Synthesis, reactivity, electrochemical behaviour, and molecular structure of crown ether cyrhetrene complexes

Godoy, Fernando; Gómez, Alejandra; Agurto, Nicolás; Munoz, M. Asuncion; Segura, Rodrigo; Silva, Carlos P.; Pavez, Jorge; Zagal, José H.; Klahn, A. Hugo; Fuentealba, Mauricio; Ibáñez, Andrés; Garland, Marı́a Teresa

doi:10.1016/j.jorganchem.2015.04.031

Cited by 9 publications

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“…Bond distances and angles along the chain and within the molecule are as expected, and confirm the E-E configuration assigned tentatively by NMR for both chalcone and imine groups. 11,15 Figure 2. Molecular structure of (η 5 -C 5 H 4 C(O)CH=CH-C 6 H 4 CH=N-benzo-15-crown-5)Fe(η 5 -C 5 H 5 ) (4a) drawn with 50% probability displacement ellipsoids.…”

Section: Introductionmentioning

confidence: 99%

“…Hydrogen atoms included as spheres of arbitrary radius. Selected bond lengths (in Å) and bond angle (in deg): C(10)-C(11), 1.459(3); C(11)-C(12), 1.484(2); C(11)-O(1), 1.229(2); C(12)-C(13), 1.325(3); C(20-N(1), 1.272(2); C(9)-C(10)-C(11), 127.14 (15); C(10)-C(11)-C(12), 117.76 (15); O(1)-C(11)-C(10), 121.35 (16); O(1)-C(11)-C(12), 120.87 (17); C(13)-C(12)-C(11), 120.30 (16).…”

Section: Introductionmentioning

confidence: 99%

“…The molecular structures for cyrhetrenyl metallo-ligands (η 5 -C 5 H 4 C(O)CH=CH-benzo-15crown-5)Re(CO) 3 The structures of complexes 2b and 4b are as expected with the Re adopting a three-legged piano-stool geometry coordinated by the three carbonyl ligands and the cyclopentadienyl ligand. 12,15,20,22 The crown ether is attached to the Cp ring via an allyl ester and benzylimine chain. For the case of 2b, the water of crystallization is hydrogen-bonded to the benzo-15crown-5 ring through hydrogen bonds to O4 and O6.…”

Section: Introductionmentioning

confidence: 99%

“…A procedure similar to that described for the synthesis of related organometallic Schiff bases was followed for the preparation of 4a-b. 15,19,20 The reaction mixtures were refluxed for 5 h. After this time, the IR spectra showed the disappearance of the absorption bands corresponding to the starting material and the appearance of new bands from the corresponding imine group ( C=N stretching 1620 cm -1 ). These spectral changes and those reported for the related complexes are in good agreement.…”

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Synthesis and characterization of organometallic chalcones functionalized with a crown ether fragment. Spectroscopic and electrochemical behavior

Agurto

Maldonado

Godoy

et al. 2017

Journal of Organometallic Chemistry

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Organometallic chalcone complexes functionalized with a macrocyclic fragment [( 5 -C 5 H 4 C(O)CH=CH-4-benzo-15-crown-5)MLn] (ferrocenyl, cyrhetrenyl, and cymantrenyl) have been synthesized. The complexes are characterized by IR spectroscopy, 1 H and 13 C NMR spectroscopies, elemental analyses, and HR-MS. The stereochemistry for the chalcone compounds was determined using the 1 H and 13 C NMR spectroscopy data, which indicated that they are isolated as a single isomer (E). In addition, the syntheses of the chalcone-imine derivatives are described, and they adopt an anti-(E,E) conformation in solution, confirmed by the X-ray crystal structures in the solid state. The UV-Visible and electrochemical behavior of the organometallic complexes are reported. Keywords: Organometallic chalcone and imine complexes, crown ether, crystal structures. examples of their application as chemosensors. Delavaux-Nicot et al. have investigated a series of ferrocenyl chalcones, mono and 1,1'-disubstituted, functionalized with an amine moiety or an aza-macrocycle. 13 These metallo-ligands have shown selectivity toward Ca 2+ and Ba 2+ in acetonitrile. Another important class of functionalized rhenium(I) complexes with aza-crown ether pendants, synthetized by Yam et al., exhibit a high specificity towardPb(II). 14 Previously, our research group reported the synthesis of new cyrhetrenyl tricarbonyl complexes functionalized with 4'-benzo-crown or 2-methyl-crown ether fragments, bridged by an imine linker. The cyclic voltammograms showed positive anodic waves arising from the Re(II)/Re(I) redox process (I). It was concluded that the size of the crown ether did not change the anodic potential significantly. Nevertheless, the metal centered redox processes of complexes that possess a methylene moiety were shifted to positive potentials compared to a benzo group. 15 In this work, we report the synthesis, X-ray structures and electrochemical and spectroscopic behaviour of new ferrocenyl, cyrhetrenyl and cymantrenyl complexes functionalized with 4'-benzo-15-crown-5 fragment. In addition we have included the synthesis of related species with a chalcone-imine as linker.2. Results and discussion. Synthesis of the organometallic chalcones 2-3.The compounds were synthesized following a procedure similar to that described for ferrocenyl and cymantrenyl chalcone derivatives. 11,16 It is based on the Claisen-Schmidt reaction involving the condensation of the organometallic ketones 1a-c and the corresponding crown ether or organic aldehydes Id-e (Scheme 1). Derivatives 2a-c and 3awere obtained by reaction of the corresponding precursors in the presence of NaOH and were dissolved in water/ethanol mixed solvent for greater solubility of the components. A modification of the experimental procedure was used for the preparation of the cyrhetrenyl derivative 3b. The carbanion containing solution was added dropwise to an ethanolic solution of terephthalaldehyde (Ie) over a period of 2 h. in order to control the proportion of nucleophile generated. The genera...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Synthesis and characterization of organometallic chalcones functionalized with a crown ether fragment. Spectroscopic and electrochemical behavior

Agurto

Maldonado

Godoy

et al. 2017

Journal of Organometallic Chemistry

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“…Our research group has reported the synthesis and electrochemical behavior of cyrhetrenyl tricarbonyl complexes functionalized with 4′‐benzo‐crown or 2′‐methyl‐crown ether fragments, bridged by an imine link . These metalloligands were designed for sodium and potassium recognition.…”

Section: Introductionmentioning

confidence: 99%

Novel organometallic chalcones functionalized with a crown ether fragment as optical ion chemosensors

Godoy

Maldonado

Flores

et al. 2017

Applied Organom Chemis

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We previously reported the synthesis and characterization of new organometallic chalcones derived from ferrocene, cyrhetrene and cymantrene functionalized with a benzo‐15‐crown‐5 fragment. The ferrocene and cyrhetrene chalcones have been investigated as chemosensors for metal ions with optical response in acetonitrile. Several metal ions were selected considering the diameter of the cavity and the charge‐to‐radius ratio of the cation. The stoichiometry of the complexes was determined using Job's method. It was found that Na+ and Ca2+ complexes have a 1:1 stoichiometry while a 2:1 (metaloligand‐to‐cation) stoichiometry was determined for Ba2+ and Pb2+ complexes. The association constants were calculated according to the stoichiometry of the complex and the results showed that they are directly affected by the electron‐withdrawing nature of the organometallic fragment. Moreover, complexes of ferrocenyl chalcone have larger association constants than those of the cyrhetrenyl analogue. This experimental observation is consistent with the electronic properties of the ferrocenyl fragment.

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Molecular recognition: Evidence of the redox role of ferrocenyl-imine derivatives in the presence of copper (II) ions

Agurto

Silva

Jara

et al. 2019

Electrochimica Acta

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Synthesis, reactivity, electrochemical behaviour, and molecular structure of crown ether cyrhetrene complexes

Cited by 9 publications

References 49 publications

Synthesis and characterization of organometallic chalcones functionalized with a crown ether fragment. Spectroscopic and electrochemical behavior

Synthesis and characterization of organometallic chalcones functionalized with a crown ether fragment. Spectroscopic and electrochemical behavior

Novel organometallic chalcones functionalized with a crown ether fragment as optical ion chemosensors

Molecular recognition: Evidence of the redox role of ferrocenyl-imine derivatives in the presence of copper (II) ions

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