Naslov
Disorder at the Chiral Cα Center and Room- Temperature Solid-State cis–trans Isomerization ; Synthesis and Structural Characterization of Copper(II) Complexes with D-allo, L-Isoleucine

Autori
Pejić, Jelena ; Vušak, Darko ; Szalontai, Gábor ; Prugovečki, Biserka ; Mrvoš-Sermek, Draginja ; Matković-Čalogović, Dubravka ; Sabolović, Jasmina

Izvornik
Crystal growth & design (1528-7483) 18 (2018), 9; 5138-5154

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
copper(II) complexes ; isoleucine ; solid-state transformations ; disorder at chiral atom, isomerism, X-ray diffraction ; NMR spectroscopy ; density functional calculation

Sažetak
Four new complexes of copper(II) with D-allo, L- isoleucine were prepared by solution and mechanochemical synthesis: three complexes of aqua cis isomers, cis-[Cu(D-allo-Ile)2(H2O)] (2), cis-[Cu(D-allo-Ile)(L-Ile)(H2O)]0.7[Cu(L- Ile)2(H2O)]0.3 (3), cis-[Cu(D-allo- Ile)2(H2O)]0.75[Cu(D-allo-Ile)(L-Ile)(H2O)]0.25 (4), and anhydrous trans-[Cu(D-allo-Ile)(L-Ile)] (5). The previously characterized orthorhombic cis-[Cu(L-Ile)2(H2O)] (1a) cocrystallized with 3 and either 2 or 4, depending on the synthetic conditions. In 2, a disorder of the side chain was found, while 3 and 4 had a rare positional disorder of two diastereomers, namely, D-allo- Ile and L-Ile, resulting in two positions of the Cα chiral center in their crystal structures. The complexes were analyzed by X-ray diffraction methods, solid-state NMR spectroscopy, and density functional theory calculated 13C and 1H Fermi contact shifts. Room-temperature solid- state cis-to-trans isomerization of Cu(D-allo- Ile)(L-Ile) occurred by liquid-assisted grinding (LAG) of 3 with methanol, by aging in methanol vapor, and by soaking 3 in methanol. The latter was a fast process. The isomerization also happened in the 140–160 °C temperature interval. Reverse trans-to-cis isomerization occurred by LAG of 5 with water and very slowly by aging in water vapor. Low activation energy for the Cu(D- allo-Ile)(L-Ile) cis–trans isomerization in the solid state could explain why subtle changes in the experimental conditions affected the final product.

Izvorni jezik
Engleski

Znanstvena područja
Fizika, Kemija

POVEZANOST RADA