Article
Chemistry, Physical
Renat Kadyrov
Summary: An efficient and simple catalytic system has been developed for the hydrogenation of carboxylic esters using commercially available Ru-salts and imidazolium salts. This combination enables the reduction of esters to alcohols at moderate temperature and pressure, offering a practical method for alcohol synthesis.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Barbara Mohar, Marko Jeran, Michel Stephan
Summary: Outfitting the 2MeBigFUS ligand with the branched/functionalized-alkoxy feature of the R-SMS-Phos design resulted in the 2RBigFUS family. Rhodium(I) complexes of these ligands exhibited enhanced activity and superior enantioselectivity in the hydrogenation of functionalized olefins, including challenging α-arylacrylic acids. The application of these catalysts to enantiomeric active pharmaceutical ingredients (APIs) and synthetic building blocks further highlighted their potential.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Antal Udvardy, Ferenc Joo, Agnes Katho
Summary: The compound 1,3,5-Triaza-7-phosphaadamantane (pta, phosphaurotropine) has played a crucial role in the development of aqueous organometallic chemistry and catalysis due to its easy synthesis, oxidation stability, versatile functionalization possibilities, and high solubility in both water and common organic solvents. It has been used to synthesize transition metal complexes and has been employed as catalysts in various important aqueous-phase processes, contributing significantly to the advancement of green chemical processes.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Ondrej Mozdiak, Jiri Tydlitat, Zdenka Ruzickova, Libor Dostal, Roman Jambor
Summary: In this study, Ru complexes with N-bound 2-pyridonato ligand were prepared and their catalytic activity in base-free transfer-hydrogenation of ketones was investigated.
Article
Chemistry, Inorganic & Nuclear
Nora Jannsen, Christian Fischer, Carmen Selle, Cornelia Pribbenow, Hans-Joachim Drexler, Fabian Reiss, Torsten Beweries, Detlef Heller
Summary: In this study, we systematically investigate and quantify the influence of solvent coordination on reactions of cationic rhodium(i) diphosphine complexes. We propose a method to analyze and quantify solvent binding using MeCN as a replacement for diolefins. By using UV-vis and P-31{H-1} NMR spectroscopy, we determine and compare stability constants of different complexes, and discuss the impact of different ligands and reaction temperature. DFT study reveals the relationship between stability and thermodynamics of the exchange reaction. Additionally, variable temperature NMR spectroscopy confirms the existence of a mixed solvate complex as an intermediate in the MeCN-MeOH exchange.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Raill R. Quinonez-Lopez, Sara A. Cortes-Llamas, J. Roberto Estrada-Flores, Jose G. Alvarado- Rodriguez, Oscar Blanco-Alonso, A. Aaron Peregrina-Lucano, Elvia Becerra-Martinez, I. Idalia Rangel-Salas
Summary: Heteroleptic [RhIIICp*(NHC)] and [IrIIICp*(NHC)] complexes with a N-amino acid functionality derived from imidazolium salts were synthesized and characterized. The structure of [RhCp*{kappa 2(C,O)-NHC}Cl] complex 3f was discussed as a pair of diastereomers. The catalysts showed good yields for the transfer hydrogenation of ketones in basic propan-2-ol, and a chromatographic method for measuring compounds in the reaction was validated. These Rh and Ir complexes provide a new approach in developing catalysts based on classical NHC precursors.
Article
Chemistry, Multidisciplinary
Chenghao Li, Shu-Xin Zhang, Yu Feng, Yan-Mei He, Qing-Hua Fan
Summary: The chiral ruthenium-catalyzed enantioselective hydrogenation of tetrapyridine-type N-heteroarenes was developed for the first time. The adjacent tetraheteroaromatic substrates showed high reactivity, enantioselectivity, and diastereoselectivity, with yields up to 93%, enantiomeric excess (>99% ee), and diastereomeric ratio of 92:8, respectively, in the presence of phosphine-free chiral cationic ruthenium diamine complexes. The potential application of chiral tetradentate pyridine-amine products as chiral ligands was demonstrated in the Cu-catalyzed asymmetric Friedel-Crafts alkylation reaction between indoles and nitroalkenes.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Duanyang Kong, Qiqige Qiqige, Wesley McNutt, Rocco Paciello, Ansgar Schaefer, Mathias Schelwies, Rylan J. Lundgren
Summary: Transition metal catalyzed hydrogenation of alkenes is a widely used technology in both laboratory and chemical industry settings. In this study, a selective mono-hydrogenation of electron-poor substrates was achieved using specific Rh(CO)(2)acac/xantphos based catalysts. This finding is significant for the design of related hydrogenation processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jianfei Yu, Haowei Zhu, Xumu Zhang, Gen-Qiang Chen
Summary: A new series of chiral ferrocene-based diphosphino-ethane ligands, f-DPE, were developed and applied in the hydrogenation of 2-substituted acrylic acids to obtain chiral propanoic acids with high yields and enantioselectivities. The synthesis of well-known anti-inflammatory drugs, such as ibuprofen, naproxen, and flurbiprofen, was also efficiently achieved using this method. The synthetic utilities of the method were demonstrated through gram-scale experiments.
Article
Chemistry, Multidisciplinary
Peng Gao, Miaolin Ke, Tong Ru, Guanfeng Liang, Fen-Er Chen
Summary: This work presents the preparation and synthetic application of a class of water-soluble PNP ligands. These ligands were incorporated into catalysts and successfully used for the regioselective hydroformylation of arylalkenes, providing efficient access to α-aryl propionaldehydes with high yield and selectivity. The synthetic methodology was further demonstrated through gram-scale synthesis and diverse transformations for non-steroidal antiinflammatory drugs.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Elizabeth M. Bolitho, Nathan G. Worby, James P. C. Coverdale, Juliusz A. Wolny, Volker Schuenemann, Peter J. Sadler
Summary: Organo-osmium(II) complexes catalyze the reduction of prochiral ketones to optically pure alcohols with high efficiency and enantioselectivity. These complexes also exhibit high turnover frequencies and conversions for the asymmetric transfer hydrogenation of acetophenone-derived substrates.
Article
Chemistry, Physical
Christian H. Schiwek, Christian Jandl, Thorsten Bach
Summary: The direct hydrogenation of aromatic systems is an important method for obtaining saturated carbo- and heterocycles. This study reports a modular approach to efficiently and selectively hydrogenate 2,5-DKPs, resulting in high yields of saturated pentacyclic 2,5-DKPs.
Article
Chemistry, Physical
Christophe M. Saudan, Aurelien Berrocosa, Julie Quintaine, Stephanie Spoehrle, Laurent Maggi, Herve Mosimann, Lionel Saudan
Summary: This paper reports a method for the regio- and chemoselective hydrogenation of conjugated dienals using a large bite-angle diphosphine and a neutral rhodium complex catalyst in the presence of a weak base. This method offers high selectivity, mild reaction conditions, and a neutral alternative to the commonly employed Claisen rearrangement for the synthesis of γ,δ-unsaturated aldehydes.
Article
Chemistry, Physical
Adrian Garcia-Zaragoza, Christian Cerezo-Navarrete, Andres Mollar-Cuni, Pascual Ona-Burgos, Jose A. Mata, Avelino Corma, Luis M. Martinez-Prieto
Summary: The catalytic properties of graphene-supported ruthenium nanoparticles have been adjusted by modifying their metal surface with pyrene-tagged N-heterocyclic-carbene ligands. The activity and selectivity of the catalyst are highly dependent on the surface coverage of the ligands, with higher coverage leading to lower activity but higher selectivity. The reactivity and stability of the catalysts can be controlled by modifying the surface with specific ligands.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Abdelghani El Mouat, Chryslain Becquet, Jeremy Ternel, Michel Ferreira, Herve Bricout, Eric Monflier, Mohammed Lahcini, Sebastien Tilloy
Summary: This study reports the reductive hydroformylation of methyl 10-undecenoate in a biphasic liquid/liquid system. Under optimized conditions, the use of a specific ionic liquid immobilized rhodium/amine catalytic system allows for high yield of primary alcohols, which can be recycled.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Dmitry Yu Aleshin, Rosa Diego, Leoni A. Barrios, Yulia Nelyubina, Guillem Aromi, Valentin V. Novikov
Summary: The study successfully observed the dynamics of two rare spin states, opening up new possibilities for information storage and processing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Ivan S. Golovanov, Anton Leonov, Vladislav K. Lesnikov, Evgeny Pospelov, Kirill Frolov, Alexander A. Korlyukov, Yulia Nelyubina, Valentin V. Novikov, Alexey Yu Sukhorukov
Summary: TAAD can form a stable Fe(iv) complex with excellent dioxygen activation ability. It can be conjugated to various functional molecules, allowing the synthesis of steroidal and peptide molecules labeled with iron(iv). Additionally, the Fe(iv)-TAAD complex shows potential as a catalyst.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Alexander A. Pavlov, Valentin V. Novikov, Igor A. Nikovskiy, Elizaveta K. Melnikova, Yulia V. Nelyubina, Dmitry Y. Aleshin
Summary: The concept of reduced paramagnetic shifts (RPS) is applied to paramagnetic complexes with different metal ions and coordination environments, enabling accurate signal assignment and evaluation of magnetic susceptibility anisotropy. This approach emerged as a powerful alternative for analyzing NMR spectra of paramagnetic compounds in various applications.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Elizaveta A. Gusarova, Alexandra Zvyagina, Alexey E. Aleksandrov, Natalia Kuzmina, Andrey Shabatin, Alexey A. Averin, Alexey R. Tameev, Maria A. Kalinina
Summary: A new method for interfacial self-assembly of graphene oxide (GO) and 10,12-pentacosadiynoic acid into nanometer-thick light-absorbing films exhibiting synergetic enhancement of conductive properties is developed.
COLLOID AND INTERFACE SCIENCE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ekaterina S. Vlasenko, Igor A. Nikovskiy, Yulia V. Nelyubina, Alexander A. Korlyukov, Valentin V. Novikov
Summary: Porous metal-organic framework ZIF-8 materials containing incorporated rhodium nanoparticles were used as catalysts for the hydroformylation reactions. The size of the substrate molecule was found to affect the selectivity and conversion of the reaction. The incorporation of catalytic nanoparticles into the pores of a metal-organic framework opens up new possibilities for regioselective hydroformylation.
MENDELEEV COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
A. M. Pak, E. N. Zakharchenko, A. A. Korlyukov, V. V. Novikov
Summary: This study focuses on the preparation of a new type of food packaging using biocompatible functional materials. The composite films are made of a hydrocolloid matrix containing kappa carrageenan and hydroxypropyl methylcellulose, with particles of the antibacterial metal-organic framework MOF-5 immobilized in the pores. The prepared films show resistance to potentially pathogenic microorganisms, indicating the potential for manufacturing antimicrobial composite materials for food packaging.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Matteo Ceppatelli, Demetrio Scelta, Manuel Serrano-Ruiz, Kamil Dziubek, Fernando Izquierdo-Ruiz, J. Manuel Recio, Gaston Garbarino, Volodymyr Svitlyk, Mohamed Mezouar, Maurizio Peruzzini, Roberto Bini
Summary: This study investigates the direct chemical reactivity between phosphorus and nitrogen under high-pressure and high-temperature conditions. Two new compounds, α-P3N5 and γ-P3N5, were discovered, and the structural and vibrational changes of γ-P3N5 during compression were analyzed. The detection of α-P3N5 suggests it as an intermediate step in the conversion from phosphorus to γ-P3N5. The findings provide important insights into the chemical reactions between phosphorus and nitrogen.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander S. Belov, Valentin V. Novikov, Anna V. Vologzhanina, Alexander A. Pavlov, Artem S. Bogomyakov, Yan V. Zubavichus, Roman D. Svetogorov, Genrikh E. Zelinskii, Yan Z. Voloshin
Summary: This study investigates the fast crystallization and structural transformation of a cobalt (II) complex. The complex undergoes a temperature-induced spin crossover and its behavior is influenced by solvent and crystal polymorphism. The findings provide insights into the synthesis and properties of cobalt complexes.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Veronika V. V. Zlobina, Alexey S. S. Kiryutin, Igor A. A. Nikovskiy, Oleg I. I. Artyushin, Vitaly P. P. Kozinenko, Alexander S. S. Peregudov, Alexandra V. V. Yurkovskaya, Valentin V. V. Novikov
Summary: Parahydrogen-induced nuclear polarization significantly enhances the sensitivity of NMR spectroscopy for medical diagnostics and enables the creation of new probes for magnetic resonance imaging. In this study, unsaturated derivatives of phosphoric acid, propargyl, and allyl phosphates, are proposed as precursors for biocompatible hyperpolarized probes. The polarization transfer to H-1 and P-31 nuclei of their hydrogenation products using ALTADENA, PASADENA, and the PH-ECHO-INEPT+ pulse sequence of NMR spectroscopy resulted in a highly amplified signal, which is among the largest for parahydrogen-induced nuclear polarization transfer to the P-31 nucleus.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Elizaveta A. Gusarova, Alexandra I. Zvyagina, Alexey E. Aleksandrov, Alexey A. Averin, Alexey R. Tameev, Maria A. Kalinina
Summary: A combinatorial method was used to fabricate functionally different 2D hybrids using the same starting set of components. The hybrids were assembled into layered nanofilms and integrated into conventional ITO-based cells. Depending on their composition, the hybrids exhibited different operational characteristics, such as photovoltaic properties or monopolar conductive layers. The strategy can be easily applied to create various hybrid nanofilms with targeted functional properties for organic electronics.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Igor A. Nikovskiy, Pavel V. Dorovatovskii, Valentin V. Novikov, Yulia V. Nelyubina
Summary: Two coordination polymers were obtained through a PCET-assisted process using the hydroxy-pyrazolyl moiety of the ligand and the iron(II) ion as sources of proton and electron. Under mild conditions, the first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines was synthesized. Under harsh solvothermal conditions, a hydrogen atom transfer resulted in the transformation of hydroxyl groups, producing the third coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines. This PCET-assisted approach can be used to produce coordination polymers and metal-organic frameworks with the SCO-active core N-3(L)MN3(L).
Article
Chemistry, Physical
Sylwia Kostera, Stefan Weber, Ines Blaha, Maurizio Peruzzini, Karl Kirchner, Luca Gonsalvi
Summary: Well-defined, bench-stable Mn(I) non-pincer-type complexes were used as catalysts for the selective reduction of CO2 to boryl-protected MeOH in the presence of pinacolborane (HBpin). High yields were achieved under mild reaction conditions without the need for base or additives, using the alkylcarbonyl Mn(I) bis(phosphine) complexes fac-[Mn(CH2CH2CH3)(dippe)(CO)3] [Mn1, dippe = 1,2-bis(diisopropylphosphino)ethane] and [Mn(dippe)(CO)2{(mu-H)2(Bpin)}] (Mn4) as precatalysts. Mechanistic insights were obtained through NMR experiments and monitoring of the catalytic reactions.
Article
Chemistry, Multidisciplinary
Alexandra M. Pak, Elena A. Maiorova, Elizaveta D. Siaglova, Teimur M. Aliev, Elena N. Strukova, Aleksey V. Kireynov, Alexey A. Piryazev, Valentin V. Novikov
Summary: In this study, a biocompatible metal-organic framework MIL-100(Fe) was used to produce composite films based on ?-carrageenan and hydroxypropyl methylcellulose loaded with the active compounds of tea tree essential oil, and ensured the uniform distribution of the filler particles. The composite films showed excellent UV-blocking properties, good water vapor permeability, and moderate antibacterial activity against both Gram-negative and Gram-positive bacteria. The use of metal-organic frameworks as containers of hydrophobic molecules of natural active compounds makes the composites made from naturally occurring hydrocolloids attractive materials for active packaging of food products.
Article
Chemistry, Multidisciplinary
Sylwia Kostera, Gabriele Manca, Luca Gonsalvi
Summary: Catalytic hydrogenation of CO2 to formate was achieved using the neutral, halide-free, coordinatively saturated tris(carbonyl) manganese pincer-type complex [Mn(PNP)(CO)(3)] as catalyst, DBU as base, and LiOTf as Lewis acid additive. The reaction conditions were mild (60 bar, 80°C). DFT calculations revealed that the activation of the precatalyst occurred through intermolecular, base-assisted dihydrogen heterolytic splitting.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexander S. S. Belov, Svetlana A. A. Belova, Nikolay N. N. Efimov, Veronika V. V. Zlobina, Valentin V. V. Novikov, Yulya V. V. Nelyubina, Yan V. V. Zubavichus, Yan Z. Z. Voloshin, Alexander A. A. Pavlov
Summary: Title: Cobalt(II) pseudoclathrochelate complexes exhibit an intermediate trigonal prismatic-trigonal antiprismatic geometry. According to PPMS data, they show SMM behavior with Orbach relaxation barriers of approximately 90 K. Paramagnetic NMR experiments confirm the persistence of these magnetic characteristics in solution. Therefore, targeted delivery of this 3D molecular platform to a specific biosystem can be accomplished through straightforward apical functionalization without significant changes.
DALTON TRANSACTIONS
(2023)
