The choice of μ-vinyliminium ligand substituents is key to optimize the antiproliferative activity of related diiron complexes

Metallomics, Год журнала: 2022, Номер 15(1)

Опубликована: Дек. 14, 2022

Abstract Diiron vinyliminium complexes constitute a large family of organometallics displaying promising anticancer potential. The [Fe2Cp2(CO)(μ-CO){μ-η1:η3-C(R3)C(R4)CN(R1)(R2)}]CF3SO3 (2a-c, 4a-d) were synthesized, assessed for their behavior in aqueous solutions (D2O solubility, Log Pow, stability D2O/Me2SO-d6 mixture at 37°C over 48 h) and investigated antiproliferative activity against A2780 A2780cisR ovarian cancer cell lines the nontumoral one Balb/3T3 clone A31. Cytotoxicity data collected 50 correlated with structural properties (i.e. different R1–R4 substituents) using partial least squares methodology. A clear positive correlation emerged between octanol–water partition coefficient relative on lines, both which appear as uncorrelated to selectivity. However, effects played by substituents allow tracing guidelines development novel, more effective compounds. Based these results, three additional (4p-r) designed, synthesized biologically investigated, revealing ability hamper thioredoxin reductase enzyme induce production reactive oxygen species.

Язык: Английский

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Tuning In Vitro Cytotoxicity in Diruthenium(I) bis‐Cyclopentadienyl Complexes

Applied Organometallic Chemistry, Год журнала: 2025, Номер 39(5)

Опубликована: Апрель 3, 2025

ABSTRACT A series of diruthenium(I) aminocarbyne complexes general formula [Ru 2 Cp (CO)(L)(μ‐CO){μ‐CNMe (Cy)}] + (L = NH 3 , [ ] ; Py, PPh 4 DMSO, 5 thiourea, 6 ) and (μ‐H)(CO) {μ‐CNMe (Cy)}], 7 were prepared from the tricarbonyl precursor (CO) (μ‐CO){μ‐CNMe . The reactivity vinyliminium complex (CO)(μ‐CO){μ‐η 1 :η ‐C (Ph)CHCNMe was also investigated, providing access to piano stool Ru (II) cyclopentadienyl with a five‐membered metallacyclic ligand containing sulfur. new compounds characterized by IR multinuclear NMR spectroscopy X‐ray diffraction (in three cases). solubility in water, lipophilicity, speciation – ]CF SO water/DMSO cell culture medium are regulated different monodentate ligands. Subsequently, tested vitro against human ovarian cancer cells (A2780 A2780cis) embryonic kidney (HEK293), demonstrating moderate potent cytotoxicity.

Язык: Английский

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Cyanide–alkene competition in a diiron complex and isolation of a multisite (cyano)alkylidene–alkene species

Dalton Transactions, Год журнала: 2021, Номер 51(5), С. 1936 - 1945

Опубликована: Дек. 27, 2021

The μ-(amino)alkylidyne complex [Fe2Cp2(CO)2(μ-CO){μ-CNMe(CH2CHCH2)}]CF3SO3, [1]CF3SO3, reacted with NBu4CN in dichloromethane affording the μ-(cyano)(amino)alkylidene [Fe2Cp2(CO)2(μ-CO){μ-C(CN)N(Me)(CH2CHCH2)}], 2, 91% yield. Decarbonylation of 2 by using Me3NO acetone at room temperature yielded [Fe2Cp2(CO)(μ-CO){μ-κ3C-C(CN)N(Me)(CH2CHCH2)}], 3, containing a multidentate alkylidene-alkene ligand occupying both bridging site and terminal site, admixture cyanide product [Fe2Cp2(CN)(CO)(μ-CO){μ-CN(Me)(CH2CHCH2)}], 4. reaction imine [Fe2Cp2(CO)(μ-CO)(NHCPh2){μ-CN(Me)(CH2CHCH2)}]CF3SO3, [7]CF3SO3, gave 3 an optimized yield 75% via elimination. According to DFT calculations, is less stable than its geometric isomer 4 13.4 kcal mol-1 quantitative conversion was achieved refluxing THF solution for hours. No replacement alkene coordination occurred upon treating CO or PPh3. previously unknown compounds [7]CF3SO3 were fully characterized analytical spectroscopic techniques structure elucidated single crystal X-ray diffraction.

Язык: Английский

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Alkyne–alkenyl coupling at a diruthenium complex

Dalton Transactions, Год журнала: 2022, Номер 51(41), С. 15703 - 15715

Опубликована: Янв. 1, 2022

Dimetallic complexes are suitable platforms for the assembly of small molecular units, and reactivity bridging alkenyl ligands has been widely investigated to model C-C bond forming processes. Here, we report unusual coupling an ligand, coordinated on a diruthenium scaffold, with series alkynes, revealing two possible outcomes. The complex [Ru2Cp2(Cl)(CO)(μ-CO){μ-η1:η2-C(Ph)CH(Ph)}], 2, was prepared in steps from [Ru2Cp2(CO)2(μ-CO){μ-η1:η2-C(Ph)CH(Ph)}]BF4, [1]BF4, 69% yield. Then, reaction 2 C2(CO2Me)2, promoted by AgCF3SO3 dichloromethane, afforded 51% yield [Ru2Cp2(CO)2{μ-η3:η2-C(Ph)CH(Ph)C(CO2Me)C(CO2Me)}]CF3SO3, [3]CF3SO3, containing ruthenacyclopentene-based hydrocarbyl ligand. On other hand, reacted alkynes AgX salts give butadienyl [Ru2Cp2(CO)2{μ-η3:η2-C(R)CH(R')C(Ph)C(Ph)}]X (R = R' H, [4]BF4; R Me, [5]CF3SO3; Ph, [6]CF3SO3; [7]CF3SO3), 42-56% yields. All products were characterized IR NMR spectroscopy, single crystal X-ray diffraction cases [3]CF3SO3 [6]BF4. DFT calculations highlighted higher stability [4-7]+-like structures respect corresponding [3]+-like isomers. It is presumable that isomers initially form as kinetic intermediates, then undergo H-migration which disfavoured presence carboxylato substituents alkyne. Such hypothesis supported computational optimization transition states H CO2Me.

Язык: Английский

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Regiocontrolled Coupling of Alkynes and Dipolar Reagents: Iron-Mediated [3 + 2] Cycloadditions Revisited

Organometallics, Год журнала: 2021, Номер 40(14), С. 2295 - 2304

Опубликована: Апрель 13, 2021

Cyclopentadienyliron dicarbonyl based allenyliron complexes were prepared, and their formal [3 + 2] cycloaddition with a number of dipolar reagents was investigated as means preparing heterocyclic compounds in regiocontrolled manner. In addition, the mechanism isomerization an complex to its propargyliron tautomer investigated. Results support both radical two-electron mechanisms for are presented.

Язык: Английский

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Alkylidyne and Alkylidene Complexes of Iron

Elsevier eBooks, Год журнала: 2021, Номер unknown, С. 210 - 257

Опубликована: Ноя. 29, 2021

Язык: Английский

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Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

Inorganic Chemistry, Год журнала: 2020, Номер 59(23), С. 17497 - 17508

Опубликована: Ноя. 18, 2020

A series of 2,3-dicarboxylato-5-acetyl-4-aminoselenophenes, 5a–j, was obtained via the uncommon assembly building blocks on a diiron platform, starting from commercial [Fe2Cp2(CO)4] through stepwise formation complexes [2a–d]CF3SO3, 3a–d, and 4a–j. The selenophene-substituted bridging alkylidene ligand in 4a–j is removed coordination upon treatment with water air under mild conditions (ambient temperature most cases), affording 5a–j good to excellent yields. This process highly selective accompanied by disruption organometallic scaffold: cyclopentadiene (CpH) lepidocrocite (γ-FeO(OH)) were identified NMR Raman analyses at end one representative reaction. straightforward cleavage linkage between Fischer two (or more) metal centers, as observed here, an unprecedented reaction chemistry: present case, carbene function converted ketone which incorporated into organic product. DFT calculations electrochemical experiments carried out give insight release selenophene-alkylidene ligand. Compounds fully characterized elemental analysis, mass spectrometry, IR, multinuclear spectroscopy X-ray diffraction cyclic voltammetry case.

Язык: Английский

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Syntheses and characterizations of rhenaindole complexes

Polyhedron, Год журнала: 2023, Номер 236, С. 116359 - 116359

Опубликована: Март 8, 2023

Язык: Английский

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