Rhodium Catalysts Based on Polyphenyl-Substituted Cp Ligands for Regioselective Annulation of Aryl Hydroxamates with Terminal Alkenes

Kharitonov V.; Antonova A.; Muratov D.; Navasardyan M.; D. A. Loginov

doi:10.1021/acs.organomet.5c00311

Publications

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Rhodium Catalysts Based on Polyphenyl-Substituted Cp Ligands for Regioselective Annulation of Aryl Hydroxamates with Terminal Alkenes

Organometallics. 2025. Vol. 44. No. 19. P. 2301–2308.

Kharitonov V., Antonova A., Muratov D., Navasardyan M., Loginov D. A.

The readily available tetraphenylcyclopentadienyl rhodium complex [CpPh4RhCl2]2 effectively catalyzes the annulation of aryl hydroxamates with terminal alkenes to selectively form 4-substituted dihydroisoquinolones. The ligand volume has a crucial influence on the selectivity and efficiency of the reaction. The use of the overloaded pentaphenylcyclopentadienyl ligand CpPh5 or its less bulky pentabenzyl analog CpBn5 resulted in a dramatic decrease in the efficiency or regioselectivity, respectively. The developed protocol was used for the synthesis of the precursor of the spermidine alkaloid cyclocelabenzine from N-(pivaloyloxy)benzamide and N-allylphthalimide. These results highlight the potential of phenyl-substituted Cp ligands for the design of efficient catalysts for C–H activation reactions.

Research target: Chemistry

Keywords: Total synthesis rhodium complexes C-H activation Homogeneous catalysis isoquinolones

Long-range machine-learning potentials with environment-dependent charges enable predicting LO-TO splitting and dielectric constants

Korogod D., Shapeev A., Novikov I., Physical Review B: Condensed Matter and Materials Physics 2026 Vol. 114 No. 2 Article 024104

We present two models with explicit long-range electrostatics in the form of Coulomb interactions. Both models include point charges depending on their local atomic environments, and the second model also conserves a total charge of an atomic system. We combine the proposed long-range models with the local moment tensor potential (MTP) and demonstrate that they ...

Added: July 22, 2026

A Way to Create Mn-Containing GdFe3(BO3)4 and the Dopant Effect on Its Magnetic Properties

Moshkina E., Molokeev M., Zolotov A. et al., Journal of Alloys and Compounds 2026 Vol. 1077 Article 189412

A wide series of substitutions in a subsystem of small radii cations M = Al, Cr, Fe, Ga, Sc is possible in rare-earth borates ReM3(BO3)4 with the huntite structure. However, the existence of these compounds where M = Mn still raises doubts. The study presents a synthetic approach developed in the framework of the flux method allowing for the required ...

Added: June 29, 2026

Incorporating Scientific Knowledge into Neural Network Density Functionals

Schneider M., Zaripov D., Dokin R. et al., Journal of Chemical Theory and Computation 2026 Vol. 22 No. 9 P. 4405–4414

Density functional theory (DFT) is the workhorse of modern reactions and materials modeling. While the exact functional remains unknown, many approximations to it have been constructed either by hand-crafting functional forms to satisfy exact constraints or by machine learning. In this work, we show how both of these approaches can be fused to build both ...

Added: June 26, 2026

Electrodeposition and electrochromic properties of hydrated mixed oxides MoxW1-xO3·2H2O films

Laurinavichyute V., Levin E. E., Mironkova A. A. et al., Surfaces and Interfaces 2026 Vol. 81 Article 108389

In this work we characterize mixed Mo-W acidic deposition solutions with Mo content ranging from 0 to 100 mol.% by Raman and UV–Vis spectroscopy. The obtained distribution diagram of mixed isopolyanions allows one to explain the observed change in film deposition rate with increase in Mo content. It was found that the initial decrease in ...

Added: June 24, 2026

Impact of heat treatment on microstructure and mechanical properties of additively manufactured aluminum bronze

Filippova A. V., Yurchenko N. Y., Smirnov S. A. et al., Journal of Alloys and Compounds 2026 No. 1074 Article 189162

This study investigates the effects of post-processing heat treatment at 300–500 °C on the microstructure, hardness, and tensile properties of laser powder bed fusion (PBF-LB) processed Al-bronze processed with energy densities (ED) in the range of 125–938 J/mm3. In the as-printed state, sharp needle-like α + β′ laths form at lower ED whereas with increasing ED, the β′ ...

Added: June 12, 2026

DFT-guided charge-state engineering of gold clusters for levodopa recognition: fundamental principles for drug delivery applications

Obijiofor O., Novikov A., New Journal of Chemistry 2026 Vol. 50 No. 23 P. 9749–9768

Rational design of gold-based nanocarriers for neurotherapeutics requires atomic-scale understanding of drug-material interactions. Density functional theory calculations were performed to investigate levodopa (L-DOPA) adsorption on small gold clusters (Au2–Au4) with cationic, neutral, and anionic charges, with additional validation on a larger Au10 cluster using multiple low-energy isomers. Binding free energies (ΔGbind), charge transfer, and electronic descriptors ...

Added: June 3, 2026

Facile and Green Approach to Synthesize Biomass-Derived Zero-/Two-Dimensional Carbon Dots/g-C3N4 Heterojunction for Efficient Photocatalytic and Photoelectrocatalytic Applications

Das A., Saikia J., Maji N. et al., ChemNanoMat 2026 Vol. 12 No. 5 Article e202500733

Developing efficient photoactive materials from bio-derived resources is vital yet challenging for achieving effective water splitting performance. In this work, nano carbon dots (CDs) of zero-dimensional (0D) were synthesized from papaya peel through a simple and eco-friendly process and subsequently anchored onto the two-dimensional (2D) layered structure of graphitic carbon nitride (g-C3N4, GCN) at various ...

Added: June 2, 2026

Optimal Design of Copper-Doped ZnO Heterostructures for Photocatalytic and Photoeletrochemical Performance: A Combined Experimental and DFT Study

Wary R. R., Mahato B., Sharma N. et al., The Journal of Physical Chemistry Letters 2026 Vol. 17 No. 17 P. 5099–5107

Development of heterojunction materials is an efficient approach for enhancing photocatalytic and photoelectrochemical processes. We develop a ZnO/CuO heterojunction via Cu doping into a ZnO matrix. Structural characterization confirmed that Cu was effectively incorporated into ZnO without any structural changes. The improved optical properties and reduced charge carrier recombination of the doped samples were confirmed ...

Added: June 2, 2026

Synergistic Multimetal Effects in a High-Entropy Perovskite Oxide Anchored on Reduced Graphene Oxide for Accelerated Water Oxidation

Ostovari Moghaddam A., Mehrabi-Kalajahi S., Hossein Vasigh S. A. et al., The Journal of Physical Chemistry Letters 2026 Vol. 17 No. 13 P. 3978–3985

Water electrolysis is a key technology for sustainable energy conversion and hydrogen generation. Recently, high-entropy oxides (HEOs) have emerged as promising materials because they allow tuning of structural, electronic, and catalytic properties in multifunctional systems. Here, we report the synthesis of a multicomponent La(FeCoCuTiNiMnMgSnZn)O3 perovskite, and its hybridization with reduced graphene oxide (rGO) to form a ...

Added: June 1, 2026

Band Gap Renormalization Drives Ultrafast Charge Separation and Slow Recombination in Covalently Functionalized Carbon Nanotubes: Nonadiabatic Molecular Dynamics Simulation

Chowdhury U., Mondal S., Dey S. et al., Journal of the american chemical society 2026 Vol. 148 No. 23 P. 24538–24550

Covalent functionalization offers a versatile platform to engineer carbon nanotube properties for optoelectronics applications. We demonstrate by atomistic quantum dynamics simulation that covalent functionalization can renormalize the CNT band gap, split the degenerate CNT band edge states, and strongly influence charge carrier separation and recombination dynamics. Open-ring CNT functionalization (O-CNT) largely retains the π-conjugation, whereas ...

Added: June 1, 2026

An IQA/QTAIM Approach to the Chalcogen Bond

Jiménez-Grávalos F., Alexander S. Novikov, Pendás Á. M., Communications in Computational Chemistry 2026 Vol. 8 No. 2 P. 203–210

Chalcogen bonds (ChBs) are often interpreted as 𝜎-hole driven electrostatic interactions between a chalcogen atom and a Lewis base, yet their covalent character remains under active discussion. Here, we present a real-space, reference-free study of prototypical X2Ch···X– complexes (X = F, Cl; Ch = O, S) using the Interacting Quantum Atoms (IQA) energy decomposition within ...

Added: May 27, 2026

Singlet oxygen-mediated oxidation of sulfides with palladium(II) porphyrinates: The effect of partly conjugated peripheral substituents

Uskov F., Korobkov S., Birin K. P. et al., Journal of Photochemistry and Photobiology A: Chemistry 2026 Vol. 474 Article 116936

Oxidation of sulfides by singlet oxygen has been extensively studied, yet the structure-photoactivity relationship of these photosensitizers remains underinvestigated. In the present work the photocatalytic performance of a set of functionalized palladium(II) porphyrinates was comprehensively investigated in the photocatalytic oxidation of sulfides to reveal mutual influence of structural peculiarities onto the photosensitizing properties. The photophysical ...

Added: May 27, 2026

Synthesis of Zwitterionic conjugates of cobalt Bis(dicarbollide) with BODIPY and their Photophysical properties and biological studies

Mezentsev I., Dudarova N., Druzina A. et al., Journal of Photochemistry and Photobiology A: Chemistry 2026 Vol. 479 Article 117316

Novel cobalt bis(dicarbollide) based terminal alkynes with charge-compensated group in a spacer were synthesized by the nucleophilic ring-opening reactions of cyclic oxonium derivatives of cobalt bis(dicarbollide) with N,N-dimethylbut-3-yn-1-amine. A series of zwitterionic conjugates of cobalt bis(dicarbollide) with BODIPY were synthesized using the copper(I)-catalyzed azide-alkyne cycloaddition reaction. The absorption-emission spectra of the synthesized fluorescent conjugates of cobalt ...

Added: May 27, 2026

Revealing Structure-Reporting Patterns of Pyruvylation Effects on 13C NMR Chemical Shifts in Natural Saccharides

Toukach P., Smirnova N. S., Zdorovenko E. L. et al., Analytical Chemistry 2026 Vol. 98 No. 15 P. 10988–10996

Pyruvylation is one of the immunochemically relevant modifications of O-antigens in bacterial and fungal cells. Therefore, fast and relatively simple analytical methods for identifying this modification are highly demanded. 13C NMR spectroscopy is the best candidate for this purpose, but its successful application requires using reference structures and reliable databases. In this work, we collected ...

Added: May 25, 2026

Sodium Hypophosphite Assisted Ruthenium Catalyzed Reductive Amination under Mild Conditions

Зверева О., Kliuev F., Lebedeva N. et al., Organic Letters 2025 Vol. 27 No. 50 P. 13711–13716

Added: May 23, 2026

TBAT as “Multitool” Catalyst for Polysiloxane Synthesis, Modification, and Recycling

Mikhail A. Losev, Andrey S. Kozlov, Afanasyev O. et al., ACS Catalysis 2026 Vol. 16 No. 10 P. 9380–9386

A convenient, stable, and non-toxic substance, tetrabutylammonium difluorotriphenylsilicate (TBAT), can be used as an organocatalyst in all stages of polymer lifetime: synthesis, modification, and recycling. The fluorine-containing initiator showed high activity in the polymerization of siloxanes compared to classic organocatalytic systems. Using kinetically controlled ROP, a high-molecular-weight PDMS (Mn up to 820 𝑘𝑔/𝑚𝑜𝑙) was prepared at room ...

Added: May 22, 2026

Reductive coupling of nitroarenes with carboxylic acids – a direct route to amide synthesis

Лосев М. А., Козлов А. С., Kliuev F. et al., Organic and Biomolecular Chemistry 2023 Vol. 21 No. 42 P. 8477–8481

A simple and atom-efficient way to prepare amides directly from carboxylic acids and nitroarenes was developed. Carbon monoxide as a sole reducing agent provides the ultimate selectivity of the protocol. A straightforward and selective way for the preparation of amides from nitroarenes and carboxylic acids using carbon monoxide as a reductant was developed. This protocol ...

Added: May 22, 2026

Dataset of solubility values for organic compounds in binary mixtures of solvents at various temperatures

Malikov D., Krasnov L., Kiseleva M. et al., Scientific data 2026 Vol. 13 Article 727

Solubility is a crucial property of organic compounds, impacting their potential applications in synthetic chemistry, materials science and drug design. Moreover, in technological processes mixtures of solvents are often utilized, making the solubility assessment more complicated. Predicting solubility values in mixtures of solvents from a molecular structure can help to address this issue, although a ...

Added: May 19, 2026

Perovskite nanoparticles Cs4PbBr6 and CsPbBr3: synthesis, analysis and peculiar optical properties

Гущина В. А., / Series chemrxiv-2023-vpzhz-v2 "ChemRxiv". 2023.

All-inorganic perovskite CsPbBr3 and Cs4PbBr6 nanoparticles are being intensively studied due to their unique properties and wide range of applications; however, however, the nature of their optical properties is not yet fully understood due to the difficulty of synthesis of singlephase nanoparticles. In this article we describe the features of the synthesis of single-phase particles ...

Added: May 14, 2026

CsPbBr3 and Cs4PbBr6 perovskite nanoparticles: hidden potential of Cs4PbBr6 or ineffective fluorescence?

Гущина В. А., Mendeleev Communications 2025 Vol. 35 No. 2 P. 193–195

All-inorganic perovskite CsPbBr3 and Cs4PbBr6 nanoparticles are intensively studied for their unique optical properties, though synthesizing single-phase nanoparticles has posed challenges. Detailed synthesis method of CsPbBr3 and Cs4PbBr6 single-phase nanoparticles and their chemical and phase analysis are described. Distinctive optical characteristics, such as photoluminescence, optical band gap and the Urbach tail region, are revealed and explained within the current ...

Added: May 14, 2026

SERS effect on the surface of ZnO nanorods coated with CsPbBr3

Гущина В. А., Physics of Complex System 2026 Vol. 7 No. 1 P. 3–15

Heterostructures based on ZnO nanorods and CsPbBr3 nanocrystals were investigated for their potential as semiconductor SERS substrates. We found that ZnO morphology governs the efficiency of interfacial energy transfer, leading to enhanced photoluminescence under 390 nm excitation and a noticeable reduction of the bandgap in the composites. Raman analysis revealed a pronounced intensity enhancement and ...

Added: May 14, 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

Synthesis of Isoquinoline-Containing 5,6-Dicyano-2,1,3-Benzothiadiazoles: Unusual Heterocyclization into Dibenzo-1,6-Naphthyridine Framework

Gribanov P., Vorobyeva D., Loginov D. A. et al., Asian Journal of Organic Chemistry 2024 Vol. 13 No. 9 Article e202400226

An efficient access to novel families of cyano-containing polyheteroaromatic D- A molecules with extended π-conjugation, including dibenzo[c,h][1,6]naphthyridine derivatives, has been elaborated. The synthetic strategy is based on the sequence of metal-catalyzed annulation and cross-coupling reactions starting from available 4-ethynyl-5,6-difluoro-7-(pmethoxyphenyl)- 2,1,3-benzothiadiazole to get a new series of isoquinoline-linked BTD-based D- A compounds, which further undergo a selective cyanation ...

Added: February 20, 2025

Rhodium Catalysts Based on Phenyl Substituted Cp Ligands for Indole Synthesis via Oxidative Coupling of Acetanilides and Alkynes

Kharitonov V., Muratov D., Rodionov A. et al., Advanced Synthesis and Catalysis 2024 Vol. 366 No. 22 P. 4729–4736

Rhodium-catalyzed oxidative coupling of acetanilides and alkynes via C􀀀 H activation is the most powerful synthetic tool for producing the indole motif from commercially available precursors. However, this reaction usually requires large catalyst loadings (5 mol% of rhodium). In this study, a 1,2-diphenylcyclopentadienyl ligand-based catalyst was developed that works well at 1 mol% loading of ...

Added: February 20, 2025