Article
Chemistry, Multidisciplinary
Ludwig Zapf, Sven Peters, Udo Radius, Maik Finze
Summary: The first examples of anionic cyclic (alkyl)(amino)carbenes (Ani-cAACs) with borane substituents have been successfully synthesized. The borane substituents modulate the sigma-donor or pi-acceptor abilities compared to their neutral analogues. A B(CN)(3)-substituted Ani-cAAC was generated and used in situ, leading to the high-yield synthesis of C2F5BF2-Ani-cAAC 6. Reactions of these novel ligands with elemental selenium and chloro(triphenylphosphine)gold(I) produced anionic selenium adducts 7 and 8 and the Ani-cAAC gold complex 9. The properties of these compounds and theoretical calculations provide insights into the electronic and steric properties of these unique and promising anionic cAACs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ekta Nag, Sridhar Battuluri, Kartik Chandra Mondal, Sudipta Roy
Summary: This study reports on the synthesis and isolation of silver nanoclusters with Ag12Cl3, Ag-29, and Ag-8 cores for the first time. It was found that these clusters exhibit different magnetic and optical properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Aditya Kulkarni, Selvakumar Arumugam, Maria Francis, Pulikanti Guruprasad Reddy, Ekta Nag, Sai Manoj N. V. T. Gorantla, Kartik Chandra Mondal, Sudipta Roy
Summary: Cyclic alkyl(amino) carbene (cAAC)-supported, structurally diverse alkali metal-phosphinidenides have been synthesized and characterized through NMR studies and X-ray diffraction. The mechanism of electron transfer process was supported by cyclic voltammetry studies and Density Functional Theory calculations. The solid state oligomerization process was found to be largely dependent on the ionic radii of alkali metal ions, steric bulk of cAAC ligands, and solvation/de-solvation/recombination of the dimeric unit.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Xinrui Ou, Giovanni Occhipinti, Eliza-Jayne Y. Boisvert, Vidar R. Jensen, Deryn E. Fogg
Summary: Ruthenium catalysts bearing cyclic (alkyl)(amino)carbene (CAAC) ligands are highly efficient in olefin metathesis due to their resistance to decomposition. However, turnover numbers in the metathesis of terminal olefins are sensitive to catalyst concentration due to the susceptibility of the methylidene species to decomposition. Understanding the partitioning of CAAC complexes between the precatalyst and the active species is critical for catalyst design.
Article
Chemistry, Physical
Antonio Del Vecchio, Jakub Talcik, Sophie Colombel-Rouen, Jan Lorkowski, Melinda R. Serrato, Thierry Roisnel, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit
Summary: New Blechert-type ruthenium complexes with cyclic(alkyl)(amino)carbene (CAAC) ligands show remarkable thermal stability in solution and excellent catalytic performances in various metathesis reactions. They exhibit high catalytic activity at low loading and can achieve high enantiomeric excess in asymmetric metathesis reactions.
Article
Chemistry, Multidisciplinary
Yang Gao, Sima Yazdani, Aaron Kendrick, Glen P. Junor, Taeho Kang, Douglas B. Grotjahn, Guy Bertrand, Rodolphe Jazzar, Keary M. Engle
Summary: In this study, a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes is described, facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. The reaction allows coupling of both alkyl- and aryl-substituted alkynes with a variety of boryl and silyl reagents with high alpha-selectivity. The versatile intermediates produced are scalable and can participate in various downstream transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Alexander V. Belyakov, Ekaterina P. Altova, Anatoliy N. Rykov, Pavel Yu. Sharanov, Igor F. Shishkov, Alexander S. Romanov
Summary: This study reports the gas-phase equilibrium molecular structure of a cyclic (alkyl)(amino) carbene (CAAC) copper(I) chloride (Cl) molecule and investigates it using experimental and computational methods. The results show that the geometry around the copper atom is not distorted in the ground state.
Review
Chemistry, Multidisciplinary
Saroj Kumar Kushvaha, Ankush Mishra, Herbert W. Roesky, Kartik Chandra Mondal
Summary: The isolation of cyclic (alkyl) amino carbenes (cAACs) in 2005 was a significant breakthrough in the field of stable carbenes. Their excellent electronic properties have led to their utilization in various areas of chemistry, including catalysis.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Nguyen Le Phuoc, Alexander C. Brannan, Alexander S. Romanov, Mikko Linnolahti
Summary: Gold-centered carbene-metal-amides (CMAs) with cyclic (alkyl)(amino)carbenes (CAACs) show potential as thermally activated delayed fluorescence (TADF) emitters. A density functional theory study of over 60 CMAs was conducted, evaluating computed parameters related to photoluminescence properties. The study revealed that TADF efficiency in CMAs is determined by an balance between oscillator strength coefficients and exchange energy. Based on the findings, promising new TADF emitters were proposed and synthesized, including the stable and highly radiative (Et2)CAAC)Au(carbazolide) complex.
Article
Polymer Science
Rui Tan, Xiaochun Mu, Haiyang Wang, Yang Li
Summary: By using (i)Pr(2)Im as a Lewis base ligand, beta-H elimination reactions in propylene polymerization were suppressed, resulting in high molecular weight polypropylene and block copolymers. DFT calculations showed that the delocalized electrons in (i)Pr(2)Im could decrease the electro positivity of active sites, providing a convenient strategy for tuning their electronic properties.
Article
Chemistry, Multidisciplinary
Julia Volk, Myron Heinz, Michael Leibold, Clemens Bruhn, Tobias Bens, Biprajit Sarkar, Max C. Holthausen, Ulrich Siemeling
Summary: Researchers have synthesized a novel cyclic compound with a 1,1'-ferrocenylene backbone, which exhibits unique structural and chemical properties. The compound's wide bond angle and redox-active backbone open up new possibilities for studying unconventional metalloradicals and oligoradicals.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Samir Kumar Sarkar, Subrata Kundu, Mohd Nazish, Johannes Kretsch, Regine Herbst-Irmer, Dietmar Stalke, Parameswaran Parvathy, Pattiyil Parameswaran, Herbert W. Roesky
Summary: Herein, the synthesis and characterization of carbene-stabilized boryl phosphinidenes 1-3 are reported. X-ray crystallography was used to confirm the structures of these compounds, and quantum mechanical studies revealed their double Lewis base properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Sudip Baguli, Subham Sarkar, Soumajit Nath, Dibyendu Mallick, Debabrata Mukherjee
Summary: In this study, two thermally stable azomethine ylides were isolated, and it was found that they formed N-picoCAAC-CuCl complexes when reacted with CuCl. Computational analysis revealed that the pendant Npy and the softer nature of Cu(I) played crucial roles in this reaction. The resulting complexes can be used as highly active Rh(I) catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jennifer Morvan, Marc Mauduit, Guy Bertrand, Rodolphe Jazzar
Summary: The discovery of cyclic (alkyl)(amino) carbenes (CAACs) in 2005 revolutionized the field of ruthenium olefin metathesis by providing stronger metal-carbene bonds and increased catalytic activity, as demonstrated in patents.
Article
Chemistry, Multidisciplinary
Corinna Czernetzki, Merle Arrowsmith, Felipe Fantuzzi, Annalena Gartner, Tobias Troster, Ivo Krummenacher, Fabian Schorr, Holger Braunschweig
Summary: The reduction of a cyclic alkyl(amino)carbene-stabilized organoberyllium chloride led to the first neutral beryllium radical, which was characterized by a variety of spectroscopic techniques and computational methods. This compound provides a new theoretical basis for studying the reactivity of related compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Saroj Kumar Kushvaha, Ankush Mishra, Herbert W. Roesky, Kartik Chandra Mondal
Summary: The isolation of cyclic (alkyl) amino carbenes (cAACs) in 2005 was a significant breakthrough in the field of stable carbenes. Their excellent electronic properties have led to their utilization in various areas of chemistry, including catalysis.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Ekta Nag, Aditya Kulkarni, Sai Manoj N. V. T. Gorantla, Nico Graw, Maria Francis, Regine Herbst-Irmer, Dietmar Stalke, Herbert W. Roesky, Kartik Chandra Mondal, Sudipta Roy
Summary: The precursor SbCl (Top) has been used for the synthesis of a distibane compound via one-electron reduction using KC8. Different alkali metals were used as reducing agents to isolate corresponding stable dimeric alkali metal antimonides. The synthesized compounds were characterized using various analytical techniques and their catalytic activity and luminescent properties were studied.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Kavita Devi, Sai Manoj N. V. T. Gorantla, Kartik Chandra Mondal
Summary: This study provides a deeper insight into the N-2 binding and the influence of carbon atoms in previously reported Fe complexes through energy decomposition analysis and natural orbital for chemical valence calculations/analyses. The role of carbon atoms in the iron-carbon site is studied using deformation electron densities, and the interaction energy between Fe and N-2 as well as the orbital interactions between them are quantitatively estimated. The sigma-donation effects of three phosphine ligands and their effects on the Fe-N-2 bond are thoroughly studied.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Saroj Kumar Kushvaha, Sai Manoj N. V. T. Gorantla, Kartik Chandra Mondal
Summary: The structure and properties of donor ligands with bent Si2C units have been revealed through theoretical calculations. The results suggest that the Si2C unit can be stabilized by a pair of donor base ligands, with electrostatic and covalent orbital interactions playing a major role in the interaction energy.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Sai Manoj N. V. T. Gorantla, Harsha S. Karnamkkott, Selvakumar Arumugam, Sangita Mondal, Kartik Chandra Mondal
Summary: The factors influencing the binding, activation, and reduction of N-2 by FeMoco of nitrogenase are not completely understood. Model complexes have been synthesized and studied, but they differ from the real Fe-sites of FeMoco. This study focuses on a series of complexes containing a weak field ligand and investigates their effect on Fe-centers and N-2 binding.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Selvakumar Arumugam, Madhuri Bhattacharya, Sai Manoj N. V. T. Gorantla, Kartik Chandra Mondal
Summary: Two new series of air stable compounds containing cAAC(X)= fluorene/indene groups were isolated and characterized. These compounds showed green light emission and solvatochromism in solution, and exhibited a quasi-reversible electron transfer process as confirmed by cyclic voltammogram and electron paramagnetic resonance studies. DFT/TDDFT calculations and energy decomposition analysis were performed to study their bonding and electronic transitions. These redox active and thermally stable organic molecules may have potential applications in molecule based spin memory devices.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Multidisciplinary Sciences
Long Huang, Marcin Szewczyk, Rajesh Kancherla, Bholanath Maity, Chen Zhu, Luigi Cavallo, Magnus Rueping
Summary: In this study, stereodivergent allylic C(sp(3))-H bond arylations were successfully developed through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. Unlike the typical photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrated the feasibility of switching the C-C double bond stereoselectivity through ligand control and steric and electronic effects.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sunil Kumar, Selvakumar Arumugam, Bjoern Schwarz, Helmut Ehrenberg, Kartik Chandra Mondal
Summary: A representative Co(II) based single ion magnet (SIM) with N2O2 donor set and distorted pseudo-tetrahedral geometry has been synthesized and characterized. The atomic and electronic structure have been studied through DC magnetometry, ab-initio multi-reference CASSCF calculations, and qualitative ligand field theory. AC magnetometry has been used for the investigation of spin-lattice relaxation with temperature and magnetic field variations.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Manoj V. Mane, Sayan Dutta, Luigi Cavallo, Bholanath Maity
Summary: In recent years, there has been a growing interest in multicomponent reactions (MCRs) as environmentally friendly and reliable synthetic strategies for drug discovery. This article discusses theoretical investigations that unravel the mechanistic pathways in IrIII-CuII dual-catalyzed MCRs, experimentally reported by MacMillan, and explains the origin of selectivity between three-component and two-component coupling products. The results suggest that N-H bond activation is the rate-limiting step and the preference for a two-component product is governed by the relative stabilities of the CuII-X center dot intermediates.
Article
Chemistry, Multidisciplinary
Sonam Suthar, Kartik Chandra Mondal
Summary: In this study, energy decomposition analysis and natural orbital for chemical valence (EDA-NOCV) were used to investigate the bonding in cyclopropane rings of 49 different organic compounds. The majority of compounds (37/49) were found to preferentially form two dative covalent C-C bonds, while a smaller portion (7/49) favored two covalent electron sharing bonds. A few compounds (5/49) showed flexibility to adopt either bonding mode. The effects of functional groups on the bonding were also studied. The bonding analyses were supported by QTAIM analyses, which revealed distinct parameters for C-3 rings compared to normal hydrocarbons. The bonding in most cyclopropane rings was found to be similar to metal-olefin systems.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Krishnamoorthy Muralirajan, Rajesh Kancherla, Bholanath Maity, Safakath Karuthedath, Frederic Laquai, Luigi Cavallo, Magnus Rueping
Summary: In this manuscript, the authors describe the development of excited-state Pd-catalyzed dehydrogenative beta-sulfonylation reactions using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer and C-S cross-coupling processes at room temperature. The reaction efficiently converts amines into stable sulfonyl-substituted enamines and provides evidence for both static and dynamic quenching, as well as inner-sphere and outer-sphere mechanisms.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Bholanath Maity, Sayan Dutta, Luigi Cavallo
Summary: C-sp3-C cross-coupling, a dream reaction in the chemical community, can be achieved by activating C-sp3-H bonds through visible light-induced transition metal-catalysis under mild reaction conditions. However, this research area is still in its early stages due to the chemical and technical complexity of this catalysis. Complementary experimental and theoretical mechanistic studies are essential for rational advances, as each approach alone is inadequate to clarify the operative mechanisms. In this tutorial review, we summarize representative experimental and computational mechanistic studies, highlighting the weaknesses, strengths, and synergies between the two approaches.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Selvakumar Arumugam, Bjoern Schwarz, Prathap Ravichandran, Sunil Kumar, Liviu Ungur, Kartik Chandra Mondal
Summary: This work investigates the dynamic magnetic properties of a complex [(Cp-Ar3)(4)(Dy2Cl4K2)-Cl-III]& BULL;3.5(C7H8) synthesized using a tri-aryl-substituted cyclopentadienyl ligand (Cp-Ar3). The Dy(III)-metallocene weakly couples via K2Cl4 and exhibits slow relaxation of magnetization below 14.5 K under zero applied dc field through KD3 energy levels with an energy barrier of 136.9/133.7 cm(-1) at the Dy sites. The coordination of two chloride ions at each Dy centre leads to geometrical distortion and reduction of the single-ion axial anisotropy energy barrier.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Rajesh Kancherla, Krishnamoorthy Muralirajan, Sayan Dutta, Kuntal Pal, Bo Li, Bholanath Maity, Luigi Cavallo, Magnus Rueping
Summary: The development of metal complexes that can function as both photocatalysts and cross-coupling catalysts is challenging. This study reports that divalent palladium can act as a light-absorbing species to achieve carbon-nitrogen cross-coupling reactions under air. Palladium acetate can be used as both the photocatalyst and cross-coupling catalyst for the selective cross-coupling amination of differently substituted aryl halides at room temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Bo Li, Liang Yi, Bholanath Maity, Jiaqi Jia, Yuqin Shen, Xiang-Yu Chen, Luigi Cavallo, Magnus Rueping
Summary: Noncovalent interactions, particularly halogen bonding, play a crucial role in organic synthesis and catalysis, including the synthesis of organoselenium compounds. By utilizing the reaction balance between an electron donor-acceptor complex and Ph2Se2, the halogen bonding interaction facilitates the formation of C-Se bonds through the capture of alkyl radicals. This synthetic strategy has been successfully applied in the transformation of various carboxylic acids, natural products, drugs, and alpha-selenoamino acids.
