbons as documented by an even/odd melting point alternation.
Keywords: coordination complexes; esters; thermodynamics
Free keywords: coordination compounds; helicate thermodynamics; weak interactions; solvent effects
Contributing organizations
Related projects
- Halogen bond: A strong and reliable alternative to coordination bond.
- Puttreddy, Rakesh
- Research Council of Finland
Ministry reporting: Yes
Reporting Year: 2020
JUFO rating: 2