Article
Chemistry, Physical
Yuki Nagashima, Shiho Ishigaki, Jin Tanaka, Ken Tanaka
Summary: The research reveals that the (CpRh)-Rh-E(III) complex stabilizes key transition states in oxidative C-H bond functionalization reactions through strong orbital interactions, and the CpRh(III) complex is more stable in the reductive elimination step for sterically demanding substrates.
Article
Chemistry, Physical
Ziqi Liu, Jiaxin Song, Yushuang Zhang, Shuhui Sun, Zhe Kun, Jianbin Chen, Congxia Xie, Xiaofei Jia
Summary: An efficient Rh/PPh3 catalyst was developed for isomerization of 1-alkenes to (E)-2-alkenes, showing high yields and good stereoselectivities. A porous organic polymer supported rhodium catalyst (Rh/POP-PPh3-SO3Na) was synthesized to address catalyst separation and recycling issues, exhibiting high activity, stereoselectivity and recyclability. The olefin isomerization process involved two possible mechanisms, alkyl and allyl mechanisms.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
A. Hernandez Martinez, E. Lopez, S. Larregola, O. Furlong, M. S. Nazzarro, L. E. Cadus, F. N. Aguero
Summary: Ni-Rh bimetallic catalysts were prepared by the citrate method and characterized. The addition of Rh modified the reducibility and oxygen mobility of the catalysts. The catalyst Rh0.02Ni0.2 showed the highest activity and stability in the ethanol steam reforming reaction.
MATERIALS TODAY CHEMISTRY
(2022)
Article
Chemistry, Organic
Han Gao, Lingfei Hu, Yanlei Hu, Xiangying Lv, Yan-Bo Wu, Gang Lu
Summary: The research investigates the influence of Cp-X ligands on Rh-catalyzed annulations with alkynes, finding that Cp-E promotes alkyne insertion by affecting the rate-determining step of the reaction. The acceleration effect of Cp-E is attributed to different factors depending on the electronic properties of the rhodacycle intermediates.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Kezhuo Zhang, Jiaxin Huang, Wanxiang Zhao
Summary: In this study, a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters is presented. This involves the allylation of aldehydes with allylic boronic esters and the Rh-catalyzed chain-walking of homoallylic alcohols. The key to the success of this approach is the protodeboronation of alkenyl borylether intermediate using a tetravalent borate anion species in the presence of KHF2 and MeOH. This method offers mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies support the involvement of tandem allylation and chain-walking processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Malcolm P. Huestis, Jean-Philippe Leclerc, Robin Larouche-Gauthier, Samuel Aubert-Nicol, Arun Yadav, Koilpitchai Sivamuthuraman
Summary: This study presents a rhodium(III)-catalyzed, site-selective, C-H alkylation of quinoline N-oxides at C8 using commercially available diazo Meldrum's acid, allowing for the synthesis of various 8-quinolinylacetic acid esters on gram scale without the need for excess air-sensitive organometallic reagents.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Andrey Zadesenets, Ilia A. Garkul, Evgeny Yu. Filatov, Aleksandr S. Sukhikh, Pavel E. Plusnin, Artem S. Urlukov, Sergey I. Uskov, Dmitriy I. Potemkin, Sergey Korenev
Summary: Double oxalates of Rh with Ni and Co were synthesized and decomposed to form nanoalloys with excellent catalytic activity in low temperature steam reforming. Ni-Rh catalyst showed higher activity compared to monometallic catalysts.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Multidisciplinary
Theodora Ramantani, Georgios Bampos, Andreas Vavatsikos, Georgios Vatskalis, Dimitris I. Kondarides
Summary: The study investigated propane steam reforming over perovskite catalysts derived from LaNiO3, La0.8Sr0.2NiO3, and noble metal-substituted perovskites. The incorporation of foreign cations in the structure led to an increase in specific surface area and improved catalytic performance, with the in situ development of new phases actively participating in the reaction. Among the catalysts tested, LSNRh0.1 exhibited the best performance with high stability, propane conversion, and hydrogen selectivity.
Article
Chemistry, Inorganic & Nuclear
Ahmed M. Mansour, Krzysztof Radacki, Ola R. Shehab
Summary: The introduction of a propyl-sulfonic acid group at N1 of the coordinated ligand gives rise to a water-soluble complex that can bind to lysozyme through non-covalent interactions. This complex shows selective moderate toxicity against Cryptococcus neoformans and exhibits no cytotoxicity to healthy HEK293 cells.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Organic
Xiaoqiang Yan, Jun Wang
Summary: CpRh complexes have shown high catalytic activity as catalysts for enantioselective C-H activation reactions. The mainstream approach is to design chiral ligands with C2 symmetry to avoid the problem of Cp face selectivity during metalation. However, recent advances have also revealed CpRh catalysts with diastereotopic or enantiotopic Cp faces, which have been successfully applied in asymmetric C-H activation. This short review summarizes these advances and provides perspectives for future development.
SYNTHESIS-STUTTGART
(2023)
Article
Biochemistry & Molecular Biology
Azza A. Hassoon, Attila Szorcsik, Ferenc Bogar, Ibolya Zita Papp, Livia Fulop, Zoltan Kele, Tamas Gajda
Summary: The study revealed that the (η5-Cp*)Rh(III) cation can induce deprotonation of amide nitrogen at physiological pH, leading to tridentate coordination with histidine-containing peptides. At pH 7.4, the binding strength of peptides with (η5-Cp*)Rh(III) depends on the presence and position of histidine in the sequence.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Engineering, Chemical
Hang Zhang, Yuhua Wang, Zizhu Wang, Caiyun Xu, Shenghu Zhou
Summary: Alumina-supported RhSn alloy nano catalysts were prepared through sequential reduction method, resulting in the transformation of Rh@Sn core-shell nanoparticles into RhSn alloy on alumina. The Rh1Sn0.7/Al2O3 catalysts exhibited enhanced catalytic efficiency for toluene hydrogenation compared to Rh/Al2O3. A methyl cyclohexane yield of 99.2% was achieved at a toluene/Rh molar ratio of 118/1, 0.1 MPa H2 pressure, and 45°C within 2.0 hours. The improved catalytic efficiency of Rh1Sn0.7/Al2O3 can be attributed to the synergistic effect between Rh and Sn.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Organic
Laura Orian, F. Matthias Bickelhaupt
Summary: Metal-mediated [2+2+2] cycloadditions are a versatile synthetic route, and computational studies have revealed important mechanistic details. Half-sandwich catalysts feature structural fluxionality, with the metal continuously 'slipping' on the ring during catalysis, impacting catalyst performance.
Article
Chemistry, Inorganic & Nuclear
Urs Fischbach, Matthias Vogt, Peter Coburger, Monica Trincado, Hansjoerg Gruetzmacher
Summary: New complexes [Rh(Me)(trop(3)P)] and [Rh(Ph)(trop(3)P)] were synthesized by adding organolithium reagents to the parent pentacoordinated chloride complex. These complexes have a unique structure and exhibit the liberation of methyl and phenyl radicals upon oxidation.
Article
Chemistry, Inorganic & Nuclear
M. Gladysheva, P. E. Plyusnin, Yu Shubin, A. A. Vedyagin, S. Korenev
Summary: A new complex salt was synthesized and characterized through various analytical methods. The compound exhibited specific crystal structure and thermal behavior, leading to the formation of trimetallic nanoalloys and metal oxide phases. The obtained alloy nanoparticles were used as catalysts and tested for their catalytic activity and stability in a CO oxidation model reaction.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Marina Perez-Jimenez, Natalia Curado, Celia Maya, Jesus Campos, Eliseo Ruiz, Santiago Alvarez, Ernesto Carmona
Summary: This study focuses on complex [Mo-2(H)(2)(mu-Ad(Dipp2))(2)] (1) and its adducts with tetrahydrofuran and pyridine. Computational studies provide insights into the coordination and electronic characteristics of the central trans-Mo2H2 unit, as well as the reactivity of the Mo-H bonds in these complexes. Reactions investigated include oxidation of the adducts by silver triflimidate to form a monohydride complex with a bridging triflimidate ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Marina Perez-Jimenez, Natalia Curado, Celia Maya, Jesus Campos, Jesus Jover, Santiago Alvarez, Ernesto Carmona
Summary: The reaction between LiAlH4 and complexes containing (H)Mo Mo cores results in the coordination of LiH molecules and the formation of Mo-H-Li three-center-two-electron bonds. The complexes exhibit a hydride-rich Mo6Li9H18 supramolecular organization that is stable and can withstand substitution of solvating molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Nereida Hidalgo, Carlos Romero-Perez, Celia Maya, Israel Fernandez, Jesus Campos
Summary: Metal-only Lewis pairs based on zinc electrophiles are of interest in Negishi cross-coupling reactions. This study explores the use of sterically hindered [Pt((PBu3)-Bu-t)(2)] (1) to access Pt/Zn bimetallic complexes, resulting in the isolation of unique compounds with different reactivity. The cooperative reactivity of 1/ZnX2 pairs (X = Cl, Br, I, and OTf) towards water and dihydrogen is also disclosed, demonstrating bimetallic frustration.
Article
Chemistry, Multidisciplinary
Marina Perez-Jimenez, Jesus Campos, Jesus Jover, Santiago Alvarez, Ernesto Carmona
Summary: LiCH3 and LiCH2CH3 react with complex [Mo-2(H)(2)(μ-Ad(Dipp2))(2)(thf)(2)] (1 center dot thf) to form complexes with coordination of LiCH2R (R=H, CH3). Computational studies reveal the existence of five-center six-electron bonding within the H-Mo(sic)Mo-C-Li metallacycles, with predominantly ionic Li-C and Li-H interactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hugo Fouilloux, Marie-Noelle Rager, Pablo Rios, Salvador Conejero, Christophe M. Thomas
Summary: This study introduces a novel material design strategy using platinum complexes to catalyze the formation of recyclable poly(silylether)s from biomass-derived building blocks under mild conditions. The obtained polymers exhibit low T-g values, thermal stability, and resistance towards uncatalyzed methanolysis, with the ability to be chemically recycled through acid-catalyzed hydrolysis or methanolysis, showing great potential as sustainable materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Pablo Rios, Salvador Conejero, Israel Fernandez
Summary: The bonding situation of sigma-E-H (E=Si, B) complexes in transition metal compounds has been studied using Density Functional Theory calculations. It was found that the coordination mode between eta(1) and eta(2) is ambiguous and depends on the strength of the backdonation. This study provides a new quantitative analysis method for understanding the bonding behavior of transition metal compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Marina Perez-Jimenez, Jesus Campos, Jesus Jover, Santiago Alvarez, Ernesto Carmona
Summary: In this study, the coordination of E-C bonds (E = Zn, Mg, Al) to the Mo atoms of dimolybdenum complexes and the formation of dimolybdenum compounds through reactions with zincocenes were explored. The bonding mechanism of the reported H-Mo strictly equivalent to Mo-E-R rings was revealed through DFT calculations and NBO analysis.
Article
Chemistry, Inorganic & Nuclear
Carlos J. Laglera-Gandara, Pablo Rios, Francisco Jose Fernandez-de-Cordova, Marina Barturen, Israel Fernandez, Salvador Conejero
Summary: The study revealed that low electron count Pt(II) complexes react with tertiary hydrogermanes to generate platinum(II) germyl derivatives. Through low-temperature NMR studies, some of the cr-GeH intermediates were detected and characterized, which further evolved into platinum-germyl species. Computational analysis suggested that the interaction between the H-Ge bond and the platinum center involves both donation and backdonation of electrons. Additionally, primary and secondary hydrogermanes also produced platinum-germyl complexes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Alejandra Pita-Milleiro, Macarena G. Alferez, Juan J. Moreno, Maria F. Espada, Celia Maya, Jesus Campos
Summary: The divergent reactivity of a cationic iridium complex toward organolithium and Grignard reagents is discussed. The Cp* ligand exhibits unexpected electrophilic behavior towards organolithium reagents and can also undergo facile deprotonation in the presence of less nucleophilic organolithium reagents. Weaker alkylating agents effectively achieve alkylation of the metal center, and the reactive iridium(III) alkyls participate in subsequent reactions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Celia Maya
Summary: Chemistry and biochemistry instructors play a crucial role in helping students develop the skills needed to visualize and analyze 3D biomolecular structures and their functions. This paper presents a series of workouts using free online resources and the PyMOL computer program, focusing on the structural characteristics of the spike protein S of the SARS-CoV-2 virus and its infection process. These activities aim to engage structural biology students in examining macromolecules and developing procedures for controlling COVID-19 and future infectious diseases. PyMOL session files and student activities are provided.
JOURNAL OF CHEMICAL EDUCATION
(2023)
Article
Chemistry, Physical
Raquel J. Rama, Celia Maya, Francisco Molina, Ainara Nova, M. Carmen Nicasio
Summary: 2-Aminobiphenyl palladacycles are successful precatalysts for Pd-catalyzed cross-coupling reactions. This study investigates the mechanism of aryl amination reactions catalyzed by a cationic 2-aminobiphenyl palladacycle supported by a terphenyl phosphine ligand. The results show that the formation of an aryl carbazolyl Pd(II) complex reduces catalyst decomposition and can be considered as an alternative precatalyst in cross-coupling reactions.
Article
Chemistry, Inorganic & Nuclear
Nazaret Santamaria, Clara Velasco, Mario Marin, Celia Maya, M. Carmen Nicasio
Summary: In this study, a series of LPdCl2(amine) complexes bearing dialkylterphenyl phosphanes (PR2Ar ') and pyridine or morpholine ligands were synthesized and characterized. These novel compounds were tested as precatalysts in aryl amination reactions. The complex [(PCyp(2)Ar(Xyl2))PdCl2(morpholine)] exhibited the best catalytic activity, enabling the room-temperature coupling of aryl bromides and chlorides with aniline.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Pablo Rios, Amor Rodriguez, Salvador Conejero
Summary: This Perspective discusses the activation and cleavage of Si-H and B-H bonds by transition metal complexes in an electrophilic manner, comparing their reactivity with boron/aluminium Lewis acids and proposing mechanisms involving electrophilic reaction pathways.
Article
Chemistry, Multidisciplinary
Rosie J. Somerville, Andryj M. Borys, Marina Perez-Jimenez, Ainara Nova, David Balcells, Lorraine A. Malaspina, Simon Grabowsky, Ernesto Carmona, Eva Hevia, Jesus Campos
Summary: This article reports a study on a complex molecule of lithium nickelate benzyne. By evaluating its reactivity, the researchers discovered that this classical molecule is actually a unique octanuclear complex and confirmed it through X-ray crystallography and NMR studies. This finding provides new insights into organonickel chemistry and catalysis.
Article
Chemistry, Inorganic & Nuclear
Maria M. Alcaide, Praxedes Sanchez, Eleuterio Alvarez, Celia Maya, Joaquin Lopez-Serrano, Riccardo Peloso
Summary: In this study, Pt(ii) alkylidene 1a was reacted with terminal alkynes to form ylide complexes 3a-d through electrophilic activation and insertion. DFT calculations demonstrated that the observed regioselectivity is determined by the nucleophilic attack of the alkyne to the alkylidene carbon.
DALTON TRANSACTIONS
(2022)
