Indenyl Compounds with Constrained Hapticity: The Effect of Strong Intramolecular Coordination

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dc.contributor.author Mrózek, Ondřej cze
dc.contributor.author Vinklárek, Jaromír cze
dc.contributor.author Růžičková, Zdeňka cze
dc.contributor.author Honzíček, Jan cze
dc.date.accessioned 2017-05-11T11:11:44Z
dc.date.available 2017-05-11T11:11:44Z
dc.date.issued 2016 eng
dc.identifier.issn 1434-1948 eng
dc.identifier.uri http://hdl.handle.net/10195/67606
dc.description.abstract A series of cyclopentadienyl and indenyl molybdenum(II) compounds with intramolecularly coordinated pyridine arms, including scorpionate-like species bearing two irreversibly coordinated arms on the indenyl core, were synthesized and characterized. All presented structural types were confirmed by X-ray diffraction analysis. Owing to the strong nucleophilicity of pyridine, the intramolecular interaction was found to be considerably stronger than that in analogous species bearing tertiary amines in the side chain. Although the starting compounds for the syntheses were isostructural, the reaction outcomes differed considerably. The cyclopentadienyl precursor gave a pentacoordinate η5:κN-compound, whereas the indenyl analogue produced a hexacoordinate species with the unprecedented η3:κN-coordination mode of the indenyl ligand and thus represents an unusual example of the so-called indenyl effect. The unusually high stability of the η3:κN-coordination compounds toward haptotropic rearrangement was clarified by theoretical calculations. As the strong intramolecular interaction prevented rotation of the indenyl moiety, it could not reach the conformation suitable for the η3 to η5 rearrangement. As a result, the low hapticity was effectively locked. eng
dc.format p. 5250-5264 eng
dc.language.iso eng eng
dc.relation.ispartof European Journal of Inorganic Chemistry, volume Neuveden, issue: 33 eng
dc.rights open access eng
dc.subject molybdenum eng
dc.subject hapticity eng
dc.subject indenyl eng
dc.subject molybden cze
dc.subject hapticita cze
dc.subject indenyl cze
dc.title Indenyl Compounds with Constrained Hapticity: The Effect of Strong Intramolecular Coordination eng
dc.title.alternative Indenylové sloučeniny s blokovanou hapticitou. Vliv silné intramolekulární interakce cze
dc.type article eng
dc.description.abstract-translated Cyklopentadienylové a indenylové komplexy molybdenu s intramolekulárně coordinovaným pyridinem byly připraveny a charakterizovány spektroskopickými metodami. Strukturní typy, uvedené v této studii, byly potvrzeny RTG difrakční analýzou. Silná nukleofilicita pyridinu způsobuje silnou intramolekulární interakci postranního řetězce. Tato práce popisuje především nové η5:κN cyklopentadienylové a η3:κN indenylové komplexy. Silní intramolekulární interakce v těchto komplexech zabraňuje haptotropnímu přesmyku, který byl dříve podrobně popsán u analogů s nesubstituovaným indenylovým ligandem. cze
dc.peerreviewed yes eng
dc.publicationstatus postprint eng
dc.identifier.doi 10.1002/ejic.201601029
dc.identifier.wos 000388494000010
dc.identifier.scopus 2-s2.0-84991666504
dc.identifier.obd 39877401 eng


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