Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution |
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Authors: | A Carel N Kwamen Marcel Schlottmann Dr David Van Craen Dr Elisabeth Isaak Julia Baums Li Shen Ali Massomi Dr Christoph Räuber Benjamin P Joseph Prof Dr Gerhard Raabe Dr Christian Göb Prof Dr Iris M Oppel Dr Rakesh Puttreddy Dr Jas S Ward Prof Dr Kari Rissanen Dr Roland Fröhlich Prof Dr Markus Albrecht |
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Institution: | 1. Institut für Organische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany;2. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany;3. University of Jyväskylä, Department of Chemistry, P.O. Box 35, Jyväskylä, 40014 Finland;4. Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149 Münster, Germany |
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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. For example, 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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Keywords: | coordination compounds helicate solvent effects thermodynamics weak interactions |
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