Article
Chemistry, Inorganic & Nuclear
Yongliang Wei, Xiaowen Yang, Minghui Tian, Xue Wang, Tongdao Wang
Summary: The coordination of the B-H bond to a transition metal is of fundamental interest due to its relevance to the transition metal-mediated B-H bond activation mechanism and catalysis. While most reported examples involve sigma-borane/borate complexes with one or two sigma-B-H bonds, compounds with three such bonds are much less common. This study presents a facile synthesis approach for rare transition metal tris(sigma-B-H) borate complexes by salt elimination using [Cp*RuCl](4) and lithium trihydroborates Li[ArBH3] with 2,6-disubstituted aryl groups. These complexes exhibit remarkable thermal stability in solution and feature the unusual sigma-complex with three labile sigma-B-H bonds.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Shintaro Takahashi, Maria Frutos, Antoine Baceiredo, David Madec, Nathalie Saffon-Merceron, Vicenc Branchadell, Tsuyoshi Kato
Summary: The synthesis of a silyliumylidene cation complex 2 stabilized by a Ni-0-based donating ligand is described. Experimental and theoretical studies show that the highly electrophilic Si-II center is stabilized by a dative Ni -> Si sigma-interaction and pi-donations from the amino- and Ni-moieties. Due to similar energy levels of the frontier orbitals localized on the Si and Ni atoms, complex 2 exhibits competitive reactivity at both Si and Ni sites.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nils Ansmann, Joshua Muench, Marcel Schorpp, Lutz Greb
Summary: A novel chelating Lewis acidic bis(amidophenolato)silane is introduced as a strong Z-type ligand in this study, enabling the characterization of the first anionic [Pd(0)-X]- ate complex. The compounds exhibit a highly unusual square planar coordination and have important implications in Pd-catalyzed cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Dinesh Nugegoda, Leigh Anna Hunt, Anthony Devdass, Hammad Cheema, Ryan C. Fortenberry, Jonah W. Jurss, Nathan Hammer, Jared H. Delcamp
Summary: This study focuses on enhancing the rate of interfacial electron transfer reactions in dye-sensitized solar cells by designing a coordination complex between a redox shuttle and an organic dye. The results demonstrate that the designed dye-binding to the redox shuttle leads to improved dye regeneration rates and significantly higher device performance under fluorescent lighting conditions.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Daniel E. Trujillo-Gonzalez, Gerardo Gonzalez-Garcia, Trevor A. Hamlin, F. Matthias Bickelhaupt, Holger Braunschweig, J. Oscar C. Jimenez-Halla, Miquel Sola
Summary: Boron-boron multiple bonds, such as diborenes and diborynes, are stabilized by sigma-donor ligands that provide electron density to these electron-deficient species. These compounds play a significant role in the study of chemical bonding and can activate small molecules like transition metals. Our density functional calculations showed that ligands with high or medium Lewis basicity effectively stabilize diborynes, while beryllium-based ligands show promise in stabilizing diborynes without affecting the triple bond character.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Yuejia Zhu, Yongzhu Hu, Zhenjiang Li, Bo Liu, Yuanyuan Qu, Zhihao Zhang, Tianfo Guo, Yongqiang Li, Luoyu Gao, Kai Guo
Summary: By introducing 3-amino-1,2,4-benzo-thiadiazine-1,1-dioxide (ABTD) as a bidentate H-bond donor and triethylamine (TEA) as a mild Lewis base, successful control of polylactide (PLA) with predictable molecular weights and extremely narrow dispersities was achieved in room temperature solutions.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Ryan J. Andrews, John R. De Backere, Douglas W. Stephan
Summary: In this study, stable thionylium dications were synthesized with high acidity comparable to BF3 and PF5. These compounds can activate C-F bonds of fluoroalkanes and effectively deoxygenate O2- through reactions with Ph3PO and CuO.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Maria Frutos, Nasrina Parvin, Antoine Baceiredo, David Madec, Nathalie Saffon-Merceron, Vicenc Branchadell, Tsuyoshi Kato
Summary: A donor-stabilized silylene with a Ni-0-based donating ligand has been synthesized, showing a peculiar behavior due to the cooperative reactivity of Si and Ni centers. Calculations indicate that the orientation of the Ni-ligands with respect to the silylene moiety is crucial in determining the role of the Ni-fragment.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Koushik Saha, Dipak Kumar Roy, Rian D. Dewhurst, Sundargopal Ghosh, Holger Braunschweig
Summary: This article discusses the coordination of an element-element sigma bond to a transition metal, focusing on its significance in metal-mediated bond activation and catalysis. Research has been conducted on sigma-borane/-borate complexes using two distinct approaches, leading to a deeper understanding of their structures and properties.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Kuldeep Jaiswal, Naveen Malik, Boris Tumanskii, Gabriel Menard, Roman Dobrovetsky
Summary: In this study, the successful synthesis and characterization of the first persistent, formally 19-e Mo radical was achieved through photodissociation reaction, with the stabilization of the radical attributed to the unique electron-withdrawing effect of the o-carboranyl substituent at the phosphorus center.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Zhi Hao Toh, Hendrik Tinnermann, Dinh Cao Huan Do, Han Vinh Huynh, Tobias Kramer, Rowan D. Young
Summary: We isolated and characterized the gold(i)-iron(0) adducts and found that the gold-iron interaction is predominantly a sigma-donation from iron to gold. The Pr-i(2)-bimy carbenic C-13 NMR signal can be used to gauge the relative donor strength of Fe(0) donors.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
T. Ilgin Demirer, Bernd Morgenstern, Diego M. Andrada
Summary: The synthesis, structure, and bonding analysis of phosphanylgallane with P-H and Ga-Cl/H substitution are reported in this study. Lewis base- and Lewis acid/base-stabilized monomeric phosphanylgallane derivatives were obtained by reacting with LiPHR or LiPHR(BH3). These findings are of significance for studying the properties and applications of this class of compounds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Md. Ataur Rahman, Torsten Cellnik, Brij Bhushan Ahuja, Liang Li, Alan R. Healy
Summary: The aldol reaction is an important carbon-carbon bond-forming transformation in organic chemistry. Researchers have been working to develop direct catalytic variants of the aldol reaction for constructing chiral building blocks. In this study, a decarboxylative aldol reaction was developed that can produce all four possible stereoisomers of the aldol product from identical reactants in one step. The reaction is mild, can be performed on a large scale, and generates carbon dioxide as the only by-product. The method is compatible with a wide range of substrates and produces chiral beta-hydroxy thioester products with practical applications.
Article
Chemistry, Multidisciplinary
Felix O'Donnell, Douglas Turnbull, Stacey D. Wetmore, Michael Gerken
Summary: The study demonstrates the novel donor-stabilised [SbF4] (+) cations prepared from the autoionisation of SbF5 with the presence of bidentate N-donor ligands. These salts exhibit remarkable stability and were characterized using spectroscopic methods. The results indicate a significant degree of electron-pair donation from N to Sb stabilizes [SbF4] (+) with the cationic charge primarily being ligand-centred.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Engineering, Environmental
Luting Yu, Tonghui Guo, Haobo Yuan, Zequn Zhang, Zhiqiang Deng, Rui Zhao, Mengke Zheng, Jing Zhang, Wenwu Xu, Xiaohui Liu, Ziyang Hu, Yuejin Zhu
Summary: The study reveals that the inorganic CsPbI2Br perovskite solar cells with thioacetamide additive exhibit the best performance and good ambient stability, demonstrating the important role of Lewis acid-base additives in improving the performance of the cells.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Dennis Rottschaefer, Beate Neumann, Hans-Georg Stammler, Tetiana Sergeieva, Diego M. Andrada, Rajendra S. Ghadwal
Summary: The study presents a new 1,4-diphosphinine-1,4-diide compound derived from an anionic dicarbene, showing an antiaromatic nature in its molecular structure, which can form gold complexes and intermediate oxidation state compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Mahendra K. Sharma, Dennis Rottschafer, Timo Glodde, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: The text discusses the isolation of the first Sn-I diradical based on an anionic dicarbene scaffold, its molecular structure, and chemical reactivity with different compounds like PhSeSePh and MeOTf. The diradical exhibits a diatropic ring current and a small singlet-triplet energy gap, indicating its potential for further study in terms of its electronic properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Arne Merschel, Timo Glodde, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: This study reports the intramolecular 1,2-Dipp migration of seven mesoionic carbenes under nickel catalysis to generate 1,3-imidazoles. The use of these compounds to access super-iMICs demonstrates their superior stereoelectronic properties. The results reveal unprecedented reaction pathways in NHC chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mahendra K. Sharma, Dennis Rottschafer, Beate Neumann, Hans-Georg Stammler, Sergi Danes, Diego M. Andrada, Maurice van Gastel, Alexander Hinz, Rajendra S. Ghadwal
Summary: Metalloradicals play important roles in synthesis, catalysis, and bioinorganic chemistry. This study reports two iron radical cation complexes and investigates their oxidation reactions and structural features.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This paper discusses the tuning of structure and properties of main-group species (E) by controlling pi-conjugation and/or pi-donation using classical N-heterocyclic vinyl (NI-IV) ligands. By selecting appropriate carbene units, the electronic structure of derived species can be precisely controlled, resulting in stable solid materials.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Henric Steffenfauseweh, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Diego M. Andrada, Rajendra S. Ghadwal
Summary: In this study, the synthesis, characterization, and reactivity of the first cyclic C2As2-diradicaloid compound were reported. The compound exhibits a planar C2As2 ring, is diamagnetic, and shows well resolved NMR signals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Falk Ebeler, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: Mesoionic dithiolates ligands were synthesized by reacting with elemental sulfur, and were then used to form germylene and catenation products with other compounds. The structures and electronic properties of these compounds were studied.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Inorganic & Nuclear
Lothar Weber, Falk Ebeler, Rajendra S. Ghadwal
Summary: Dipnictenes, molecules with a double bond between two Group 15 elements, have made remarkable progress in recent years. The introduction of new ligand systems and non-carbon donor substituents has led to the discovery of numerous dipnictenes with diverse properties. Stable N-heterocyclic carbenes and other singlet carbenes have also been utilized in the synthesis of related unsaturated species. A comprehensive understanding of the structure, bonding, and reactivity of dipnictenes and the influence of substituents on their properties is crucial for advancements in the field.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Henric Steffenfauseweh, Dennis Rottschaefer, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Dariusz W. Szczepanik, Rajendra S. Ghadwal
Summary: A bordeaux-red solid compound based on an anionic dicarbene (ADC) with a central six-membered C4Sb2 ring is reported. The compound undergoes 2 e-oxidation to form a brick-red solid with unpaired electrons and lone pairs. The diradical character of the compound is calculated to be 36-39% according to different methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Arne Merschel, Dennis Rottschaefer, Beate Neumann, Hans-Georg Stammler, Mark Ringenberg, Maurice Van Gastel, T. Ilgin Demirer, Diego M. M. Andrada, Rajendra S. S. Ghadwal
Summary: In this study, we have successfully synthesized and isolated two stable anions K[SIPrBp] (4 a-K) and K[IPrBp] (4 b-K). These anions, derived from classical N-heterocyclic carbenes (NHCs), exist as violet crystalline solids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This review article aims to highlight recent advances in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. The synthetic viability and use of vicinal C4,C5-anionic dicarbenes (ADCs) based on a 1,3-imidazole framework are also presented. iMICs and ADCs have the potential to push the limit of classical NHCs by enabling access to conceptually new main-group heterocycles, radicals, molecular catalysts, ligand sets, and more.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Arne Merschel, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: Cyclic organoalane compounds [(ADC(Ar))AlH2](2) based on anionic dicarbene (ADC) frameworks have been reported. These compounds are stable crystalline solids and soluble in organic solvents. They exhibit annulated tricyclic structures with a planar central C4Al2-core embedded between two peripheral 1,3-imidazole rings.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Falk Ebeler, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: The decarbonylation of a cyclic bis-phosphaethynolatostannylene [(ADC)Sn(PCO)](2) based on an anionic dicarbene framework and under UV light results in the formation of a Sn2P2 cluster compound [(ADC)SnP](2). The [(ADC)SnP](2) compound binds reversibly with CO2 and enables catalytic hydroboration reaction with CO2. Additionally, it reacts with elemental selenium and Fe-2(CO)(9) to form corresponding compounds.
Article
Chemistry, Multidisciplinary
Arne Merschel, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: An unprecedented ring-opening of mesoionic carbenes (iMICs) based on an 1,3-imidazole scaffold to yield N-ethynylformimidamide (eFIM) derivatives as crystalline solids. The eFIMs are thermally stable under an inert atmosphere and show moderate air stability. They are excellent surrogates of iMICs and readily undergo ring-closing click reactions with a variety of main-group as well as transition metal Lewis acids to form challenging iMIC-compounds in good to excellent yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Arne Merschel, Yury V. Vishnevskiy, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: Phosphino-functionalized mesoionic olefins derived from a 1,3-imidazole-based mesoionic carbene have been reported. They exhibit remarkable basicity and their chemical properties and structures have been characterized.
DALTON TRANSACTIONS
(2022)
