A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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-tekijät tai -toimittajat
Julkaisun tiedot
Julkaisun kaikki tekijät tai toimittajat: Kwamen, Carel; Schlottmann, Marcel; VanCraen, David; Isaak, Elisabeth; Baums, Julia; Shen, Li; Massomi, Ali; Räuber, Christoph; Joseph, Benjamin; Raabe, Gerhard; et al.
Lehti tai sarja: Chemistry : A European Journal
ISSN: 0947-6539
eISSN: 1521-3765
Julkaisuvuosi: 2020
Volyymi: 26
Lehden numero: 6
Artikkelin sivunumerot: 1396-1405
Kustantaja: Wiley
Julkaisumaa: Saksa
Julkaisun kieli: englanti
DOI: https://doi.org/10.1002/chem.201904639
Julkaisun avoin saatavuus: Avoimesti saatavilla
Julkaisukanavan avoin saatavuus: Osittain avoin julkaisukanava
Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/66470
Tiivistelmä
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.
YSO-asiasanat: kompleksiyhdisteet; esterit; termodynamiikka
Vapaat asiasanat: coordination compounds; helicate thermodynamics; weak interactions; solvent effects
Liittyvät organisaatiot
Hankkeet, joissa julkaisu on tehty
- Halogeenisidos: vahva ja luotettava vaihtoehto koordinaatiosidokselle.
- Puttreddy, Rakesh
- Suomen Akatemia
OKM-raportointi: Kyllä
Raportointivuosi: 2020
JUFO-taso: 2