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• W2016516250 abstract "Komplexe des Vanadium(V) von Typ VO5–nNn (n = 0–2), VO6–nNn (n = 0–3) und VO7–nNn (n = 0–2) mit ein- bis fünfzähnigen, Sauerstoff- und Stickstoff-funktionellen Liganden zeigen chemische Verschiebungen δ(51V) zwischen – 380 und – 750 ppm (relativ zu VOCl3), wobei die höchsten Abschirmungen in Komplexen mit Dreiringstrukturen (Peroxo- und Hydroxyl-amido-Komplexe) erreicht werden. In den Komplexen V★O(OR)- (LL)2 [LL = N-Phenylbenzylhydroxamat(1–), pbha; 8-Hydroxychinolinat(1–), oxin; 3-Hydroxy-2-methyl-4-pyronat(1–), mal] wird in der Reihe R = CH2R′, CH(R′R″), CR′(R″)2 zunehmende Abschirmung beobachtet. die Komplexe werden durch Umsetzung ein- und mehrwertiger, darunter auch cyclischer Alkohole mit [VO(oxin)2]2(μ-O) bzw. VOCl(pbha)2, oder direkt aus Vanadat und den Liganden erhalten. Chirale Alkohole (R★OH) geben Anlaß zu zwei Kernresonanzsignalen für die beiden diastereomeren Enantiomerenpaare. Die Ergebnisse der Untersuchungen in der Reihe VO(OR)(oxin)2 erlauben eine Beurteilung auch der Koordination einiger Nucleoside (R = Inosin, Uridin und 2′- Desoxyuridin). VOCl(pbha)2 kristallisiert in der monoklinen Raumgruppe P21/n mit den folgenden Zellparametern: a = 1184.3, b = 1564.1, c = 1364.4 pm; β = 91.94°. Die Koordinationsgeometrie ist verzerrt oktaedrisch; der V-O-Doppelbindungsabstand ist mit 180.1 pm bemerkenswert lang. Vanadium(V) complexe with OO and ON Ligands as Models for Vanadium Coordination sites in Biomolecules: The Dependence of 51V Shielding on Streric Effects Vanadium(V) complexes of the type VO5–nNn (n = 0–2), VO6–nNn (n = 0–3) und VO7–nNn (n = 0–2) containing mono to pentadentate oxygen and nitrogen ligands exhibit chemical shifts δ(51V) of – 380 to 750 ppm (relative to VOCl3) with the highest shielding found in complexes with 3-membered ring structures (peroxo and hydroxylamido complexes). In the complexes V★O(OR)(LL)2 [LL = N-phenylbenzylhydroxamate(1–), pbha; 8-hydroxychinolate(1–), oxin; 3-hydroxy-2-methyl-4-pyronate (1–), mal], shielding increases in the order CH2R′, CH(R′R″), CR′(R″)2. The compounds were obtained from the reaction of mono- and polyhydric (including cyclic) alcohols with [VO-(oxin)2]2(μ-O) or VOCl(pbha)2, or directly from vanadate and the ligands. Chiral alcohols (R★OH) give rise to two resonance signals corresponding to the two diastereomeric pairs of enantiomers. The findings from the complex series VO(OR)(oxin)2 also allow for the assessment of the mode of coordination of several nucleosides (R = inosine, uridine and 2′-deoxyuridine). VOCl(pbha)2 crystallizes in the monoclinic space group P21/n with the following cell parameters: a = 1184.3, b = 1564.1, c = 1364.4 pm; β = 91.94°. The coordination geometry is distorted octahedral; the VO double bond (180.1 pm) is remarkably long." @default.
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• W2016516250 date "1989-02-01" @default.
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• W2016516250 title "Vanadium(V)‐Komplexe mit OO‐ und ON‐Chelatliganden als Modelle für die Vanadium‐Koordination in Biomolekülen: Die Abhängigkeit der Abschirmung des Kernes ⁵¹ V von sterischen Faktoren" @default.
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• W2016516250 doi "https://doi.org/10.1002/cber.19891220205" @default.
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