Article
Chemistry, Multidisciplinary
Zhongzheng Cui, Beining Wang, Junxia Li, Ronglin Pang, Yanrui Kang, Xu-Qiong Xiao
Summary: The steric and electronic properties of N-heterocyclic carbenes can be modified by using nido-C2B9 carborane anions as backbones, leading to the formation of N-heterocyclic carbene precursors and ligands, which can further form Au(I) NHC complexes. DFT calculations reveal the strong sigma-donating abilities of the carbene ligands.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sara Sabater, David Schmidt, Heidi (nee Schneider) Schmidt, Maximilian W. Kuntze-Fechner, Thomas Zell, Connie J. Isaac, Nasir A. Rajabi, Harry Grieve, William J. M. Blackaby, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Udo Radius, Michael K. Whittlesey
Summary: Addition of various phosphines to two-coordinate nickel species leads to a series of terminal phosphido nickel complexes with unique geometries. Smaller NHCs and phosphines facilitate the formation of bis-phosphido complexes, while DFT calculations show that P-P activation can be achieved through unconventional phosphine adducts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Lin-Jun Qi, Chong-Yang Shi, Peng-Fei Chen, Long Li, Gang Fang, Peng-Cheng Qian, Chao Deng, Jin-Mei Zhou, Long-Wu Ye
Summary: The study presents a novel gold-catalyzed 1,1-carboalkoxylation method for the synthesis of valuable cyclic compounds, enabling asymmetric synthesis through a chirality-transfer strategy. Further mechanistic insight into the distinct migration into gold carbenes is supported by theoretical calculations.
Article
Chemistry, Multidisciplinary
Francis Bru, Mathieu Lesieur, Albert Poater, Alexandra M. Z. Slawin, Luigi Cavallo, Catherine S. J. Cazin
Summary: The synthesis and isolation of [Pd(NHC)(PhC equivalent to CPh)] complexes were reported, which are new 14-electron Pd(0)-complexes that serve as key synthons for known palladium(0) and palladium(II) species and allow access to unprecedented mixed NHC-phosphite palladium(0) complexes. These complexes are also capable of catalyzing the facile hydrosilylation of allenes. DFT calculations provided insights into the relatively weak interaction between the metal and the diphenylacetylene ligand, comparing it with other ligands with varying coordinating power, structure, and electronic properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Paul Schmid, Felipe Fantuzzi, Jonas Klopf, Niklas B. Schroeder, Rian D. Dewhurst, Holger Braunschweig, Volker Engel, Bernd Engels
Summary: This issue features the research work of Bernd Engels, Holger Braunschweig, Volker Engel and their coworkers at University of Wurzburg on bridged boron compounds, highlighting the fascinating relationships between their composition, geometrical structures, and electronic structures.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Marcos A. S. Francisco, Felipe Fantuzzi, Thiago M. Cardozo, Pierre M. Esteves, Bernd Engels, Ricardo R. Oliveira
Summary: This study discusses the design principles and computational investigation of new organometallic platforms containing stable manganese-manganese bonds. The analysis focuses on the metal-carbene interaction and auxiliary coordination to generate short metal-metal bonds, closed-shell singlet multiplicities, and positive singlet-triplet energy gaps. The research identifies two classes of viable synthetic targets with thoroughly investigated electrostructural properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jing Zhang, Astrid Schaly, Jean-Claude Chambron, Bruno Vincent, Nathalie Zorn, Emmanuelle Leize-Wagner, Marion Jean, Nicolas Vanthuyne
Summary: Chiral gold(I) acetylide trinuclear complexes 1-3 based on the cyclotribenzylene platform and terminal PR3 ligands exhibited different emission spectra under various solvent conditions, with aggregation-induced green emission possibly originating from Au-Au interactions. The AIE spectrum of compound 3 was only observed in solutions containing 99% of MeOH, correlating with its solid state emission. Additionally, the AIE profiles of the enantiomers of 1 differed from that of rac-1, indicating the latter is a true racemate.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jing Zhang, Astrid Schaly, Jean-Claude Chambron, Bruno Vincent, Nathalie Zorn, Emmanuelle Leize-Wagner, Marion Jean, Nicolas Vanthuyne
Summary: Chiral gold(I) acetylide trinuclear complexes based on the cyclotribenzylene platform were characterized and their light emission properties were studied. Aggregation-induced green emission was observed in solvent mixtures, and differences in AIE profiles between enantiomers and racemate indicate the latter is a true racemate.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jana M. Holthoff, Elric Engelage, Adrian Ruff, Laura Galazzo, Enrica Bordignon, Stefan M. Huber, Robert Weiss
Summary: Carbenes with conjugatively connected redox system are capable of acting as auto-umpolung ligands and stabilizing open-shell species. In this study, the first neutral radical of such kind in the form of a dialkylamino-substituted bis(dicyanomethylene)cyclopropanide is described. The radical exhibits stability in solution and has been characterized through EPR measurements.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Ryohei Doi, Koji Shimizu, Yuma Ikemoto, Masashi Uchiyama, Mikiko Koshiba, Atsushi Furukawa, Katsumi Maenaka, Satoshi Watanabe, Yoshihiro Sato
Summary: This study reports a nickel-catalyzed cascade reaction to construct a 3-acylbenzo[b]furan skeleton. Through reaction condition optimization, the catalyst loading could be reduced to 5-10 mol %, leading to the synthesis of various functionalized compounds. Stoichiometric study of nickel complexes and DFT calculations were conducted to support a possible reaction mechanism.
Article
Chemistry, Multidisciplinary
Mukundam Vanga, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: A unique four-coordinate, classical gold(I)-carbonyl complex with substantial backdonation from gold has been isolated using a special ligand. The study of its lighter analogs of silver(I) and copper(I) enabled the investigation of trends in the coinage-metal family. Computational analysis revealed multiple components in the AuI-CO bonds. The complexes with the special ligand displayed remarkably low C-O stretching frequencies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Nikita M. Ankudinov, Denis A. Chusov, Yulia Nelyubina, Dmitry S. Perekalin
Summary: A new method for synthesizing chiral diene rhodium catalysts has been introduced, with one catalyst showing efficient asymmetric insertion of diazoesters into B-H and Si-H bonds with high yields and enantiomeric purity. The stereoselectivity of separation and catalytic reaction can be predicted by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yunlong Lu, Yuanhao Liu, Zhenlin Liang, Xiaoyan Ma, Lijuan Liu, Zhenfan Wen, Iogann Tolbatov, Alessandro Marrone, Wukun Liu
Summary: In this study, a bioorthogonal catalyst, Pd(PPh3)2Cl2, was used to convert the stable N-heterocyclic carbene (NHC)-gold(I)-alkyne complex 5 to its active species in biological environments. The active species effectively inhibits thioredoxin reductase (TrxR) and exhibits significant anticancer bioactivity in hepatocellular carcinoma (HCC).
CHINESE CHEMICAL LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Mengting Liu, Xiongda Xie, Ming Bao, Zhijing Zhang, Wenhao Hu, Yu Qian, Xinfang Xu
Summary: A gold-catalyzed carbocyclization/imidization cascade reaction has been developed for the synthesis of functionalized nitrones. The resulting products can be further converted into substituted naphthalenol analogues and exhibit potential tumor suppression activity.
MOLECULAR DIVERSITY
(2023)
Article
Chemistry, Multidisciplinary
Wen-Hao Li, Jiarui Yang, Hongyu Jing, Jian Zhang, Yu Wang, Jiong Li, Jie Zhao, Dingsheng Wang, Yadong Li
Summary: By designing and synthesizing a single-atomic-site catalyst with strong electronic metal-support interaction effects, researchers achieved highly selective conversion of electronically unbiased alkynes. Through studying reaction mechanisms, they demonstrated the exciting potential of EMSI in regulating regioselectivity in homogeneous catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mamata Ojha, Moumita Banerjee, Souvik Ray, Amit Kumar Singh, Anakuthil Anoop, N. D. Pradeep Singh
Summary: A phenothiazine-based photoremovable protecting group (PRPG) was developed for the single and dual release of carboxylic acids. The change in the oxidation state of the phenothiazine PRPG resulted in the generation of singlet oxygen instead of photorelease. The difference in photochemistry between oxygen-free and oxygen-functionalized phenothiazine was investigated and supported by DFT calculations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Nirmalya Podder, Subhasis Dey, Anakuthil Anoop, Sukanta Mandal
Summary: Four copper(II)-flavonolate compounds were developed as enzyme-substrate models. The study showed that the reactivity of the compounds is dependent on the substituent group, with -OMe exhibiting the highest reactivity. Experimental and theoretical studies revealed that the reactive flavonoxy radical (fla(center dot)) is generated through a single-electron transfer pathway.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Biswajit Sen, Saikat Roy, Sujay Garai, Sayan Roy, Anakuthil Anoop, Saumen Hajra
Summary: The reductive Heck cyclization of nonracemic benzylidene gamma-butyrolactone was investigated for the asymmetric synthesis of aryltetralin lignans. The stereochemistry of the benzylidene lactone was found to determine the mode of cyclization.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Akhil S. Nair, Anakuthil Anoop, Rajeev Ahuja, Biswarup Pathak
Summary: This study investigates the role of relativistic effects in nanocluster catalysis and finds that relativistic effects have significant impacts on cluster structure and catalytic activity, resulting in different phase diagrams and structural features for high coverage oxygenated clusters. While the overall catalytic activity of the cluster is not drastically affected by relativistic effects, they play crucial roles in the rate-determining step, transition-state configuration, and energetics of elementary reaction pathways.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Sunanda Panda, Devipriya Sivadasan, Nisha Job, Aland Sinjari, Krishnan Thirumoorthy, Anakuthil Anoop, Venkatesan S. Thimmakondu
Summary: This study theoretically investigated various structural isomers of MgC3H and MgC3H+, and found that the global minimum geometry of MgC3H is a cyclic isomer, while the global minimum of MgC3H+ is a linear isomer with four saddle points.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Saikat Roy, Anakuthil Anoop
Summary: By using density functional theory calculations and stochastic simulation analysis, we investigated the process of forming active palladium catalyst species from palladium acetate dimer. We found that the dimeric form can transform into experimentally observed monomeric species through sequential ligand addition, and analyzed the bonding in the dimeric form and the role of palladium in its stability. Additionally, we discovered that the dimeric form may serve as a potential catalytic precursor in palladium acetate-catalyzed coupling reactions.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Maya Khatun, Sayan Paul, Saikat Roy, Subhasis Dey, Anakuthil Anoop
Summary: In this study, popular density functionals (DFAs) and three-part corrected methods (3c-methods) were compared for their efficiency and accuracy in geometry optimization and energy evaluation. TPSS method showed accuracy and mPWPW method showed comparable speed and accuracy. Hybrid range-separated DFAs were the best option for relative energies of the clusters, with CAM-B3LYP excelling and B3LYP performing poorly. LC-BLYP was a balanced performer in terms of both geometry and relative stability, but lacked diversity. 3c-methods were fast but less impressive in relative stability.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Physics, Atomic, Molecular & Chemical
Sayon Satpati, Tarun Roy, Sandip Giri, Anakuthil Anoop, Venkatesan S. Thimmakondu, Subhas Ghosal
Summary: This paper investigates nine unusual isomers of the molecular formula C5H4 and studies their stability and novel bonding patterns. It is found that one of the planar tetra-coordinated carbon compounds is more stable than its tetrahedral counterpart and possesses a high dipole moment, which may aid in experimental detection in the laboratory or in low-temperature regions of the interstellar medium.
Article
Chemistry, Multidisciplinary
Sunanda Panda, Ayusman Chiranjibi, Devesh Awasthi, Subhas Ghoshal, Anakuthil Anoop
Summary: Using density functional theory, this study explores the potential energy surface of C2H3NO isomers, identifying 33 isomers with 11 low-energy isomers. Through bimolecular reaction analysis, it predicts Oxiran-2-ylazanide (9) and isocyanomethanol (48) as the kinetically favored products. This research significantly contributes to the understanding of prebiotic chemistry and the possible chemical processes that led to the emergence of life.
ACS EARTH AND SPACE CHEMISTRY
(2023)
Article
Physics, Atomic, Molecular & Chemical
Laura Torrejon-Rodriguez, Anna Parra-Llorca, Alejandro Pinilla-Gonzalez, Inmaculada Lara-Canton, Abel Albiach-Delgado, Maria Cernada, Raquel Escrig, Julia Kuligowski, Marta Aguar Carrascosa, Maximo Vento Torres
Summary: Fourteen reactive isomers of C5H and their ionic counterparts have been theoretically investigated. Two isomers have been detected in the Taurus Molecular Cloud-1, and theoretical calculations suggest the possible detection of another isomer in the interstellar medium.
Article
Chemistry, Physical
Maya Khatun, Pratik Sarkar, Sunanda Panda, Lazumla T. Sherpa, Anakuthil Anoop
Summary: In this study, the structural and energetic properties of nanoclusters and nanoalloys composed of group 13 elements (B, Al, and Ga) were investigated. Different density functionals and post-Hartree-Fock methods were compared, and the M06/def2-SVP method was recommended as the preferred approach.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Maya Khatun, Sayan Paul, Saikat Roy, Subhasis Dey, Anakut Anoop
Summary: This study compares popular density functionals (DFAs) and three-part corrected methods (3c-methods) in computational studies of gold thiolate clusters. The efficiency and accuracy of the DFAs and 3c-methods in geometry optimization and energy evaluation were compared. Some methods had difficulty locating different minima, while TPSS and mPWPW showed good accuracy and speed. For relative energies, hybrid range-separated DFAs were the best option, with CAM-B3LYP performing well and B3LYP performing poorly. LC-BLYP was a balanced performer, but lacked diversity, while 3c-methods were fast but less impressive in relative stability.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Organic
Anakuthil Anoop, Venkataraman Ganesh
Summary: This study presents a revised mechanism for the tropylium-catalyzed carboxylic acid O-H insertion with diazoesters, based on density functional theory calculations. The role of homoaromaticity in the reaction is described, and the energy profiles of four different pathways are compared to determine the plausible reaction pathway.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Saikat Roy, Anakuthil Anoop
Summary: We studied the formation steps and kinetics of active palladium catalyst species from palladium acetate dimer using density functional theory calculations, automated reaction search, and stochastic simulation analysis. We found that the dimeric form of palladium acetate is a resting state of the catalyst, and ligand addition led to the formation of monomeric species. Bonding analysis and the role of Pd in stabilizing the dimeric species were investigated. Our analysis suggests that the dimeric form of the catalyst can be a potential catalytic precursor in palladium acetate-catalyzed coupling reactions under experimental conditions.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Venkatesan S. Thimmakondu, Aland Sinjari, Diego Inostroza, Pothiappan Vairaprakash, Krishnan Thirumoorthy, Saikat Roy, Anakuthil Anoop, William Tiznado
Summary: While search algorithms are suitable for identifying low-energy isomers, fixing constraints is necessary for the successful operation of any structural search program. The number of explored candidates, choice of method, and availability of CPU time are limiting factors in solving the problem of structural isomerism. Chemical intuition can lead to new structures, but it requires increasing variables in the program. Therefore, an integrated approach between search algorithms and chemical intuition is necessary.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
