Shedding light on the interaction of hydrocarbon ester substituents upon formation of dimeric titanium(IV) triscatecholates in DMSO solution
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
Published inChemistry : A European Journal
Shen, Li |
© 2019 The Authors
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. ...
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Related funder(s)Academy of Finland
Funding program(s)Postdoctoral Researcher, AoF
Additional information about fundingWe are grateful for funding by the international graduate school Seleca (Deutsche Forschungsgemeinschaft) and for financial support from the Academy of Finland (RP: grant no. 298817) and the University of Jyväskylä.
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