Mono- and polynuclear ferrocenylthiosemicarbazones: Synthesis, characterisation and antimicrobial evaluation

Baartzes, Nadia; Stringer, Tameryn; Okombo, John; Seldon, Ronnett; Warner, Digby F.; Kock, Carmen de; Smith, Peter J.; Smith, Gregory S.

doi:10.1016/j.jorganchem.2016.06.032

Cited by 13 publications

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References 46 publications

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“…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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confidence: 99%

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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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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“…Thiosemicarbazons and their metal complexes are studied intensely since the 1950s, mainly for their interesting biological properties. Antitumor, antibacterial, antiviral, and antifungal effects have been reported [1][2][3][4][5][6][7][8][9][10][11]. A general formula for a thiosemicarbazone (Scheme 1A) reveals a chelate NˆS binding pocket for the coordination to metals.…”

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confidence: 99%

[2 × 2] Molecular Grids of Ni(II) and Zn(II) with Redox-Active 1,4-Pyrazine-Bis(thiosemicarbazone) Ligands

et al. 2018

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Tetranuclear complexes [M 4 (L R) 4 ] with M = Ni(II) or Zn(II), with a [2 × 2] grid-type structure, were assembled in good yields and purity from the easily accessible but unprecedented pyrazine-bridged bis(thiosemicarbazone) protoligands (ligand precursors) H 2 L R (1,4-pyrazine-2,5bis(R-carbaldehyde-thiosemicarbazone); R = Me, Et, i Pr, or Ph). The complexes were characterised in solution by NMR, MS, IR, and UV-Vis absorption spectroscopy and (spectro)electrochemical methods. HR-MS spectra unequivocally reveal that the tetranuclear species are very stable in solution and any measurements represent these species. Only at higher temperatures (fragmentation in solution: MS and in the solid: TG-DTA) or upon the addition of protons (acidic UV-Vis titrations) can the tetrameric entities be decomposed. Single crystal XRD measurement remained preliminary. Rapid loss of co-crystallised solvent molecules within the [2 × 2] grid-type structures resulted in crystals of very poor quality, but the results were qualitatively in line with spectroscopy, electrochemistry, and quantum chemical (DFT) calculations. IR and NMR spectroscopy point clearly to a thiolate coordination of dianionic (deprotonated) ligands. The electrochemistry reveals four electronically coupled and reversible one-electron reductions centred largely at the pyrazine bridges. EPR and UV-Vis spectroelectrochemical measurements in combination with DFT calculation support the assignment.

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Tertiary phosphine‐appended transition metal ferrocenyl dithiocarbamates: Syntheses, Hirshfeld surface, and electrochemical analyses

Singh

Dutta

Singh

et al. 2020

Applied Organom Chemis

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Five new heteroleptic complexes of Cu(I), Ag(I), and Ni(II) having formulae [Cu3(dtc)2(dppf)2]PF6 (Cu‐I), [Cu3(dtc)2(dppe)2]PF6 (Cu‐II), [Cu(PPh3)2(dtc)] (Cu‐III), [Ag3(dtc)2(PPh3)2]NO3 (Ag‐I), and [Ni(dtc)(dppf)]PF6 (Ni‐I) (dtc = N‐ethanol‐N‐methylferrocenyl‐dithiocarbamate; dppf = 1,1′‐bis(diphenylphosphino)ferrocene; dppe = 1,1′‐bis(diphenylphosphino)ethane; PPh3 = tripheylphosphine) have been synthesized and characterized using elemental analysis, Fourier‐transform infrared, multinuclear nuclear magnetic resonance, UV–Vis spectroscopy, and single‐crystal X‐ray diffraction. The single‐crystal X‐ray diffraction studies indicate that Ag‐I forms a rare trinuclear cluster in which the geometry around the two silver centers Ag1 and Ag3 is distorted tetrahedral, whereas the third silver center Ag2 shows a distorted trigonal planar geometry. The Ni‐I complex has a distorted square‐planar geometry around the Ni center. In addition, a side product [Ag2{S2(dppf)2}] (Ag‐II) was obtained during an attempt to synthesize [Ag(dppf)(dtc)], where the two Ag centers are bridged by two sulfido centers and coordinated with two phosphorus centers of the dppf ligand to give rise to a distorted tetrahedral geometry. The solid‐state structures of Ag‐I, Ni‐I, and Ag‐II are stabilized by a variety of weak interactions. The nature of these interactions has been addressed with the help of Hirshfeld surface analyses. In addition, the weak argentophilic interaction in Ag‐I and Ag‐II have been studied using quantum theory of atoms in molecules and natural bond orbital calculations. The electrochemical properties of the complexes have been investigated using cyclic voltammetry, where Cu‐I and Cu‐II exhibited two quasi‐reversible waves, whereas Cu‐III, Ag‐I, Ag‐II, and Ni‐I exhibited only one quasi‐reversible peak.

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Mono- and polynuclear ferrocenylthiosemicarbazones: Synthesis, characterisation and antimicrobial evaluation

Cited by 13 publications

References 46 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

[2 × 2] Molecular Grids of Ni(II) and Zn(II) with Redox-Active 1,4-Pyrazine-Bis(thiosemicarbazone) Ligands

Tertiary phosphine‐appended transition metal ferrocenyl dithiocarbamates: Syntheses, Hirshfeld surface, and electrochemical analyses

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