Article
Chemistry, Inorganic & Nuclear
Srabani Srotoswini Mishra, Dillip Kumar Chand
Summary: A low-symmetry binuclear complex and an extremely rare trinuclear complex of palladium were synthesized through self-assembly reactions. The exclusive formation of specific isomers was predicted and confirmed experimentally. NMR study revealed conformational changes within the formed isomers.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Kamal Hossain, Amit Majumdar
Summary: The synthesis and reactivity of a binuclear zinc complex and an unprecedented binuclear zinc pentasulfido complex were studied. The reaction produced various sulfur compounds through oxidation-reduction reactions. The coordinated ligands and chains in the complexes can be used as catalysts to generate organic sulfur compounds.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Alexander Brand, Stephen Schulz, Alexander Hepp, Jan J. Weigand, Werner Uhl
Summary: The sterically constrained tricyclic phosphine 3a shows a highly negative reduction potential, forming a dianionic species reversibly. Reaction of 3a with Li/naphthalene results in a phosphaindole derivative dilithium compound, which can be used as a starting material for synthesizing new heterocyclic molecules. Treatment with H2O2 leads to oxidative cleavage of a strained PC4 ring to produce a bicyclic phosphinic acid.
Article
Chemistry, Physical
Marcel J. P. Schmitt, Sebastian V. Kruppa, Simon P. Walg, Werner R. Thiel, Wim Klopper, Christoph Riehn
Summary: Binuclear coinage metal phosphine complexes were studied to understand their noncovalent binding, structural properties, and electronic spectra. The observed order of electronic transitions was correlated with the intermetallic distance, but the high sensitivity of spectroscopic shifts towards metal composition could not be fully explained by this factor alone.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Tilak Naskar, Nabhendu Pal, Amit Majumdar
Summary: The synthesis and characterization of new binuclear Zn(ii) complexes with various ligands were presented in the study. It was found that Zn(ii) cannot mediate the cleavage of thiolates, leading to the isolation of binuclear Zn(ii)-thiolate complexes. Further investigations showed the formation of a new binuclear Zn(ii) complex featuring a bridging S-3(2-) unit through redox reactions involving thiolates and externally added elemental sulfur.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Margarita Escudero-Casao, Giulia Licini, Manuel Orlandi
Summary: A novel catalytic system based on copper(I) and chiral bis(phosphine) dioxides has been developed for the arylation of silyl enol ethers, yielding enolizable alpha-arylated ketones with high yields and enantiomeric excess up to 95%. This method is applicable to noncyclic ketones and complements other palladium-catalyzed approaches. Optimization of ligand structure was achieved through rational design driven by correlation analysis, and preliminary mechanistic hypotheses were evaluated to understand the role of chiral bis(phosphine) dioxides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Polymer Science
Jinxin Nie, Feiyang Ren, Zhen Li, Kun Tian, Hui Zou, Xiaohua Hou
Summary: Several binuclear vanadium complexes were synthesized and investigated as catalysts for ethylene (co)polymerization. The binuclear complexes exhibited higher activities than the mononuclear analogues in ethylene polymerization and showed moderate activity in copolymerization with polar vinyl monomers.
Article
Biochemistry & Molecular Biology
Maria V. Kashina, Andrei A. Karcheuski, Mikhail A. Kinzhalov, Konstantin V. Luzyanin, Svetlana A. Katkova
Summary: A series of platinum complexes with phosphine and isocyanide ligands were synthesized and evaluated as catalysts for photocatalytic hydrosilylation of alkynes. The phosphine-isocyanide complexes showed high yields under violet light irradiation, while the parent phosphine complexes were more efficient under blue light irradiation.
Article
Chemistry, Multidisciplinary
Patrick Herr, Christoph Kerzig, Christopher B. Larsen, Daniel Haussinger, Oliver S. Wenger
Summary: Metal complexes with d(6) valence electron configuration often exhibit luminescent metal-to-ligand charge transfer (MLCT) excited states, useful for various applications. Iron(ii) has been suggested as an Earth-abundant alternative, but no iron(ii) complex has been reported to show MLCT emission. In this study, manganese(I) complexes with isocyanide chelate ligands were found to exhibit MLCT luminescence in solution at room temperature, showing promising applications in energy and electron transfer reactions.
Article
Chemistry, Organic
Bence Varga, Peter Szemesi, Petra Nagy, Reka Herbay, Tamas Holczbauer, Elemer Fogassy, Gyorgy Keglevich, Peter Bagi
Summary: Secondary phosphine oxides with various aryl and alkyl groups were synthesized in racemic form and optically resolved using TADDOL derivatives. The resolution method showed good scope under optimized conditions, with successful preparation of enantiopure compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Clayton J. Curtis, Andrei Astashkin, Jeanet Conradie, Abhik Ghosh, Elisa Tomat
Summary: Oligopyrroles are a versatile class of redox-active ligands capable of stabilizing radicals, and dipyrrindiones are emerging as a compact platform for one-electron redox chemistry in transition metal complexes. The synthesis and deprotonation-driven S dimerization of a bis(aqua) palladium(II) dipyrrindione complex are reported, along with the characterization of its two quasi-reversible ligand-centered reduction processes. The resulting cobaltocenium salt features a diradical with weak antiferromagnetic exchange coupling, leading to a predominantly triplet state at measured temperatures.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Liesa Eickhoff, Pascal Kramer, Jonas Bresien, Dirk Michalik, Alexander Villinger, Axel Schulz
Summary: In the solution, Pacman chlorophosphane (2Cl) demonstrates rapid exchange of the endo/exo-orientation of the two P-Cl bonds in the molecule, which shows cooperativity. Experimental and quantum mechanical investigations confirm the crucial role of chloride ions in this dynamic process. Homologous Pacman halogen-phosphanes 2X were prepared through halogen exchange reactions (X = F, Br, and I) to validate the results, revealing accelerated dynamic behavior for heavier analogues and significant differences in the molecular structure, including the formation of an endo-endo substituted Pacman fluorophosphane as well as dicationic species by phosphorus halogen bond dissociation.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Simon G. Rachor, Robert Mueller, Philipp Wittwer, Martin Kaupp, Thomas Braun
Summary: Gold(I) fluoride complexes with phosphine ligands were synthesized from their iodide precursors. Quantum-chemical comparisons between phosphine and N-heterocyclic carbene complexes yielded similar bonding situations. Experimental and calculated F-19 NMR chemical shifts showed good agreement, with phosphine complexes displaying approximately 40 ppm low-field shifts compared to NHC complexes. Reactivity studies of water-sensitive gold(I) fluoride complexes demonstrated metal substitution using trimethylsilyl reagents. The compounds were characterized using NMR and X-ray diffraction methods.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Dandan Zhao, Yixuan Wu, Wenxin Huang, Silin Gong, Zhanfen Chen
Summary: A binuclear Schiff base copper(II) complex with potential antitumor activity and DNA cleavage ability was synthesized and characterized.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jeanette A. Adjei, Michael A. Kerr, Paul J. Ragogna
Summary: Dimethyl 2-vinylcyclopropane-1,1-dicarboxylate can undergo hydrophosphination reaction with primary or secondary phosphine without the need for a free radical initiator, under photolytic conditions. The resulting tertiary phosphines, after derivatization with S-8, can be obtained in a 27%-73% yield as moisture and air stable yellow or colorless oils. Control reactions suggest that this UV-induced hydrophosphination reaction proceeds through a radical mechanism.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Nicholas P. Taylor, Jorge A. Gonzalez, Gary S. Nichol, Andres Garcia-Dominguez, Andrew G. Leach, Guy C. Lloyd-Jones
Summary: The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured, leading to the development of a nucleofugality scale. The utility of this scale has been demonstrated by correlating substituent parameters with hydrolyses rates of MIDA boronates, identifying compounds with unusual kinetic lability or stability to hydrolysis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kang Yuan, Daniel Volland, Sven Kirschner, Marina Uzelac, Gary S. Nichol, Agnieszka Nowak-Krol, Michael J. Ingleson
Summary: This article develops an enhanced N-directed electrophilic C-H borylation methodology to access azaborine containing helicenes. The borylation process utilizes the protonation of an aminoborane with bistriflimidic acid. The synthesized helicenes show increased strain and racemization half-life, as well as improved fluorescence efficiency due to the incorporation of BN units.
Article
Chemistry, Multidisciplinary
Nicole Y. Meredith, Stefan Borsley, Ivan Smolyar, Gary S. Nichol, Christopher M. Baker, Kenneth B. Ling, Scott L. Cockroft
Summary: This study used synthetic molecular balances to quantify the energetics of amine/amide H-bonds in different solvents, effectively isolating the typically dominant influence of the solvent. The correlations between experimental and computed energies were found to vary depending on the solvent, but excellent correlations were achieved after dissecting solvent effects using Hunter's solvation model. Changes in the fitted constants revealed the energetics of secondary local interactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Yali Zhou, Gary S. Nichol, Jennifer A. Garden
Summary: Four novel homo- and heterometallic sodium and/or aluminium complexes based on the TrenSal ligand have been synthesized and characterized. The heterometallic compound [LNaAlMe] exhibited good catalytic activity and control in rac-lactide polymerization, while the homometallic sodium complexes showed higher activity but poorer control. Overall, the heterometallic complex [LNaAlMe] provided a balance of good activity and control compared to its homometallic analogues.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Helen M. O'Connor, William J. Tipping, Julia Vallejo, Gary S. Nichol, Karen Faulds, Duncan Graham, Euan K. Brechin, Paul J. Lusby
Summary: The study of host-guest chemistry in coordination cages is of great importance for applications such as drug delivery, sensing, and catalysis. This paper demonstrates the use of various techniques to investigate the host-guest chemistry of a novel Pd2L4 cage, which has high affinity for selectively binding dicyanoarene guests through hydrogen bonding and other weak interactions. Additionally, Raman spectroscopy is shown to be a valuable tool for analyzing coordination cages, using alkyne and nitrile reporter functional groups.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Adrian Moreno Gonzalez, Kieran Nicholson, Natalia Llopis, Gary S. Nichol, Thomas Langer, Alejandro Baeza, Stephen P. Thomas
Summary: In this study, high oxidation-state carbonyl coupling partners were reacted with enones using two-fold organoborane catalysis to directly obtain aldol-type products. This new retrosynthetic disconnection method is compatible with enolisable coupling partners and achieves excellent chemoselectivity and substrate scope.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Craig F. Steven, Martin Lee, Gary S. Nichol, Paul R. J. Davey, Elisabetta Chiarparin, Valerie G. Brunton, Alison N. Hulme
Summary: The fraction of sp(3)-hybdrised carbons (Fsp(3)) has been proposed to be an important consideration in medicinal chemistry. Small-molecule probes for Raman imaging are not optimized for biological applications. The study introduced modifications to a highly Raman-active motif and investigated the correlation between compound aggregation, Fsp(3), and crystal packing. Cellular imaging by stimulated Raman scattering microscopy provided insights for future Raman probe design.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Amy N. Price, Victoria Berryman, Tatsumi Ochiai, Jacob J. Shephard, Simon Parsons, Nikolas Kaltsoyannis, Polly L. Arnold
Summary: The article explores whether low-coordinate f-block molecules become more planar or pyramidal under pressure using high-pressure crystallography, with the result being dictated by the dipole moment of the complex and the volume of the planar form.
NATURE COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Jacob J. Shephard, Victoria E. J. Berryman, Tatsumi Ochiai, Olaf Walter, Amy N. Price, Mark R. Warren, Polly L. Arnold, Nikolas Kaltsoyannis, Simon Parsons
Summary: The study shows that pressure can distort actinide-oxygen bonding, and the effects vary for different actinide elements due to their atomic size. Electronic structure calculations reveal that the increased contributions of metal 6d and 5f orbitals to the metal-oxygen bonding result in the shortening of these bonds and enhance the flexibility of MO4 cores.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Amy N. Price, Ankur K. Gupta, Wibe A. de Jong, Polly L. Arnold
Summary: The chemistry of the tris-carbene anion phenyltris(3-alkyl-imidazoline-2-yliden-1-yl)borate, [C3(Me)](-) ligand, for f-block metal cations was investigated. Neutral, molecular complexes were formed for cerium(iii), while a separated ion pair was formed for ytterbium(iii). Computational analyses demonstrated the stronger s donation and greater covalency in the metal-carbon bonds of the [C3(Me)](-) complexes compared to the Tp(Me,Me) complexes. DFT calculations confirmed the crucial role of THF solvent in accurately reproducing the observed molecular and ion-pair geometries for the Ce and Yb complexes.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Amy E. Kynman, Stella Christodoulou, Erik T. Ouellette, Appie Peterson, Sheridon N. Kelly, Laurent Maron, Polly Arnold
Summary: Simple lanthanide cyclopentadienyl (Cp) complexes can photochemically cleave the sp3 carbon-chlorine bond of unactivated chlorinated hydrocarbons including polyvinyl chloride (PVC). The long excited state lifetimes and efficient light absorption by the Cp ligand enhance the photocatalytic reactivity of cerium complexes and enable light reactivity for neighboring lanthanide congeners.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Amy E. Kynman, Luca K. Elghanayan, Addison N. Desnoyer, Yan Yang, Laurent Severy, Andrea Di Giuseppe, T. Don Tilley, Laurent Maron, Polly L. Arnold
Summary: The controlled functionalization of a single fluorine in a CF3 group is difficult and rare. This study demonstrates the importance of metal-ligand cooperativity in organometallic photocatalysis.
Article
Chemistry, Multidisciplinary
Eleftheria Agapaki, Mukesh K. Singh, Angelos B. Canaj, Gary S. Nichol, Juergen Schnack, Euan K. Brechin
Summary: The sentence describes a complex compound with an aesthetically pleasing wheel-like structure, exhibiting ferromagnetic nearest neighbour exchange.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Mukesh K. Singh, Alvaro Etcheverry-Berrios, Julia Vallejo, Sergio Sanz, Jose Martinez-Lillo, Gary S. Nichol, Paul J. Lusby, Euan K. Brechin
Summary: This study presents a method for modulating the magnetic properties of metal cages through host-guest chemistry. By replacing the captured salt ions, antiferromagnetic exchange can be induced, resulting in a change in the magnetic properties of the complex.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Nicholas P. Taylor, Jorge A. Gonzalez, Gary S. Nichol, Andres Garcia-Dominguez, Andrew G. Leach, Guy C. Lloyd-Jones
Summary: The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured to develop a nucleofugality scale that can quantify and predict the leaving group ability of various Lewis bases. The study also explores the unusual kinetic stability or instability of MIDA boronates under hydrolysis conditions by correlating substituent parameters with hydrolysis rates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
