A Case Study of Supramolecular Organization: One Ferrocene Substituted Iminodiacetamide and its Chloroform Solvate

Juraj, Natalija Pantalon; Pennec, Jeremy Le; Perić, Berislav; Kirin, Srećko I.

doi:10.5562/cca3270

Cited by 4 publications

(7 citation statements)

References 21 publications

(27 reference statements)

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“…However, a single-crystal structure of L2 was determined (Figure S3). In the solid state, ligand L2 features intramolecular hydrogen bonding, forming an eight-membered ring [graph set notation S(8)], also described in the literature for other imda ligands. , In the crystal structure of L2 , intermolecular hydrogen bonds contribute to the formation of two-dimensional layers.…”

Section: Resultsmentioning

confidence: 99%

Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands

et al. 2019

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Metal complexes of iminodiacetamide (imda) ligands and metal ions Zn(II), Cu(II), Ni(II) and Co(II) were prepared, using eight imda ligands (L1-L8) substituted with groups of different steric and electronic properties on the central amine nitrogen atom (hydrogen atom, methyl, isopropyl, benzyl) and the para-position of phenyl rings (nitro, dimethylamino). The effect of these substituents on the stoichiometry (ML, ML2), geometry and stereochemistry (mer, transfac, cis-fac) of the complexes was studied in solid state, in solution and by DFT calculations. X-Ray single crystal and powder diffraction, thermogravimetry, and IR spectroscopy showed that in the solid state imda ligands preferentially form transfac ML2 complexes, with the exception of the cis-fac complex 7Zn. NMR spectroscopy of diamagnetic Zn(II) and paramagnetic Co(II) complexes revealed the formation of both ML and ML2 complexes in solution. Variable temperature NMR was used to study the effect of the substituent on the central amine nitrogen on the Zn─N bond strength and nitrogen inversion. Relative stabilities of isomers were rationalized by computations and the optimized structures used for the geometry analysis.

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Section: Resultsmentioning

confidence: 99%

Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands

et al. 2019

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“…Reactions were carried out in ordinary glassware and chemicals were used as purchased from commercial suppliers without further purification. 2-Chloro- N -phenylacetamide, 61 2,2- N , N -dipicolyl-glycine sodium salt, 62 N -acetyl- l -phenylalanine, 63 and N , N -bis(2-pyridylmethyl)ethanediamine 64 were prepared according to previously reported procedures. Bpa ligands were stored under inert gas.…”

Section: Methodsmentioning

confidence: 99%

Tuning the coordination properties of chiral pseudopeptide bis(2-picolyl)amine and iminodiacetamide ligands in Zn(ii) and Cu(ii) complexes

et al. 2022

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“…DIPEA was added dropwise in order to neutralize the reaction mixture. Deprotected amine 6 was used without further purification 30 …”

Section: Methodsmentioning

confidence: 99%

“…> 250 C. 1 H NMR (300 MHz, DMSO) δ 10.69 (s, 2H, NH), 7.68 (d, J = 7.7 Hz, 4H, Ar-H), 7.35 (t, J = 7.9 Hz, 4H, Ar-H), 7.08 (t, J = 7.4 Hz, 2H, Ar-H), 4.20 (s, 5H, Fc-CH), 4.00 (s, 4H, CH 2 ), 3.87 (s, 2H, Fc-CH), 3.79 (s, 2H, Fc-CH). 13 8) 30 Prepared from 2-chloro-N-phenylacetamide (203 mg, 1.2 mmol, 2.5 equiv. ), KI (80 mg, 0.5 mmol, 1 equiv.…”

Section: Nn-di(n-phenylacetamide) Aminoferocene (2)mentioning

confidence: 99%

“…The bis(2-dipicolyl) amine product 7 was obtained by microwave-assisted alkylation with 2-picolyl chloride hydrochloride, while 8 was prepared by using a previously reported procedure. 30 N,N-Dipropargyl derivative 9 was prepared by an alkylation reaction in acetonitrile using K 2 CO 3 as a base and subsequently used as a terminal alkyne in CuAAC reactions with aromatic azides. Four bis-1,2,3-triazole derivatives were prepared to elucidate a possible influence of the N-1 substituent on the biological activity.…”

Section: Synthesis and Characterization Of Ligandsmentioning

confidence: 99%

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Late transition metal complexes of ferrocene‐containing nitrogen ligands: Coordination chemistry, electron transfer properties, and tumor cell viability

Jakopec,

Pantalon Juraj,

Jadreško

et al. 2024

Applied Organom Chemis

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Bis(2‐picolyl)amine (bpa), iminodiacetamide (imda), and bis‐1,2,3‐triazole (bta) ferrocene ligands (L) with and without an aliphatic linker were prepared by multi‐step synthesis. The cis‐fac, trans‐fac, or mer stereochemistry of their ML2 complexes with Ni(II), Cu(II), Cd(II), and Zn(II) was studied in the solid state (infrared [IR] and single‐crystal X‐ray diffraction [SC‐XRD]), in solution (nuclear magnetic resonance [NMR] and cyclic voltammetry [CV]) and by density functional theory (DFT) calculations. Crystal structures were determined for bpa ligand 7, and complexes [Ni(1)2](NO3)2 (1Ni), [Cu(8)2]OTf2 (8Cu), [Ni(10b)2](NO3)2 (10bNi), and [Cu(10b)2]OTf2 (10bCu). The bond strength of the central metal ion to the ligand amine nitrogen atom was studied by NMR, electrochemistry, and DFT. The information on redox‐active centers, electron transfer properties of ferrocene ligands (L), and their in situ complexation with zinc(II) and nickel(II) ions were obtained by voltammetric analysis. In addition, DFT calculations showed that the electron ionization in ML2 complexes occurs from one of the ferrocene units, leaving the electronic structure of the other ligand intact, while some of the expelled electron density is recovered by the adjacent amine through resonance. This effect is more pronounced in the free ligands, because the eventual amine resonance in ML2 needs to balance its Zn(II) coordination participation, which justifies why they show higher ionization energies over free ligands. Moreover, due to lower steric hindrance, the N(amino)–Zn(II) coordination is additionally stronger in 1:1 ML complexes, which makes their electron depletion further more demanding. If compared with the clinical drug cisplatin, complexes of bpa 1Ni and imda 2Ni showed a better effect on the viability of different tumor cell lines and better selectivity towards normal cells. Treatment with 1Ni and 2Ni causes an increase of cells in the S phase of the cell cycle and leads to the accumulation of cells in G0/G1. A decrease in the expression level of anti‐apoptotic marker Bcl‐2 upon treatment with both compounds together with increased amount of Annexin V‐FITC positive cells implied apoptosis as the mode of cell death.

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A Case Study of Supramolecular Organization: One Ferrocene Substituted Iminodiacetamide and its Chloroform Solvate

Cited by 4 publications

References 21 publications

Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands

Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands

Tuning the coordination properties of chiral pseudopeptide bis(2-picolyl)amine and iminodiacetamide ligands in Zn(ii) and Cu(ii) complexes

Late transition metal complexes of ferrocene‐containing nitrogen ligands: Coordination chemistry, electron transfer properties, and tumor cell viability

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