Review
Chemistry, Multidisciplinary
Julien Monot, Enrico Marelli, Blanca Martin-Vaca, Didier Bourissou
Summary: The chemistry of (P,C)-cyclometalated complexes derived from naphthyl phosphines [(Np)(P,C)M] is reviewed and analysed in this paper. The three main synthetic approaches, P-chelation assisted C-H activation, oxidative addition and transmetalation, are described and compared. These complexes exhibit high thermal and chemical robustness, and have been shown to be competent catalysts in various transformations, as well as key intermediates in others.
CHEMICAL SOCIETY REVIEWS
(2023)
Review
Biochemistry & Molecular Biology
Antonio Zucca, Maria I. Pilo
Summary: Rollover cyclometalation is a unique reaction where a chelated heterocyclic ligand undergoes internal rotation to activate a remote C-H bond, forming a novel cyclometalated complex with unique properties. The rollover ligand, with an uncoordinated donor atom, displays multiple personalities and enables a series of distinct reactions, leading to potential applications in catalysis, organic synthesis, and advanced materials.
Article
Biochemistry & Molecular Biology
Lukas Kletsch, Rose Jordan, Alicia S. Koecher, Stefan Buss, Cristian A. Strassert, Axel Klein
Summary: The three complexes containing the tridentate ligand were synthesised using a base-assisted C-H activation method. Cyclic voltammetry showed increasing oxidation potentials along the series, while DFT calculations confirmed the character of molecular orbitals and contributions from various orbitals in the complexes. UV-vis absorption band energies also increased along the series, with different metal-to-ligand charge transfer properties observed.
Article
Chemistry, Multidisciplinary
Chinky Binnani, Sumangla Arora, Bhanu Priya, Puneet Gupta, Sanjay K. Singh
Summary: A class of 2-hydroxypyridine based ligands have been explored to enhance the catalytic activity of [(eta(6)-p-cymene)RuCl2](2) catalyst for ortho-C-H bond activation/arylation reaction in water. Among the studied ligands, 5-trifluoromethyl-2-hydroxypyridine (L6) showed significant enhancement in the catalytic activity of Ru(II) catalyst for ortho C-H bond arylation of 2-phenylpyridine. NMR and mass investigations suggested the involvement of ligand coordinated Ru(II) species in the C-H bond activation reaction. DFT calculations confirmed the important role of 2-hydroxypyridine based ligands in Ru(II) catalyzed C-H bond arylation of 2-phenylpyridine with lower energy barrier.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Leo Payen, Lukas Kletsch, Tobias Lapic, Mathias Wickleder, Axel Klein
Summary: Ni(II), Pd(II), and Pt(II) complexes containing the tridentate N<^>C<^>N-cyclometalating terpyridine ligand were synthesized through C-H activation. The terpy ligands showed higher ligand-centred reduction potentials compared to the prototypical dpb ligand. The metal-centred oxidations were facilitated by the dpb ligand. The cyclometalated terpy derivatives displayed reduced trans influence.
Article
Chemistry, Applied
Fatemeh Niroomand Hosseini, S. Masoud Nabavizadeh, Peyman Hamidizadeh, Fatemeh Niknam, Mahdi M. Abu-Omar
Summary: This study investigates the activation of C-H and N-H bonds in 2-(2'-pyridyl)benzimidazole upon coordination to a Pt(II) precursor complex, with a preference for N-H bond activation. The results show that the reaction occurs through substitution of one DMSO by the nitrogen atom of the pyridine ring, followed by N-H activation to form a new coordination compound.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Rapti Pal, Prasenjit Ghosh
Summary: In this study, the role of C-vacancies on a TiC(001) surface in methane activation and nonoxidative coupling to form C-2 hydrocarbons was investigated using density functional theory calculations and ab initio thermodynamic analysis. It was found that the first C-H bond cleavage is relatively easy and insensitive to the concentration of C-vacancy, while the dissociation of subsequent C-H bonds strongly depends on the vacancy concentration and becomes difficult with fewer vacancies. Among the two vacancy concentrations considered, it was determined that the catalyst with a vacancy concentration of 12.5% may be a good candidate for further C-C coupling studies.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Nikolaus Gorgas, Andrew J. P. White, Mark R. Crimmin
Summary: This study reports the reaction of an Fe-Al complex with a series of substituted pyridines. Depending on the substitution pattern of the substrate, site-selective sp(2) or sp(3) C-H bond activation is observed. A range of reaction products are formed, involving C-Al bond formation, C-C bond formation by nucleophilic addition, or deprotonation of the beta-diketiminate ligand. A divergent set of mechanisms involving a common intermediate is proposed.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
M. Arif Sajjad, Peter Schwerdtfeger, John A. Harrison, Alastair J. Nielson
Summary: DFT calculations revealed significant pi-syndetic donation in a nickel(II) complex with a chelating iminophosphane ligand, where a pendant aromatic ring forms a weak agostic interaction. The study also showed that electron withdrawing groups minimally affect the agostic and pi-syndetic donations, while electron donation switches off the pi-syndetic donation. Increasing the size of the substituent ortho to the agostic carbon causes rotation of the ring and a decline in both donations.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yazmin Varela, Gonzalo Ramirez-Garcia, J. Oscar C. Jimenez-Halla, Mariana Segovia-Mendoza, Heriberto Prado-Garcia, Katarzyna Wrobel, Kazimierz Wrobel, Silvia Gutierrez-Granados, Cristina Lemini, Oracio Serrano
Summary: In this study, a rollover iridacycle complex cis-[Ir(kappa(2)-C-N-L-1)(kappa(2)-N-N-L-1)Cl-2] was synthesized by reacting two equivalents of a new 2-(6-bromopyridin-2-yl)imidazo[1,2-a]pyridine (L-1) type ligand and IrCl3 in dimethylformamide. The rollover complex exhibited an unusual kappa(2)-C-N-cyclometallated ligand fragment involving C-H bond activation and a classic kappa(2)-N-N-donor mode. The structure of the complex was characterized using NMR, IR, and high-resolution mass spectrometry. The complex showed antiproliferative activities against breast cancer lines, and Density Functional Theory (DFT) calculations provided insights into the C-H bond activation process.
NEW JOURNAL OF CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Alexander D. Ryabov
Summary: The exchange of cyclometalated ligands is a versatile reaction that can be used for synthesizing cyclopalladated complexes and other metalacyclic derivatives, offering attractive synthetic possibilities and aiding in understanding key mechanistic pathways associated with C-H bond activation and C-M bond cleavage by transition metal complexes.
Article
Chemistry, Inorganic & Nuclear
Yufang Xie, Qiyi Miao, Wenhao Deng, Yilei Lu, Yinuo Yang, Xiaohui Chen, Rong-Zhen Liao, Shengfa Ye, Chen-Ho Tung, Wenguang Wang
Summary: A diamido-bridged dicobalt complex supported by a diamidonaphthalene ligand, Cp*Co2(2)(mu-1,8-C10H8(NH)(2)) (1), was synthesized and its reactivity towards redox transformations of the Co2N2 core was investigated. It was found that the Co(II)-Co(II) bond can be protonated, resulting in the formation of a bridging hydride [1H](+). The diamidonaphthalene ligand stabilizes the Co(II)Co(III) mixed-valent state (1(+)), which can bind CO to form [1-CO](+). Surprisingly, the mixed-valent complex also activates H2O to give a Co(III)Co(III) hydroxy complex [1-OH](+), accompanied by the release of H2.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Zekeriya Dogan, Nursel Acar Selcuki, Simon J. Coles, Abdurrahman Sengul
Summary: This study reports the synthesis and characterization of a coordination compound formed by platinum ions with a sterically hindered N4-donor ligand, exhibiting a diamond-shaped structure. The molecular units in the lattice form dimers in a head-to-tail fashion through hydrogen bonding, with the solvent molecule playing a key role in stabilizing the structure through hydrogen bonding. The DFT and TD-DFT results are consistent with experimental observations, showing stable hydrogen bond interactions between the monomers.
INORGANICA CHIMICA ACTA
(2022)
Review
Chemistry, Multidisciplinary
Bo Su, John F. Hartwig
Summary: This review discusses the rapid development and significance of enantioselective silylation and borylation of C-H bonds, emphasizing the importance of designing and developing chiral ligands for these reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jiaxin Lin, Yinwu Li, Zhuofeng Ke
Summary: A high-dimensional structure-activity relationship study was conducted on Lewis acid-transition metal (LA-TM) catalysts for hydrogen activation using density functional theory calculations. The Ga-Ni system showed the lowest free energy of activation, indicating the optimal combination of Lewis acid sites and transition metal centers. Multivariable analysis revealed that the combination of basic elemental properties and global features can better explain the activity of LA-TM catalysts, specifically the ratio of ionization energies between Lewis acids and transition metals, and the chemical hardness.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Iogann Tolbatov, Alessandro Marrone
Summary: The study aims to investigate the coordination of Pb(II) in aqueous solutions containing thiols through classical molecular dynamics simulations and test the application of cationic dummy atom schemes. It was found that the PB3 scheme can effectively model the binding of Pb(II) to a specific protein, indicating its potential value in coordination simulations.
THEORETICAL CHEMISTRY ACCOUNTS
(2021)
Article
Chemistry, Inorganic & Nuclear
Iogann Tolbatov, Damiano Cirri, Matteo Tarchi, Tiziano Marzo, Cecilia Coletti, Alessandro Marrone, Luigi Messori, Nazzareno Re, Lara Massai
Summary: In this study, the interactions between the anticancer metallodrug AP-1 and proteins were investigated using experimental and theoretical approaches. The results showed that AP-1 formed adducts with proteins, and in some cases, the formed adducts lacked the arsenic center. The theoretical analysis revealed that AP-1 attacks its biological targets by exchanging the chloride ligand, and only neutral histidine and deprotonated cysteine and selenocysteine can effectively replace the chloride ligand.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Iogann Tolbatov, Alessandro Marrone
Summary: Density functional theory approaches were used to investigate the structure and reactivity of four half-sandwich metal complexes, which are proposed as anticancer metallodrugs targeting Cys or Sec-containing proteins. The calculations revealed that all complexes preferentially target Cys or Sec via chloro exchange, with cym-bound and Cp*-bound complexes showing different affinities for neutral or anionic forms of these soft protein sites. Further analysis highlighted the significant role of solvation in determining the overall reactivity and selectivity of these metallodrugs.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Iogann Tolbatov, Alessandro Marrone
Summary: Transition metal atoms have the unique ability to induce significant changes in the electronic structure of their ligands, resulting in substantial modification of their chemical behavior, which explains well their evolutionary incorporation into living matter. The complexity of metal atom behaviors on the electronic level has led to the development of various quantum chemistry strategies for their description, while comprehensive understanding of the interaction between metal and biological matter requires adequate modeling of chemical phenomena and sometimes support from classical or semiempirical computational methods.
INORGANICA CHIMICA ACTA
(2022)
Article
Biochemistry & Molecular Biology
Lorenzo Chiaverini, Alessandro Pratesi, Damiano Cirri, Arianna Nardinocchi, Iogann Tolbatov, Alessandro Marrone, Mariagrazia Di Luca, Tiziano Marzo, Diego La Mendola
Summary: Auranofin (AF) is a chrysotherapeutic agent used for treating rheumatoid arthritis and is being repurposed for bacterial infections. The replacement of the thiosugar moiety with different ligands can expand its medicinal profile. The AF analogue, AF-AcCys, retains antibacterial effect against Staphylococcus aureus similar to AF, but is less effective against Staphylococcus epidermidis. AF-AcCys can induce protein metalation and bind to a specific peptide of hTrxR. The higher strength of the Au-S bond in AF-AcCys may contribute to its pharmacological differences. Lipophilicity may be a key feature for the different antibacterial activity between AF and AF-AcCys.
Article
Biochemistry & Molecular Biology
Lorenzo Chiaverini, Damiano Cirri, Iogann Tolbatov, Francesca Corsi, Ilaria Piano, Alessandro Marrone, Alessandro Pratesi, Tiziano Marzo, Diego La Mendola
Summary: Ammonium trichloro (dioxoethylene-O,O ') tellurate (AS101) is a potential therapeutic prodrug with immunomodulatory properties. This study investigates the activation process of AS101 and its analogues in the presence of water. The results demonstrate that water triggers the conversion of AS101 to the pharmacologically active species, and the effect is influenced by the halogens present. The study provides valuable insights into the chemical and mechanistic implications of AS101 activation.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Inorganic & Nuclear
Iogann Tolbatov, Alessandro Marrone
Summary: In this study, the kinetics of reaction between dirhodium and diruthenium paddlewheel complexes and protein nucleophiles were investigated using density functional theory. The results revealed the binding selectivity displayed by these complexes and supported the idea of using carboxylate ligands to yield dual acting metallodrugs.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Iogann Tolbatov, Loriano Storchi, Alessandro Marrone
Summary: This study investigates the effects of Bi3+ on the nsp13 protein and finds that it can decrease the interaction between nsp13 and nsp12, suggesting a potential anti-SARS-CoV-2 activity.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Iogann Tolbatov, Alessandro Marrone, William Shepard, Lorenzo Chiaverini, Mousumi Upadhyay Kahaly, Diego La Mendola, Tiziano Marzo, Lidia Ciccone
Summary: Inorganic drugs can tightly interact with proteins and this ability can be useful for solving protein structures. Using inorganic drugs with specific metal centers and ligands can drive binding towards desired regions of the protein target. Theoretical approaches can also contribute to protein structure determination. Here, we describe an integrated experimental-theoretical approach using metallodrugs for protein structure solving.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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
Chemistry, Inorganic & Nuclear
Luisa Ronga, Iogann Tolbatov, Ester Giorgi, Paulina Pisarek, Christine Enjalbal, Alessandro Marrone, Diego Tesauro, Ryszard Lobinski, Tiziano Marzo, Damiano Cirri, Alessandro Pratesi
Summary: A panel of four gold(I) complexes, inspired by auranofin, were reported by the research group. These complexes showed similarities to auranofin but exhibited distinct features, such as lower log P values. Experimental and theoretical studies revealed that structural modifications on the phosphine ligand of auranofin can impact the chemical properties and biological mode of action of the derivatives.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Alessandro Marrone, Richard H. Fish
Summary: This review focuses on the utilization of [Cp*Rh(bpy)H](+) complex as a biomimetic hydrogenase and regeneration reagent for the reduction of biomimetic NAD+ cofactors. The regeneration reaction with 1,4-NADH biomimetics is used in tandem with enzymes for organic synthesis. DFT mechanism studies and site-directed mutagenesis are discussed to explore the catalytic reactions and molecular recognition process.
Article
Pharmacology & Pharmacy
Iogann Tolbatov, Alessandro Marrone
Summary: Recently, the metallodrug auranofin has been found to restore penicillin and cephalosporin sensitivity in resistant bacterial strains by inhibiting the NDM-1 beta-lactamase through Zn/Au substitution in its bimetallic core. Density functional theory calculations revealed the unusual tetrahedral coordination of the two ions resulting from the substitution. The experimental X-ray structure of the gold-bound NDM-1 is consistent with either Au(I)-Au(I) or Au(II)-Au(II) bimetallic moieties, suggesting the most probable mechanism for the auranofin-based Zn/Au exchange in NDM-1.
Review
Chemistry, Inorganic & Nuclear
Iogann Tolbatov, Elisabetta Barresi, Sabrina Taliani, Diego La Mendola, Tiziano Marzo, Alessandro Marrone
Summary: This article provides an overview of the application of diruthenium(ii,iii) paddlewheel complexes for anticancer purposes. The use of this coordinative construct allows for combining the pharmacological properties of the dimetallic ruthenium center with specific carboxylate ligands to produce new entities with improved biological profiles. These systems also enable multiple drug deliveries to the target site, but chemico-physical aspects need to be considered for effective complex design.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Proceedings Paper
Computer Science, Software Engineering
Iogann Tolbatov, Alessandro Marrone
Summary: Metallodrugs are essential in contemporary medicinal chemistry as they provide a crucial inventory of therapeutic agents against various cancers and infections. Their unique features, such as the ability to transform ligands and attack targets through ligand substitution mechanism, make them valuable in multitarget therapy.
COMPUTATIONAL SCIENCE AND ITS APPLICATIONS, ICCSA 2022 WORKSHOPS, PT VI
(2022)
