Article
Chemistry, Organic
Boxiang Liu, Zhicong Lin, Tairan Cheng, Tongxiang Cao, Shifa Zhu
Summary: In this study, a highly atom- and step-economical stereoselective synthesis of E-dienyl esters is reported. This approach involves rhodium catalysis and utilizes carboxylic acid and acetylene as C2 synthon through a cascade of cyclometalation and C-O coupling. The protocol demonstrates mild conditions, excellent functional group tolerance, exclusive E-stereoselectivity, and proves useful for late-stage modification of pharmaceuticals and natural products.
Article
Chemistry, Organic
Han Gao, Wujie Wang, Xiangying Lv, Gang Lu, Yuliang Li
Summary: The mechanism of Co(iii)-catalyzed annulation of N-chlorobenzamide with styrene was computationally studied, focusing on the effects of chiral cyclopentadienyl (Cp) ligands on enantioselectivity using energy decomposition analysis (EDA). The study revealed a spin-crossover event of Co complexes in the computed energy profile, with the triplet state of Co species being favored in most intermediates and transition states. The irreversible styrene migratory insertion was identified as the enantioselectivity-determining step, with steric effects being the dominant factor for high-level enantiocontrol, emphasizing the importance of additional bulky substituents on the Cp ring of trisubstituted BINOL-Cp ligands.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Bengi Ozgun Ozturk, Begum Sariaslan, Mina Askun, Zeynep Tunali, Solmaz Karabulut Sehitoglu
Summary: In this study, a sequential one-pot alkyne dimerization/hydration protocol was developed for the regioselective synthesis of alpha,beta-unsaturated ketones in quantitative yields. The reactions proceeded with high regioselectivity and rapid conversion, producing the corresponding unsaturated ketones within 15 minutes. Different arylacetylene derivatives could be efficiently converted to alpha,beta-unsaturated ketones in quantitative yields using this method.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Ana M. Geer, Janeth Navarro, Pablo Alaman-Valtierra, Nathan T. Coles, Deborah L. Kays, Cristina Tejel
Summary: Enhancing catalytic activity through synergic effects is a current challenge in homogeneous catalysis. In addition to the well-established metal-metal and metal-ligand cooperation, we showcase an example of self-activation by the substrate in controlling the catalytic activity of a two-coordinate iron complex. This behavior was observed in the regioselective cyclotrimerization of aryl acetylenes. Two kinetically distinct regimes were observed dependent upon the substrate-to-catalyst ratio, showing positive substrate cooperativity.
Article
Chemistry, Inorganic & Nuclear
Kate L. Flint, David M. Huang, Oliver M. Linder-Patton, Christopher J. Sumby, F. Richard Keene
Summary: In this study, ligands containing a 1,4-disubstituted 1,2,3-triazole unit were used to form triple-stranded dinuclear Ru(II) complexes with stereoisomeric mixtures. The introduction of a more flexible spacer resulted in the detection of isomeric mixtures and successful separation of mesocate and helicate forms. Additionally, photoconversion behavior was observed in these Ru(II) compounds. Partial separation of compounds containing a different spacer was achieved via chromatographic resolution, confirming the existence of a mesocate/helicate pair.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Julian Perdomenico, Natalia Levin, Anabella C. Fierro, Oswaldo A. Cordero Chernek, Thomas Weyhermueller, Leonardo D. Slep
Summary: The synthesis and characterization of a new ruthenium nitrosyl compound based on a pentadentate ligand has been reported. This compound exhibits redox processes in acetonitrile and aqueous solution, with spectroscopic characterization supporting the experimental findings. The study adds to the library of ruthenium nitrosyl species and confirms correlations found in related compounds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Uddhav Kanbur, Ryan J. Witzke, Jiayi Xu, Magali S. Ferrandon, Timothy A. Goetjen, A. Jeremy Kropf, Frederic A. Perras, Cong Liu, T. Don Tilley, David M. Kaphan, Massimiliano Delferro
Summary: A series of electrophilic organoruthenium complexes were synthesized and applied to selective hydrosilylation of olefins. Material 4 showed good catalytic activity and selectivity, and could be recycled multiple times without significant loss of activity.
Article
Chemistry, Multidisciplinary
Markus Bursch, Jan-Michael Mewes, Andreas Hansen, Stefan Grimme
Summary: This work provides best-practice guidance on various methodological and technical aspects of DFT calculations, including how to choose computational protocols, functionals, basis sets, and achieve an optimal balance between accuracy, robustness, and efficiency through multi-level approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Alice Palo, Giuseppina La Ganga, Francesco Nastasi, Massimo Guelfi, Marco Bortoluzzi, Guido Pampaloni, Fausto Puntoriero, Sebastiano Campagna, Fabio Marchetti
Summary: Mononuclear and dinuclear ruthenium complexes incorporating potentially catalytic and photosensitive subunits were synthesized and characterized. Some compounds showed catalytic water oxidation activity, while others did not exhibit catalytic processes due to the high oxidation potential induced by specific structural moieties.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Sagar Arepally, Ponnusamy Nandhakumar, Gisela A. Gonzalez-Montiel, Alina Dzhaparova, Gyeongho Kim, Ahyeon Ma, Ki Min Nam, Haesik Yang, Paul Ha-Yeon Cheong, Jin Kyoon Park
Summary: Electrochemical access to organometallic redox reagents allows for selective synthesis of various benzene derivatives with different regioisomers. A unified electrochemical strategy is presented for the selective cyclotrimerization of terminal alkynes to access both 1,3,5- and 1,2,4-regioisomeric trisubstituted benzene derivatives. The regiocontrol can be switched by the addition of a carboxylic acid.
Article
Chemistry, Multidisciplinary
Lia Sotorrios, Fedor M. Miloserdov, Anne-Frederique Pecharman, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey
Summary: The syntheses, reactivity, and electronic structure analyses of [Ru(PPh3)(2)(ZnMe)(4)H-2] and [Ru(PPh3)(2)(ZnPh)(4)H-2] are reported. [Ru(PPh3)(2)(ZnMe)(4)H-2] exhibits an 8-coordinate Ru center with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in [Ru(PPh3)(2)(ZnMe)(4)H-2] undergo facile, sequential exchange with ZnPh2 to give [Ru(PPh3)(2)(ZnPh)(4)H-2], which shows a 3 : 1 arrangement of ZnPh ligands. Mechanisms for ZnMe/ZnPh exchange and isomerization are proposed using DFT calculations, and the relationships of these {Ru(ZnR)(4)H-2} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Padinjare Veetil Saranya, Mohan Neetha, C. M. A. Afsina, Gopinathan Anilkumar
Summary: Multicomponent reactions (MCRs) can form highly functionalized compounds through the reaction between three or more reactants in a one-pot manner, providing products with the utilization of lesser resources and energy. MCRs adhere to the principles of green chemistry and have diverse applications across various fields.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yi Liu, Lianrui Cheng, Yi Huang, Yuting Yang, Xianfa Rao, Shuqing Zhou, Tayirjan Taylor Isimjan, Xiulin Yang
Summary: A metal-organic framework-derived strategy of constructing a Pt-free catalyst with Ru clusters anchored on porous Cu-Cu2O@C is proposed. The designed Ru/Cu-Cu2O@C exhibits superior alkaline hydrogen oxidation/evolution reaction (HOR/HER) performance, surpassing state-of-the-art Pt/C by 24 times in HOR activity and outperforming most documented Ru-based electrocatalysts in HER performance. Systematic characterization and density functional theory (DFT) calculations indicate that efficient electron transfer between Ru and Cu species contributes to the enhanced HOR and HER kinetics.
Review
Chemistry, Physical
Yunfei Guo, Mikko Muuronen, Frederic Lucas, Rint P. P. Sijbesma, Zeljko Tomovic
Summary: The formation of isocyanurate via cyclotrimerization of isocyanates is widely reported to provide polyurethane materials with improved properties. The review summarizes catalysts for the cyclotrimerization of isocyanates, categorizing them into two main classes and providing detailed information on catalyst structures, reaction conditions, and trimerization efficiency. The review aims to stimulate the design of more efficient catalysts and further understanding of the trimerization mechanism.
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: This study presents a rhodium-catalyzed electrochemical reaction for the selective synthesis of structurally diverse hexasubstituted arenes. The method demonstrates excellent selectivity and high atom economy.
Article
Multidisciplinary Sciences
Connor J. Clarke, Jemma A. Gibbard, Lewis Hutton, Jan R. R. Verlet, Basile F. E. Curchod
Summary: This study presents a detailed investigation of the photochemistry of isolated pyruvate anions. It reveals that the photoexcitation of pyruvate anions by UVA light leads to the formation of CO2, CO, and CH3-, which may have significant consequences for atmospheric chemistry.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Andrew T. Turley, Promeet K. Saha, Andrew Danos, Aisha N. Bismillah, Andrew P. Monkman, Dmitry S. Yufit, Basile F. E. Curchod, Marc K. Etherington, Paul R. McGonigal
Summary: This study investigates the relationship between solid-state luminescence and photocyclization of oligoaryl alkene chromophores by modulating the conjugation length. It is found that the emission of heptaaryl cycloheptatriene is turned off upon breaking the conjugation, but extended polycyclic frameworks can be formed. This method can be used to manipulate emission properties and selectively cyclize aromatic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Federica Agostini, Basile F. E. Curchod
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Sylvain Sudan, Damien W. Chen, Cesare Berton, Farzaneh Fadaei-Tirani, Kay Severin
Summary: A water-soluble coordination cage with a short PEG chain was synthesized by reacting Pd(NO3)(2) with a 1,3-di(pyridin-3-yl)benzene ligand. The cage exhibited high selectivity for chloride binding and displayed a significantly higher association constant compared to other chloride receptors. The introduction of a fluorinated dipyridyl ligand further enhanced the chloride binding affinity by a factor of 3.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Paul Varava, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Dimitrios A. Pantazis, Gerard P. Van Trieste, David C. Powers, Kay Severin
Summary: In this study, we report the structural characterization of copper complexes with both bridging and terminal alkenylidene ligands. The complexes were obtained by irradiation of Cu-I complexes with N-heterocyclic diazoolefin ligands. The isolation and structural characterization of the complex with a terminal alkenylidene ligand were achieved through crystalline matrix isolation and in crystallo photolysis at low temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Fang-Che Hsueh, Thayalan Rajeshkumar, Bastiaan Kooij, Rosario Scopelliti, Kay Severin, Laurent Maron, Ivica Zivkovic, Marinella Mazzanti
Summary: We report two unique thorium arenide complexes prepared by reduction of a Th-IV-siloxide complex in presence of naphthalene. The stored electrons in these complexes enable the reduction of a broad range of substrates. The reactivity can be tuned by the arenide binding mode, as shown in the reaction of complex 1 with diazoolefin IDipp=CN2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Paul Varava, Tak Hin Wong, Zhaowen Dong, Anastasia Yu. Gitlina, Andrzej Sienkiewicz, Wolfram Feuerstein, Rosario Scopelliti, Farzaneh Fadaei-Tirani, Kay Severin
Summary: The head-to-tail dimerization of N-heterocyclic diazoolefins is discussed, leading to the formation of strongly reducing quinoidal tetrazines. The oxidation of these tetrazines occurs stepwise, resulting in the isolation of a stable radical cation and diamagnetic dications. The latter can also be obtained by oxidative dimerization of diazoolefins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Michael R. R. Wozny, Andrea Di Luca, Dustin R. R. Morado, Andrea Picco, Rasha Khaddaj, Pablo Campomanes, Lazar Ivanovic, Patrick C. C. Hoffmann, Elizabeth A. A. Miller, Stefano Vanni, Wanda Kukulski
Summary: The endoplasmic reticulum and mitochondria play crucial roles in eukaryotic membrane biogenesis through lipid exchange at membrane contact sites. However, the mechanisms underlying this process are not well understood. In this study, researchers used integrative structural biology techniques to investigate the molecular organization of the endoplasmic reticulum-mitochondria encounter structure (ERMES) in yeast cells. They found that ERMES forms discrete bridge-like complexes at contact sites, consisting of synaptotagmin-like mitochondrial lipid binding protein domains. This study provides important insights into the supramolecular architecture and lipid transfer mechanisms involved in inter-organelle communication.
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Zhaowen Dong, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Kay Severin
Summary: Bent (hetero)allenes, such as carbodicarbenes and carbodiphosphoranes, have diverse applications in coordination chemistry as neutral C-donor ligands. N-Heterocyclic diazoolefins function similarly to L-type ligands, and in this study, the synthesis and reactivity of anionic diazoolefin are described. The anionic diazoolefin displays distinct reactivity, allowing for the preparation of diazo compounds via protonation, alkylation, or silylation. It can also be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes, resulting in the formation of a stable phosphinocarbene through the extrusion of dinitrogen.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiri Janos, Ivo S. Vinklarek, Jozef Rakovsky, Deb Pratim Mukhopadhyay, Basile F. E. Curchod, Michal Farnik, Petr Slavicek
Summary: In this study, the influence of photon energy on the photochemistry of CF3COCl molecule was investigated using nonadiabatic ab initio molecular dynamics techniques and velocity map imaging experiment. The results reveal that selective release of CO and Cl can be achieved by controlling the excitation wavelength.
ACS EARTH AND SPACE CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Kay Severin
Summary: Recent studies have discussed the recent advances in using nitrous oxide as an oxidant in metal-catalyzed reactions, focusing on reactions that occur under mild conditions in homogeneous solutions.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sylvain Sudan, Farzaneh Fadaei-Tirani, Kay Severin
Summary: A penta-stranded helicate was synthesized by combining [Pd(CH3CN)(4)](BF4)(2) with La(NO3)(3) and a polydentate ligand. The helicate exhibited low symmetry in both solution and solid state. By adjusting the metal-to-ligand ratio, a dynamic interconversion between the penta-stranded helicate and a symmetrical, four-stranded helicate was achieved.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Emanuele Petretto, Pablo Campomanes, Stefano Vanni
Summary: Understanding the dispersion stability and aggregation propensity of self-assembled monolayer gold NPs at a molecular level is crucial for rational design and optimal surface functionalization. Coarse-grained (CG) molecular dynamics (MD) simulations provide important insights into the molecular interactions in these systems. However, current CG models have limitations. Here, we develop a CG model compatible with the SPICA/SDK force field that accurately describes the behavior of AuNPs with different ligands and successfully predicts their aggregation and self-assembly in aqueous solution.
Article
Chemistry, Inorganic & Nuclear
Anastasia Yu. Gitlina, Farzaneh Fadaei-Tirani, Kay Severin
Summary: The isomerization of iridium(iii) complexes with metalated N-heterocyclic carbene (NHC) ligands was investigated. The fac isomers of complexes with 1-phenyl-3-methylbenzimidazolin-2-ylidene or 1-phenyl-3-benzylbenzimidazolin-2-ylidene ligands can be cleanly transformed into the mer isomers using HNTf2 and then NEt3. However, an iridium complex with a 1-phenyl-1,2,4-triazolo[4,3-f]phenanthridine-based carbene ligand could not undergo isomerization under similar conditions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Jack T. Taylor, David J. Tozer, Basile F. E. Curchod
Summary: Conical intersections are fundamental to understanding ultrafast, nonadiabatic processes in photochemistry. However, accurately calculating potential energy surfaces near conical intersections remains a challenge for popular electronic structure methods. This study focuses on conical intersections between excited electronic states and evaluates the performance of different methods in describing their topology and topography.
JOURNAL OF CHEMICAL PHYSICS
(2023)