FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W1978802132> ?p ?o ?g. }

• W1978802132 endingPage "527" @default.
• W1978802132 startingPage "520" @default.
• W1978802132 abstract "Abstract The diastereomeric hemicryptophane oxidovanadium(V) complexes ( P )‐( S , S , S )‐ 3 and ( M )‐( S , S , S )‐ 4 have been synthesized. 1 H and 51 V NMR spectra in solution are consistent with the formation of Λ and Δ forms of the propeller‐like vanatrane moiety, leading to two diastereomeric conformers for each complex: that is, ( P )‐( S , S , S‐ Λ)‐ 3 /( P )‐( S , S , S‐ Δ)‐ 3 and ( M )‐( S , S , S‐ Λ)‐ 4 /( M )‐( S , S , S‐ Δ)‐ 4 . The Λ/Δ ratio is rather temperature‐insensitive but strongly dependent on the solvent (the de of ( M )‐( S , S , S )‐ 4 changes from 0 in benzene to 92 % in DMSO). The solvent therefore controls the preferential clockwise or anticlockwise orientation of the propeller‐like atrane unit. The energy barriers for the Λ⇄Δ equilibrium were determined by NMR experiments, and the highest Δ G ≠ value (103.7 kJ mol −1 ) was obtained for ( P )‐( S , S , S )‐ 3 , much higher than those reported for other atrane derivatives. This is attributed to the constraints arising from the cage structure. Determination of the activation parameters provides evidence for a concerted, rather than a stepwise, interconversion mechanism with entropies (Δ S ≠ ) of −243 and −272 J mol −1 K −1 for ( P )‐( S , S , S )‐ 3 and ( M )‐( S , S , S )‐ 4 , respectively. The molecular structure of the ( P )‐( S , S , S‐ Λ)‐ 3 isomer was solved by X‐ray diffraction and shows a distorted structure with one of the linkers located in the CTV cavity. Complementary quantum chemical calculations were carried out to obtain the energy‐minimized structures of ( P )‐( S , S , S )‐ 3 and ( M )‐( S , S , S )‐ 4 . Our density functional theory calculations suggest that the ( P )‐( S , S , S‐ Λ)‐ 3 is favored, in agreement with experimental data. For the M series, a similar strategy was used to extract molecular structures and relative energies. As in the case of the P diastereomer, the Λ form dominates over the Δ one." @default.
• W1978802132 created "2016-06-24" @default.
• W1978802132 creator A5003469584 @default.
• W1978802132 creator A5010669990 @default.
• W1978802132 creator A5012399595 @default.
• W1978802132 creator A5049779217 @default.
• W1978802132 date "2009-12-28" @default.
• W1978802132 modified "2023-10-18" @default.
• W1978802132 title "Controlling Helical Chirality in Atrane Structures: Solvent-Dependent Chirality Sense in Hemicryptophane-Oxidovanadium(V) Complexes" @default.
• W1978802132 cites W1970520894 @default.
• W1978802132 cites W1974482729 @default.
• W1978802132 cites W1978420545 @default.
• W1978802132 cites W1982500281 @default.
• W1978802132 cites W1984589370 @default.
• W1978802132 cites W1988343763 @default.
• W1978802132 cites W1996677239 @default.
• W1978802132 cites W1998078687 @default.
• W1978802132 cites W2005986993 @default.
• W1978802132 cites W2015073980 @default.
• W1978802132 cites W2018512226 @default.
• W1978802132 cites W2027369193 @default.
• W1978802132 cites W2030379812 @default.
• W1978802132 cites W2031182997 @default.
• W1978802132 cites W2032267556 @default.
• W1978802132 cites W2035814331 @default.
• W1978802132 cites W2037834729 @default.
• W1978802132 cites W2039960199 @default.
• W1978802132 cites W2041697043 @default.
• W1978802132 cites W2046015418 @default.
• W1978802132 cites W2047554793 @default.
• W1978802132 cites W2055090447 @default.
• W1978802132 cites W2059549391 @default.
• W1978802132 cites W2064583767 @default.
• W1978802132 cites W2067162104 @default.
• W1978802132 cites W2069300781 @default.
• W1978802132 cites W2080149984 @default.
• W1978802132 cites W2082783972 @default.
• W1978802132 cites W2084003905 @default.
• W1978802132 cites W2089277691 @default.
• W1978802132 cites W2095349748 @default.
• W1978802132 cites W2122102685 @default.
• W1978802132 cites W2124817352 @default.
• W1978802132 cites W2128179591 @default.
• W1978802132 cites W2134149462 @default.
• W1978802132 cites W2146221474 @default.
• W1978802132 cites W2148066840 @default.
• W1978802132 cites W2171738893 @default.
• W1978802132 cites W2952179347 @default.
• W1978802132 cites W2952328950 @default.
• W1978802132 cites W2952650369 @default.
• W1978802132 cites W340877871 @default.
• W1978802132 cites W4214665292 @default.
• W1978802132 cites W82558385 @default.
• W1978802132 doi "https://doi.org/10.1002/chem.200901976" @default.
• W1978802132 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19918819" @default.
• W1978802132 hasPublicationYear "2009" @default.
• W1978802132 type Work @default.
• W1978802132 sameAs 1978802132 @default.
• W1978802132 citedByCount "44" @default.
• W1978802132 countsByYear W19788021322012 @default.
• W1978802132 countsByYear W19788021322013 @default.
• W1978802132 countsByYear W19788021322014 @default.
• W1978802132 countsByYear W19788021322015 @default.
• W1978802132 countsByYear W19788021322016 @default.
• W1978802132 countsByYear W19788021322017 @default.
• W1978802132 countsByYear W19788021322019 @default.
• W1978802132 countsByYear W19788021322020 @default.
• W1978802132 countsByYear W19788021322021 @default.
• W1978802132 countsByYear W19788021322022 @default.
• W1978802132 crossrefType "journal-article" @default.
• W1978802132 hasAuthorship W1978802132A5003469584 @default.
• W1978802132 hasAuthorship W1978802132A5010669990 @default.
• W1978802132 hasAuthorship W1978802132A5012399595 @default.
• W1978802132 hasAuthorship W1978802132A5049779217 @default.
• W1978802132 hasConcept C103319777 @default.
• W1978802132 hasConcept C121332964 @default.
• W1978802132 hasConcept C124668440 @default.
• W1978802132 hasConcept C1276947 @default.
• W1978802132 hasConcept C138716334 @default.
• W1978802132 hasConcept C178790620 @default.
• W1978802132 hasConcept C185592680 @default.
• W1978802132 hasConcept C18705241 @default.
• W1978802132 hasConcept C20621625 @default.
• W1978802132 hasConcept C2776568683 @default.
• W1978802132 hasConcept C2778564446 @default.
• W1978802132 hasConcept C2780471494 @default.
• W1978802132 hasConcept C32909587 @default.
• W1978802132 hasConcept C4839761 @default.
• W1978802132 hasConcept C62520636 @default.
• W1978802132 hasConcept C67787023 @default.
• W1978802132 hasConcept C71240020 @default.
• W1978802132 hasConcept C7602139 @default.
• W1978802132 hasConcept C8010536 @default.
• W1978802132 hasConceptScore W1978802132C103319777 @default.
• W1978802132 hasConceptScore W1978802132C121332964 @default.
• W1978802132 hasConceptScore W1978802132C124668440 @default.
• W1978802132 hasConceptScore W1978802132C1276947 @default.
• W1978802132 hasConceptScore W1978802132C138716334 @default.

• next