Planar chiral rhodium complexes of 1,4-benzoquinones

Ankudinov N.; Nelyubina Y.; Dmitry S. Perekalin

doi:10.1002/chem.202200195

Publications

?

Planar chiral rhodium complexes of 1,4-benzoquinones

Chemistry - A European Journal. 2022. Vol. 28. No. 18. Article e202200195.

Ankudinov N., Nelyubina Y., Dmitry S. Perekalin

Diene rhodium complexes are important catalysts in modern organic synthesis. Herein, we report a new approach to the such complexes with the uncommon planar chirality. The synthesis is achieved by face-selective coordination of the prochiral 2,5-disubstituted-1,4-benzoquinones (R2-Q) with rhodium precursors containing the chiral auxiliary ligand S-salicyl-oxazoline (S-Salox). Such coordination leads to the formation of (R,R-R2-Q)Rh(S-Salox) complexes in high yields and with exceptional diastereoselectivity (d.r. > 20:1). Subsequent replacement of the auxiliary ligand provides various benzoquinone rhodium complexes with retention of the planar chirality. Combined theoretical and experimental studies show that due to their electron-withdrawing nature benzoquinones bind metals stronger than the related 1,4-cyclohexadiene, but weaker than other common diene ligands, such as cyclooctadiene.

Research target: Chemistry

Keywords: rhodium родий chirality planar chirality Хиральность dienes диены

Machine Learning Approach to Anticancer Activity Prediction of Transition-Metal Complexes Based on a Large-Scale Experimental Database

Krasnov L., Malikov D., Kiseleva M. et al., Journal of Medicinal Chemistry 2026 Vol. 69 No. 8 P. 8838–8851

In this work, we developed a straightforward data-driven approach to predict the cytotoxicity of metal complexes based entirely on their (metal + ligands) composition. To this end, we have manually curated MetalCytoToxDB─a comprehensive experimental database comprising 26,500 IC50 values for 7050 metal complexes against 754 cell lines from 1921 articles. Based on these, machine learning ...

Added: April 23, 2026

Cu(I) acetylide clusters decorated with pyridylphosphine ligands: structural diversity, cuprophilic interactions and phosphorescence properties

Novikov A., Inorganic Chemistry Communications 2026 Article 116670

The reaction of copper(I) phenylacetylide [PhC ≡ CCu]n with the 2-pyridylphosphines (tBu2PyP and Ph2PyP) offers a straightforward route to structurally diverse clusters. With tBu2PyP, a trinuclear cluster [Cu3(C ≡ CPh)3(tBu2PyP)3] featuring a Cu3 triangular was isolated. Surprisingly, the reaction of [PhC ≡ CCu]n with Ph2PyP yields two isomeric clusters [Cu4(C ≡ CPh)4(Ph2PyP)4] with tetrahedral or zigzag-arranged Cu4 cores. Upon prolonged storage in acetonitrile, the tetrahedral Cu4 cluster converts to ...

Added: April 22, 2026

Rapid synthesis of redox-responsive trithiocyanuric acid-based nanocarriers: in vitro multidrug resistance reversal and In vivo safety assessment

Kopoleva E., Sergey A. Tsymbal, Kuchur O. et al., Drug Delivery and Translational Research 2026 P. 1–16

Multidrug resistance (MDR) remains one of the principal challenges in cancer chemotherapy, necessitating new strategies to restore drug efficacy. In this study we developed and characterize a redox-responsive nanoplatform based on trithiocyanuric acid and polyethylene glycol (TTCA-PEG NPs) as a potential tool to overcome MDR and provide a biocompatible delivery system for conventional antitumor drugs. ...

Added: April 20, 2026

Dipolar [3+2] Cycloaddition of Nitrones to 3-Aroylpyrrolo[2,1-c][1,4]benzothiazine-1,2,4-triones

Novikov A., Russian Journal of Organic Chemistry 2026 Vol. 62 Article 12

The dipolar [3+2]-cycloaddition reactions of 3-aroylpyrrolo[2,1-c][1,4]benzothiazine-1,2,4-triones with diarylnitrones lead to the formation of benzo[b]isoxazolo[5',4':2,3]pyrrolo[1,2-d][1,4]thiazines. The reac- tion proceeds stereoselectively to form exclusively the (2aS*,3R*,5aS*) diastereomers. Density functional theory computations for the model reaction showed that the (2aS*,3R*,5aS*) diastereomers are both kinetically and thermodynamically preferred over the alternative (2aS*,3S*,5aS*) diastereomers. At room temperature in solution, the ...

Added: April 19, 2026

Modeling cosolvent effects on solubility in supercritical CO2 using data-driven approaches

Makarov D. M., Kalikin N., Gurikov P. et al., Journal of Supercritical Fluids 2026 Vol. 235 Article 106979

Supercritical CO2 (scCO2 ) is an environmentally friendly solvent, but its low polarity limits the solubility of polar compounds. Cosolvents are commonly used to enhance solvation capability, yet comprehensive datadriven studies are scarce. We compiled the largest dataset to date — 4401 experimental solubility records with 22 cosolvents for 93 nonionic solutes, plus 4855 records ...

Added: April 19, 2026

Theory of capillary-induced self-coacervation in zwitterionic polymer solutions

Kalikin N., Брандышев П. Е., Budkov Y., Journal of Chemical Physics 2026 Vol. 164 Article 154904

This study presents a mean-field theory for zwitterionic polymer solutions confined within attractive slit-like nanopores. Building upon our prior model for self-coacervation [Budkov et al., Soft Matter 19, 3281–3289 (2023)], we demonstrate that strong electrostatic dipole–dipole correlations between monomeric units, coupled with attraction to pore walls, can induce capillary-driven liquid–liquid phase separation inside the pore—a ...

Added: April 18, 2026

Exploring the luminescent and thermometric potentials of samarium(iii) diketonate complexes with extended fluoroalkyl chains

Metlina D., Metlin M., Korshunov V. et al., Dalton Transactions 2025 Vol. 54 No. 9 P. 3812–3826

We synthesized and investigated a new series of Sm3+ 1,3-diketonate complexes with CnF2n+1-homologous thiophene-containing ligands. A clear correlation was found between the number of fluorine atoms in the 1,3-diketone's carbon chain and the luminescent properties of the samarium(III) complexes. The ligand modification method employed facilitates targeted and significant enhancements in the photoluminescence quantum yield (PLQY). ...

Added: March 24, 2026

Combining materials design and deep learning: AI-enhanced luminescence thermometry with a novel Eu3+/Tb3+polymeric coordination compound

Polikovskiy T., Gontcharenko V., Korshunov V. et al., Materials Chemistry Frontiers 2025 Vol. 9 No. 23 P. 3443–3459

Conventional thermal sensors often face limitations due to their reliance on direct contact and restricted measurement ranges, leading to the emergence of novel techniques like luminescence thermometry. However, sensitivity of luminescent thermometers is limited by the only used Boltzmann-based Mott–Seitz model, which is imperfect. To overcome this, we complemented Mott–Seitz model applying machine learning algorithms, ...

Added: March 24, 2026

Harvesting Magneto-Acoustic Waves Using Magnetic 2D Chromium Telluride (CrTe3)

Chowde Gowda C., Alexey Kartsev, Tiwari N. et al., Small 2024 Vol. 20 No. 47 Article 2405197

A vast majority of electrical devices have integrated magnetic units, which generate constant magnetic fields with noticeable vibrations. The majority of existing nanogenerators acquire energy through friction/mechanical forces and most of these instances overlook acoustic vibrations and magnetic fields. Magnetic two-dimensional (2D) tellurides present a wide range of possibilities for devising a potential flexible energy ...

Added: March 16, 2026

Non-thermal magnetic deicing using two-dimensional chromium telluride

Chowde Gowda C., Alexey Kartsev, Tiwari N. et al., Journal of Materials Chemistry C 2024 Vol. 12 No. 46 P. 18691–18703

Two-dimensional (2D) chromium telluride Cr2Te3 exhibits strong ferromagnetic ordering with high coercivity at low temperatures and paramagnetic behavior when approaching room temperature. The spin states of monolayer Cr2Te3 show ferromagnetic ordering in the ground state. In situ Raman analysis reveals a reversible structure transformation and hence proves ferromagnetic to paramagnetic transition during low-temperature heating cycles (0–25 °C). The magnetic ...

Added: March 16, 2026

Simultaneous enhancement of thermoelectric performance and mechanical properties in lead-free cubic GeTe-based composite materials

Xu Z., Guo Z., Zhang P. et al., Journal of Materials Chemistry A 2025 Vol. 13 No. 41 P. 35284–35291

GeTe is a promising mid-temperature thermoelectric material that exhibits excellent thermoelectric performance. However, the rhombohedral-to-cubic phase transition occurring near 700 K causes a change in the coefficient of thermal expansion, leading to internal stresses in the device and affecting its working efficiency. In this work, we reported the alloying of Ge0.81Mn0.15Bi0.04Te with AgSbTe2 to further reduce ...

Added: March 16, 2026

Электронные и магнитные свойства двухкомпонентных твердых растворов Cr(ClxF1-x)3

Лебедев И. С., Кудрявцев А. В., Карцев А. И. et al., Журнал радиоэлектроники 2025 № 11 Статья 30

n this paper, the effect of doping on the electronic and magnetic properties of a monolayer compound Cr(ClxF1-x)3 is studied based on a first-principles calculation. The densities of electronic states, the values of the band gap, the constants of the crystal lattice and the difference in total energies for ferromagnetic and antiferromagnetic configurations at different mutual ...

Added: March 16, 2026

Effect of doping on structure and functional properties of SrFe12-xInxO19 hexaferrite nanoparticles for biomedical applications

Shchetinin I., Nikolenko P., Nizamov T. et al., Ceramics International 2026 Vol. 52 No. 3 P. 3500–3511

In this work, we comprehensively investigated the influence of Indium doping on the structure, magnetic and functional properties of strontium M-type hexaferrites SrFe12-xInxO19 nanoparticles (where x = 1.7, 1.8, 2.0). Colloidally stable SrFe12-xInxO19 nanoparticles (∼10 nm) were synthesized using a combination of the citrate method and high-energy ball milling. We demonstrate that doping reduces both the specific saturation magnetization and, ...

Added: March 16, 2026

Formation of a Pt-Ni Catalyst in the Structure of a Silicon Micro-Fuel Cell

Starkov V., Gosteva E., Alexey Kartsev et al., Molecules 2026 Vol. 31 No. 3 Article 499

This paper demonstrates the results of constructive technological research on the development of a catalyst with a Ni/PSi@Pt structure. This catalyst eliminates the use of gold in the structure of μ-FC electrodes. This work uses the main technological solutions for the formation of a gold-containing “core–shell” structure on the inner surface of pores. Comparative data ...

Added: March 16, 2026

Tackling the challenge of ML-assisted antibacterial activity prediction: One step closer to controlled quaternary ammonium compounds design via neural networks model

Ilin E., Frolov N., Seferyan M. et al., Bioorganic Chemistry 2025 Vol. 167 Article 109175

The ongoing rise of resistant bacterial pathogens poses a significant threat to current antibacterials' effectiveness putting millions of people's lives at risk. However, modern machine learning (ML) tools promise to tip the scales in the never-ending development of antimicrobial agents' pipelines. Herein we present a novel approach for quaternary ammonium compounds (QACs) antibacterial activity prediction ...

Added: March 16, 2026

Aqueous solutions of La1−xPrxPO4 nanoparticles: microwave‑assisted hydrothermal synthesis, X‑ray excited UV‑C luminescence, and colloidal properties

Шайдулин А. Т., Orlovskaya E., Popov A. et al., Journal of Nanoparticle Research 2025 Vol. 27 Article 320

Nanoparticles (NPs) exhibiting X-ray excited UV-C luminescence can be used in radia tion therapy to deactivate cancer cells through pho tochemical reactions of DNA with UV-C quanta. Colloidal solutions of monoclinic La1−xPrxPO4 NPs (x = 0.01–0.3), luminescent in the UV-C range (220–280 nm), with different morphologies, from nanofiber (diameter and length not larger than 15 and ...

Added: March 13, 2026

Do chemists control plane packing, i.e. two-dimensional self-assembly, at all scales?

Chinaud-Chaix C., Marchenko N., Fernique Т. C. et al., New Journal of Chemistry 2023 Vol. 47 No. 15 P. 7014–7025

Two-dimensional (2D) self-assembly (SA) is an efficient strategy to organize building blocks in a simple and efficient way. Actually, different communities of chemists or physicists use 2D SA, with different systems at different scales: molecules, nanoobjects, micron-sized colloidal particles, and even millimetric plastic shapes. Although, the cases of study and the perspectives are different, general ...

Added: March 11, 2026

Синтез и физико-химические свойства солей магния с 4Н-пирановыми кислотами

Козин С. В., Кравцов А. А., Киндоп В. Н. et al., Журнал неорганической химии 2025 Т. 70 № 2 С. 191–200

В результате взаимодействия 4-оксо-4H-пиран-2,6-дикарбоновой (хелидоновой) кислоты с ацетатом магния было получено сокристаллическое соединение - хелидонат магния. Изучение процесса термоокислительной деструкции хелидоната магния показало, что его дегидратация осуществляется в два этапа, а термодеструкция органической части сопровождается ярко выраженными тепловыми эффектами. В структуре хелидоната магния вокруг катиона магния имеется как внутренняя, так и внешняя координационная сфера. Во ...

Added: March 10, 2026

Straightforward Access to Stable One-Dimensional Coordination Polymers of Iridium(III) with Bridging Triiodide Anions

Bezzubov S., Kiseleva M., Inorganic Chemistry 2026 Vol. 65 No. 1 P. 13–20

Here, we present a new reaction of common octahedral iridium(III) complexes, [Ir(C^N)2(acac)] (C^N is the cyclometalated ligand, acac is acetylacetonate) with iodine, resulting in the high-yield preparation of unique crystalline polymers, [Ir(C^N)2I3]n, in which the Ir(C^N)2+ fragments are linked by triiodide bridges. The solid polymers show good photo- and thermal stability up to 200 °C in ...

Added: February 17, 2026

Accessing inherently chiral multifunctional structures by desymmetrization of a wide-rim calix[4]arene triamine

Bezzubov S., Vatsouro I., Alekseev I. et al., Organic Chemistry Frontiers 2026 Vol. 13 No. 3 P. 851–865

An efficient strategy is presented for the synthesis of rare-type inherently chiral calix[4]arenes having an asymmetric arrangement of functional groups at the wide rim of the cone macrocycle and possessing virtually unlimited functionalization capabilities. Selective protection of two proximal amino groups in the Cs-symmetrical wide-rim calixarene triamine by tert-butoxycarbonyl groups is suggested as the key synthesis step, ...

Added: February 17, 2026

Synthesis of cyclopentadienyl rhodium catalysts by co-cyclization of two different alkynes

Kolos A., Nelyubina Y., Godovikova M. et al., Chemistry - A European Journal 2025 Vol. 31 No. 41 Article e202501793

Cyclopentadienyl rhodium complexes (C5R5)RhLx are widely used as homogeneous catalysts. Herein we report the synthesis of such complexes with structurally diverse cyclopentadienyl ligands in one step directly from alkynes. Specifically, reactions of bulky terminal alkynes (tert-butylacetylene or trimethylsilylacetylene) with activated internal alkynes (ethyl 2-butynoate or dimethyl acetylenedicarboxylate (DMAD)) and [(cod)RhCl]2 produce either cyclopentadienyl or pentalene-type ...

Added: February 15, 2026

Catalytic insertion of nitrenes into B-H bonds

Ankudinov N., Alexeev N., Podyacheva E. et al., Chemical Science 2025 Vol. 16 No. 15 P. 6298–6306

Organic compounds with boron–nitrogen bonds are widely used as fluorescent sensors and semiconducting materials. This paper presents a new approach for the formation of B–N bonds via catalytic insertion of nitrenes into B–H bonds. The reaction proceeds most selectively for cyclic boranes with a 2-phenylpyridine framework and nitrenes generated in situ by the oxidation of ...

Added: February 15, 2026

Synthesis of chiral boranes via asymmetric insertion of carbenes into B–H bonds catalyzed by the rhodium(I) diene complex

Ankudinov N., Komarova A., Evgeniya S. Podyacheva et al., Chemical Communications 2024 Vol. 60 No. 65 P. 8601–8604

Molecules with chiral boron atoms have been scarcely studied due to limited synthetic access. Herein, we report a new method for their synthesis via asymmetric insertion of arydiazoacetates into the B–H bonds of prochiral carbene–boranes NHC–BH2R. The reaction is catalyzed by the rhodium(I) complex with the chiral diene ligand tBu2-TFB, which can be conveniently prepared by ...

Added: February 23, 2025

Planar-chiral arene ruthenium complexes: synthesis, separation of enantiomers, and application for catalytic C–H activation

Mikhail A. Boym, Pototskiy R., Evgeniya S. Podyacheva et al., Chemical Communications 2024 Vol. 60 No. 33 P. 4491–4494

Heating tert-butyl-tetraline with [(p-cymene)RuCl2]2 produces the racemic complex [(arene)RuCl2]2, which can be separated into enantiomers by chromatography of its diastereomeric adducts with chiral phosphine ligand. The resolved chiral complex catalyzes C–H activation of N-methoxy-benzamides and their annulation with N-vinyl-pivaloyl amide giving dihydroisoquinolones in 50–80% yields and with 40–80% enantiomeric excess. ...

Added: January 23, 2025