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- W656261623 abstract "The titled Rh(η4-cod)-enantiopure aminocarboxylate complexes, [Rh(η4-cod) (AA)] {cod = cycloocta-1,5-diene; AA = L-prolinato (1) and D-4-hydroxy-phenylglycinato (2)}, are synthesized from the reaction of enantiopure aminocarboxylate with [Rh(η4-cod) (acetate)]2. Polarimetric measurements confirm the enantiopurity or very similar enantiomeric excess of the complexes in chloroform. Electronic spectra in different solvents exhibit a negative solvatochromism in the solvents of increasing polarity or acceptor number. DSC analyses show an exothermic peak at 269 °C (ΔH = −72.42 kJ M−1) for 2, corresponding to an irreversible phase transformation. Cyclic voltammograms reveal a quasi-reversible one electron transfer for [Rh(η4-cod) (l-prolinate)]/[Rh(η4-cod) (l-prolinate)]+ couple in acetonitrile. Electronic spectra calculated by TDDFT reveal the bands at relatively lower energy (>230 nm) due to combined d–d, MLCT and LLCT transitions, while the bands at higher energy only for LLCT, which are very similar to the experimental results. X-ray structure demonstrates a distorted square-planar geometry with N,O-chelation of the l-prolinate ligand to the Rh(η4-cod)-fragment in 1. The crystal packing is evidenced by charge-assisted intermolecular N–H···O and C–H···O interactions to the non-coordinated carboxylate oxygen atom. Hydrogen bonding leads to the formation of supramolecular chains along the a direction of the unit cell. The interchain packing is governed mostly by van-der-Waals forces and reminiscent of a 'herring-bone' packing." @default.
- W656261623 created "2016-06-24" @default.
- W656261623 creator A5017677891 @default.
- W656261623 creator A5026995371 @default.
- W656261623 creator A5078721934 @default.
- W656261623 creator A5090644272 @default.
- W656261623 date "2015-11-01" @default.
- W656261623 modified "2023-10-16" @default.
- W656261623 title "Syntheses, spectroscopy, X-ray and DFT/TDDFT investigations of Rh(η4-cod)-enantiopure aminocarboxylate complexes" @default.
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- W656261623 doi "https://doi.org/10.1016/j.molstruc.2015.06.040" @default.
- W656261623 hasPublicationYear "2015" @default.
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