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- W2005688631 abstract "While each of the three organosamarium(III) title complexes: [Cp 2 Sm{μ-OC 10 H 19 }] 2 ( 5 ; Cp = C 5 H 5 , OC 10 H 19 = isomenthoxide), [Cp 2 Sm{μ-OCH(Me)COO i BU}] 2 ( 6 ) and [Cp 3 SmOS(Me)- p -C 6 H 4 Me] ( 7 ) contains a chiral ligand atom (i.e. C or S) next to the metal-bonded oxygen atoms, only the dinuclear compounds 5 and, even better, 6 display (below ca. 600 nm) significant circular dichroism of discrete ff-crystal field transitions. According to a successful single-crystal X-ray study of 5 , the cyclohexyl ring of its (1S,2R,5R)-isomenthoxide ligand adopts a conformation with axial OSm- and i Pr-substituents, which is energetically less favourable at least for neat (1S,2R,5R)-isomenthol. Obwohl jeder der drei neuen Organosamarium(III)-Komplexe: [Cp 2 Sm{μ-OC 10 OH 19 }] 2 ( 5 ; Cp = C 5 H 5 , OC 10 H 19 = Isomentholat), [Cp 2 Sm{μ-OCH(Me)COO i BU}] 2 ( 6 ) und [Cp 3 SmOS(Me)- p -C 6 H 4 Me] mindestens ein chirales Ligandenatom (C oder S) unmittelbar am metallkoordinierten O-Atom enthält, zeigen nur die dimeren Systeme 5 und noch ausgeprägter 6 (unterhalb von ca. 600 nm) signifikanten Circulardichroismus von ff-Kristallfeldübergängen des Sm 3+ -Ions. Auf Grund einer erfolgreichen Kristallstrukturanalyse von 5 liegt der Cyclohexylring des (1S,2R,5R)-Isomentholatliganden ausschließlich in der Konformation mit axialen OSm- und i Pr-Substituenten vor, die für freies (1S,2R,5R)-Isomenthol energetisch deutlich unvorteilhafter ist." @default.
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- W2005688631 date "1996-03-01" @default.
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- W2005688631 title "Chiroptische effekte von lanthanoidorganylen mit optisch aktiven liganden III. Erschließung wohldefinierter chiraler organosamarium(III)-verbindungen durch umsetzung von tris(cyclopentadienyl)samarium mit (1S,2R,5R)-Isomenthol, (R)-(+)-Isobutyllactat und (R)-(+)-Methyl-p-tolylsulfoxid" @default.
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- W2005688631 doi "https://doi.org/10.1016/0022-328x(95)05922-c" @default.
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