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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F16%3A39901717" target="_blank" >RIV/00216275:25310/16:39901717 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/ejic.201601029" target="_blank" >http://dx.doi.org/10.1002/ejic.201601029</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejic.201601029" target="_blank" >10.1002/ejic.201601029</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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 ?5:?N-compound, whereas the indenyl analogue produced a hexacoordinate species with the unprecedented ?3:?N-coordination mode of the indenyl ligand and thus represents an unusual example of the so-called indenyl effect. The unusually high stability of the ?3:?N-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 ?3 to ?5 rearrangement. As a result, the low hapticity was effectively locked.

Název v anglickém jazyce

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

Popis výsledku anglicky

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 ?5:?N-compound, whereas the indenyl analogue produced a hexacoordinate species with the unprecedented ?3:?N-coordination mode of the indenyl ligand and thus represents an unusual example of the so-called indenyl effect. The unusually high stability of the ?3:?N-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 ?3 to ?5 rearrangement. As a result, the low hapticity was effectively locked.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

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Projekt

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Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

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Svazek periodika

Neuveden

Číslo periodika v rámci svazku

33

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

15

Strana od-do

5250-5264

Kód UT WoS článku

000388494000010

EID výsledku v databázi Scopus

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