Article
Chemistry, Inorganic & Nuclear
Takuya Harada, Shinji Ando, Shigeki Kuwata
Summary: A ruthenium complex with an o-benzoquinone dioximate dianion was isolated, and the redox chemistry of its ligand was elucidated. The complex underwent ligand exchange and oxidation reactions, and the reduced ligand was regenerated through a catalytic reduction process with the aid of a base.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Austin P. Lanquist, Sayak Gupta, Kathlyn F. Al-Afyouni, Malik Al-Afyouni, Jeremy J. Kodanko, Claudia Turro
Summary: A series of five ruthenium complexes containing triphenyl phosphine groups were synthesized and characterized, with one complex showing enhanced cytotoxicity upon irradiation with blue light due to apoptosis mechanism. These findings highlight the enhancement of photochemotherapy by -CF3 groups and provide insight for future design of photocages for photochemotherapeutic drug delivery.
Article
Chemistry, Inorganic & Nuclear
Ranjeesh Thenarukandiyil, Eno Paenurk, Anthony Wong, Natalia Fridman, Amir Karton, Raanan Carmieli, Gabriel Menard, Renana Gershoni-Poranne, Graham de Ruiter
Summary: Metal-ligand cooperation is crucial in earth-abundant metal catalysis, with ligands acting as electron reservoirs to enhance redox chemistry. Iron BDI complexes were found to exhibit a wide range of oxidation states, with structural characterization revealing the redox noninnocence of the BDI ligand. Spectroscopic and computational studies further elucidated the electronic structure of the isolated complexes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Stephen Mensah, Joseph D. Rosenthal, Mamta Dagar, Tyson Brown, Jonathan J. Mills, Christopher G. Hamaker, Gregory M. Ferrence, Michael I. Webb
Summary: The evolution of high virulence bacterial strains has led to the development of novel therapeutic agents. Metal-based therapeutics, with their structural variability and unique modes of action, show great promise. This study focused on the preparation and evaluation of ruthenium(ii)-arene complexes containing Schiff base ligands with an attached ferrocene, and identified a complex with prominent activity against clinically relevant bacterial strains.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
Joy H. Farnaby, Tajrian Chowdhury, Samuel J. Horsewill, Bradley Wilson, Florian Jaroschik
Summary: This review summarizes the progress in organo-f-element chemistry in 2019, focusing on the discovery of new types of complexes, diverse reactivities of lanthanide metals, and reports on novel catalytic reactions. Advancements in hydrocarbyl complexes of the actinides are also highlighted.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
David Jago, Mark C. Walkey, Emma E. Gaschk, Peter R. Spackman, Matthew J. Piggott, Stephen A. Moggach, George A. Koutsantonis
Summary: The switching properties of several ruthenium organometallic complexes were studied. The spectroscopic and electrochemical properties of these complexes were determined by cyclic voltammetric and spectroelectrochemical experiments. Multiple stable redox states and switching states were achieved through acidochromism and/or photoisomerization. The alkynyl complexes exhibited more accessible switching states than the analogous vinyl complexes, as shown by spectroscopic, spectroelectrochemical, and X-ray crystallographic studies.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Marc Schnierle, Marie Leimkuhler, Mark R. Ringenberg
Summary: The bidentate ligand TzPy showed noninnocent behavior and could be modified by dienophiles. The kinetic analysis of the reaction between [1](+) and ViFc yielded Delta G double dagger(298 K) = 67 kJ mol(-1), while that of [1](+) and EthFc was Delta G double dagger(298 K) = 83 kJ mol(-1). The electrochemical reduction mechanism of [1Fc](+) was studied using cyclic voltammetry and UV-vis SEC experiments, supported by DFT calculations.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Reese A. Clendening, Stephanie S. Delancey, Andrew T. Poore, Shan Xue, Yisong Guo, Shiliang Tian, Tong Ren
Summary: Ferric bis-alkynyl complexes bearing redox-active substituents were characterized and the mixed valent properties of the singly oxidized species were investigated. The nature of the supporting macrocyclic ligand strongly influenced the degree of valence delocalization through the metal center. A tetraimine macrocycle enhanced valence delocalization, which was related to the altered ground state of the unoxidized complexes. The study provides insights into macrocyclic ligand-dependent valence delocalization and the role of π-acidity in the electronic structure of the complexes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Marzena Fandzloch, Tomasz Jedrzejewski, Liliana Dobrzanska, Gines M. Esteban-Parra, Joanna Wisniewska, Agata Paneth, Piotr Paneth, Jerzy Sitkowski
Summary: Three half-sandwich organometallic ruthenium(II) complexes containing purine analogs have been synthesized and characterized. The most active complex, [(eta(6)-p-cym)Ru(HmtpO)Cl-2], showed high cytotoxicity against HeLa cells and lower toxicity to normal fibroblast cells. This complex also exhibited antimetastatic activity and high antiparasitic effect, making it a promising candidate for further research.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Angelina Z. Petrovic, Dusan C. Cocic, Dirk Bockfeld, Marko Zivanovic, Nevena Milivojevic, Katarina Virijevic, Nenad Jankovic, Andreas Scheurer, Milan Vranes, Jovana V. Bogojeski
Summary: This paper presents the synthesis and structural characterization of three newly synthesized osmium(ii) complexes; investigates the kinetics of substitution reactions, binding properties, and interactions with biomolecules such as CT-DNA and HSA; further explores the binding mechanism through fluorescence competition experiments and molecular docking studies. In vitro cytotoxicity and redox status experiments on cancer cell lines provide insight into the potential molecular mechanisms of these complexes.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Luca Muenzfeld, Adrian Hauser, Pauline Haedinger, Florian Weigend, Peter W. Roesky
Summary: A homoleptic lanthanide quadruple-decker was synthesized for the first time, with the inner Sm ion in a divalent state and the outer ions in a trivalent state. Quantum chemical calculations and mechanistic studies provided insights into the formation pathways and transformations of this complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Feriannys Rivas, Andrea Medeiros, Cristina Quiroga, Diego Benitez, Marcelo Comini, Esteban Rodriguez-Arce, Ignacio Machado, Hugo Cerecetto, Dinorah Gambino
Summary: The study synthesized new Pd-Fe heterobimetallic compounds that showed promising activity against Trypanosoma brucei. A quantitative structure-activity relationships study highlighted the importance of electronic effects, lipophilicity, and metal type in determining the anti-T. brucei activity of compounds.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Beatrice Battistella, Linda Iffland-Muehlhaus, Maximillian Schuetze, Beatrice Cula, Uwe Kuhlmann, Holger Dau, Peter Hildebrandt, Thomas Lohmiller, Stefan Mebs, Ulf-Peter Apfel, Kallol Ray
Summary: In many metalloenzymes, sulfur-containing ligands play a role in catalytic processes, particularly in electron transfer reactions. By mimicking biological systems, we demonstrate the significance of S-ligation in cobalt-mediated oxygen reduction reactions (ORR). A comparison between the catalytic ORR capabilities of two cobalt complexes, one with nitrogen ligands and the other with sulfur ligands, shows that the introduction of chalcogen improves the catalytic performance. The involvement of sulfur in the O-2 reduction process is found to be the key for the enhanced catalytic ORR capabilities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jairus L. Lamola, Adedapo S. Adeyinka, Frederick P. Malan, Paseka T. Moshapo, Cedric W. Holzapfel, Munaka Christopher Maumela
Summary: The electronic and steric properties of newly developed biaryl phosphacycles were quantified using various experimental and theoretical methods. The study found moderate to good correlations between electronic descriptors derived from P-31-Se-77 coupling constants, C-O stretching frequency, computed bond enthalpies, molecular electrostatic potentials, and the unique steric parameterization studies of phospho-selenides.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Aleksandr A. Chamkin
Summary: This work was motivated by a recent report on the substitution process of the cyclopentadienyl ring in [CpIr(COD)Br](+) with P(OMe)(3) under mild conditions. The study demonstrates that the first step involves an exergonic exo-addition of P(OMe)(3) to the carbon in the Cp-ring, followed by the substitution of a non-chelating (eta(4)-C5H5P(OMe)(3)) ligand.
NEW JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Arijit Singha Hazari, Shubhadeep Chandra, Sanjib Kar, Biprajit Sarkar
Summary: Metal complexes of multi-porphyrins and multi-corroles have unique and interesting properties. The chemistry of metal complexes of bis-porphyrins and bis-corroles has been relatively underexplored. Despite the challenging synthesis, the exciting properties of these compounds make a strong case for further research.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Inorganic & Nuclear
Victoria A. Vaillard, Pablo D. Nieres, Santiago E. Vaillard, Fabio Doctorovich, Biprajit Sarkar, Nicolas Neuman
Summary: Metallocorroles have emerged as interesting and versatile catalysts for various redox reactions, with their diversity and richness offering endless possibilities for research.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Hanna E. Wagner, Nils Frank, Elham Barani, Christopher E. Anson, Lea Bayer, Annie K. Powell, Karin Fink, Frank Breher
Summary: This study describes the synthesis and characterization of novel 1,1'-difunctionalized ferrocene metalloligands. The functionalization of one cyclopentadienyl ring with different aryl moieties and the reaction with various metals yielded corresponding complexes. The electrochemical behavior of the ligands and complexes was investigated, and the influence of functional groups on the reaction of complexes was confirmed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Thomas Ruppert, Soeren Schlittenhardt, Nithin Suryadevara, Olaf Fuhr, Christopher E. Anson, Mario Ruben, Annie K. Powell
Summary: Four new heterometallic trinuclear complexes were synthesized and analyzed, revealing the variation of M-Dy-M angles and M···M distances with different metal M. Magnetic susceptibility measurements showed ferromagnetic interactions between Co-II and Cu-II at low temperatures.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Multidisciplinary
Andreas C. Hans, Patrick M. Becker, Johanna Haussmann, Simon Suhr, Daniel M. Wanner, Vera Lederer, Felix Willig, Wolfgang Frey, Biprajit Sarkar, Johannes Kaestner, Rene Peters
Summary: This article discloses a catalyst type that enables highly efficient direct 1,4-additions. The catalyst is a zwitterionic entity, with acetate binding to negatively charged Cu-II and serving as a counterion for benzimidazolium. All three functionalities are involved in the catalytic activation. The productivity of maleimides increased by a factor greater than 300 compared to the literature (TONs up to 6700). High stereoselectivity and productivity were achieved for a wide range of other Michael acceptors as well. The polyfunctional catalyst, accessible in only 4 steps from N-Ph-benzimidazole with an overall yield of 96%, remained robust during catalysis, allowing for multiple reuse with nearly constant efficiency. Mechanistic studies, particularly using DFT, provided a detailed understanding of how the catalyst operates. The benzimidazolium unit stabilizes the coordinated enolate nucleophile and prevents the dissociation of acetate/acetic acid from the catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Jan Hormann, Olga Verbitsky, Xiaoyu Zhou, Beatrice Battistella, Margarete van der Meer, Biprajit Sarkar, Cunyuan Zhao, Nora Kulak
Summary: We synthesized and characterized Cu(ii) complexes CuL1-CuL6 with cyclen-based ligands. The ligands L-1-L-6 comprise different donor sets including S and O atoms. The substitution of N donor atoms with hard donor O atoms leads to efficient oxidative nucleases, but dissociation of the complex upon reduction. We are showing that the rational combination of O and S atoms next to two nitrogen donors within the macrocycle leads to the stabilization of both redox states, resulting in the highest oxidative DNA cleavage activity within this family of cyclen-based Cu(ii) complexes.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Felix Stein, Simon Suhr, Arijit Singha Hazari, Robert Walter, Maite Noessler, Biprajit Sarkar
Summary: The synthesis and characterization of cationic azide-substituted 1,2,3-triazolium salts and their reactivity towards triphenylphosphine were reported. These salts were used as building blocks to develop unsymmetrical MIC-triazene-NHC/MIC' compounds which can be converted to radicals. The investigation of these radicals using various techniques sheds new light on the stabilization ability of MICs and their pi-accepting ability.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Felix Stein, Maite Noessler, Arijit Singha Hazari, Lisa Boeser, Robert Walter, Hang Liu, Elias Klemm, Biprajit Sarkar
Summary: In recent years, terpyridines (tpy) and mesoionic carbenes (MIC) have been widely used in metal complexes. In this study, a new class of complexes was obtained by combining PFC substituted tpy and MIC ligands within the same platform, and their structural, electrochemical and UV/Vis/NIR spectroelectrochemical properties were investigated. The resulting metal complexes were found to be potent electrocatalysts for CO2 reduction, with CO exclusively formed and a faradaic efficiency of 92%. A preliminary mechanistic study, including the isolation and characterization of a key intermediate, was also reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xiang Zhong, Zhao-Bo Hu, Tong-Kai Luo, Yan Peng, Sui-Jun Liu, Christopher E. Anson, Annie K. Powell, He-Rui Wen
Summary: Three one-dimensional Ln(III) complexes based on hydrazone Schiff-base ligands were reported. The Dy-III analogue exhibited a field-induced SMM behavior with U (eff) = 43 K, while the Gd-III analogue showed a significant magnetic thermal effect with a maximum -ΔS(m) value of 21.32 J kg(-1) K-1 at 3 K and 7 T. The structures of the complexes were also characterized. The SMM behavior in the Dy-III compound was attributed to its single-ion properties, which was confirmed by comparing it with the Y/Dy diluted complex. On the other hand, the magnetocaloric effect in the Gd-III analogue was observed, with a maximum entropy change -ΔS(m) of 21.32 J kg(-1) K-1 at ΔH = 7 T and 3 K.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Maite Noessler, Rene Jaeger, David Hunger, Marc Reimann, Tobias Bens, Nicolas I. Neuman, Arijit Singha Hazari, Martin Kaupp, Joris van Slageren, Biprajit Sarkar
Summary: Due to their ability to form stable molecular complexes, terpyridine ligands with tailor-made properties are of great interest in chemistry and material science. By synthesizing two terpyridine ligands with different fluorinated phenyl rings, we were able to prepare Co-II and Fe-II complexes and investigate their properties using various analytical techniques. Our findings revealed the structural characteristics, electrochemical behavior, and magnetic properties of these complexes, providing valuable insights into their applications and potential uses.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Simon Suhr, Nicolai Schroter, Merlin Kleoff, Nicolas Neuman, David Hunger, Robert Walter, Clemens Lucke, Felix Stein, Serhiy Demeshko, Hang Liu, Hans -Ulrich Reissig, Joris van Slageren, Biprajit Sarkar
Summary: Two homoleptic Fe(II) complexes with superbasic terpyridine derivatives as ligands were studied to investigate the relationship between spin state and electrochemical/spectroscopic behavior. Antiferromagnetic coupling between a ligand-centered radical and the high-spin metal center resulted in an anodic shift of the first reduction potential and a mixed valency species with a moderately intense intervalence-charge-transfer band. The different spin states also influenced the electrochemical reactivity, with the low-spin species acting as a precatalyst for electrocatalytic CO2 reduction and showing a Faradaic efficiency of 37% for CO formation, while the high-spin species only catalyzed proton reduction with a modest Faradaic efficiency of approximately 20%.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tobias Bens, Jasmin A. Kubler, Robert R. M. Walter, Julia Beerhues, Oliver S. Wenger, Biprajit Sarkar
Summary: We have developed new synthetic strategies to obtain a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands. By replacing bpy ligands in [Ru(bpy)3]2+ with pyridyl-MIC ligands, we were able to isolate three new complexes. We analyzed their properties using NMR spectroscopy, single-crystal X-ray diffraction analysis, cyclic voltammetry, and other techniques. These complexes showed potential applications in photocatalysis and photosensitization.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Crystallography
Firas Khalil Al-Zeidaneen, Christopher E. Anson, Annie K. Powell
Summary: This article reports the crystal structure of a nickel complex, in which the ligand undergoes an unexpected and unsymmetrical reaction. The structure and coordination geometry of the ligand are described in detail, and the intermolecular interactions in the molecule are revealed.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Ghulam Abbas, Francisco C. Franco Jr, S. Janani, J. N. Cheerlin Mishma, A. Manikandan, S. Muthu, Christopher E. Anson
Summary: A new dimeric complex was synthesized through a one-pot reaction in MeOH and characterized by infrared spectroscopy, elemental analysis, and single crystal X-ray diffraction. The theoretical study and molecular docking analysis revealed the structural properties and potential biological activity of the complex.
JOURNAL OF MOLECULAR STRUCTURE
(2024)
Article
Chemistry, Multidisciplinary
Ramananda Maity, Biprajit Sarkar
Summary: This paper provides an overview of recent developments in the field of 1,2,3-triazolylidene-type Mesoionic carbenes (MICs). These compounds are popular due to their modular synthesis and strong donor properties, and have found applications with both transition metals and main group elements. The paper discusses various aspects of MIC-containing compounds, including their synthesis, spectroscopic properties, and potential applications in catalysis and small-molecule activation.
