Article
Chemistry, Inorganic & Nuclear
Christian Ritter, Nick Michel, Alina Rinow, Benjamin Ringler, Carsten von Hanisch
Summary: The stepwise synthesis of novel molecules containing As-Sb and As-Bi bonds was achieved by reacting tBu(2)ECl with tBuAs(H)Li to prepare binary interpnictogen compounds, followed by lithiation to obtain dimeric compounds. Compound 5 was found to be suitable for the preparation of longer chains, and the synthesis was confirmed through experiments.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Jizhou He, Xiaodong Hu, Zonghao Liu, Wei Chen, Giulia Longo
Summary: Inorganic-organic hybrid lead halide perovskites have potential applications in solar cells, but their toxicity and poor stability limit their practical use. Therefore, searching for lead-free alternatives with similar advantages has become important in this field. Bismuth/antimony chalcohalides are of interest due to their similar electronic structures to lead. This review summarizes the properties and performance of ternary pnictogen chalcohalides and quaternary compounds, focusing on different preparation strategies.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Vikas Kumar, Rajesh G. Gonnade, Cem B. Yildiz, Moumita Majumdar
Summary: Compound 1, stabilized by 5,6-bis(diisopropylphosphino)acenaphthene, exhibited nucleophilic behavior towards coinage metals with the fugitive antimony (I) cation. Synthesized strategically at room temperature from SbCl3, the bis(phosphine), and trimethylsilyl trifluoromethanesulfonate, compound 1 involves a two-electron oxidation of the ligand to form a P-P bonded diphosphonium dication, which is separated to give both products in pure form in moderate yields. Despite its overall positive charge, compound 1 was found to bind to metal centers, forming complexes with Au-I, Ag-I, and Cu-I.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Green & Sustainable Science & Technology
D. Luo, M. Fernandez de Labastida, J. L. Cortina, J. Lopez
Summary: In the copper pyrometallurgical industry, the use of ion-exchange resins for treating the electrolyte can prevent the precipitation of un-soluble slimes containing bismuth, arsenic and antimony. A selective precipitation process was developed to recover antimony and bismuth from the eluate, considering the presence of high contents of As(V). Treatment with SO2(g) or NaHSO3(s) was used to reduce As(V) and Sb(V) before obtaining antimony oxychloride (Sb4O5Cl2) and bismuth oxychloride (BiOCl) with high purity using appropriate pH control.
JOURNAL OF CLEANER PRODUCTION
(2023)
Review
Chemistry, Multidisciplinary
Fabrizio Ortu
Summary: This review provides an overview of the important starting materials and ligands used in rare earth synthetic chemistry, covering their preparations and applications in modern synthetic methodologies.
Review
Geochemistry & Geophysics
Alvaro Aracena, Miguel Veliz, Oscar Jerez, Eduardo Balladares, Manuel Perez-Tello
Summary: This paper reviews the fundamentals of current treatments for removing arsenic, antimony, and bismuth from copper concentrates under roasting conditions. The behavior of these elements during the experiments is analyzed based on a literature survey and experimental findings.
Article
Chemistry, Multidisciplinary
Hritwik Haldar, Cem. B. Yildiz, Moumita Majumdar
Summary: Bis(alpha-iminopyridine) L acts as a redox non-innocent Schiff-base ligand to coordinate with cationic antimony(III) and bismuth(III) centers. Mono- and di-cationic compounds have been synthesized and characterized using single crystal X-ray crystallography and solution-state NMR studies. The tri-cationic species of bismuth forms a heteroleptic compound coordinated by two types of Schiff-base donors.
Review
Chemistry, Multidisciplinary
Qingqing Fang, Yan Xu, Xiaosheng Yan, Tao Jiang, Yunbao Jiang
Summary: Metal-coordination-directed macrocyclic complexes have potential applications in biosensing and therapeutics, but current synthetic methods face challenges in controlling the formation of uncontrolled multicyclic cages and linear oligomers/polymers. This mini-review outlines state-of-art synthetic approaches using foldable ligands or amphiphilic ligands to achieve predictable and controllable structures of metal-coordination-directed macrocyclic complexes.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jonas Bresien, Axel Schulz, Lilian Sophie Szych, Alexander Villinger, Ronald Wustrack
Summary: The synthesis and reactivity of sterically demanding phosphaarsanes were described in this study, with a new structural motif phosphane arsanyldithiocarboxylate being discovered. An alternative synthetic route was reported to enable access to a wider range of phosphane arsanyldithiocarboxylates. The interpnictogen dithiocarboxylates showed an interesting bonding situation with significantly elongated As-S bond due to negative hyperconjugation within the molecule.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Andrey Y. Baranov, Elena A. Pritchina, Alexey S. Berezin, Denis G. Samsonenko, Vladimir P. Fedin, Nataliya A. Belogorlova, Nina P. Gritsan, Alexander V. Artem'ev
Summary: The discovery of a novel triply bridging phosphine ligand in coordination with copper atoms has resulted in complexes with outstanding blue phosphorescence and potential practical applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Roberta Cargnelutti, Ricardo F. Schumacher, Andrei L. Belladona, Jean C. Kazmierczak
Summary: This review provides an overview of pyridyl-selenium compounds and their metal complexes in the fields of pharmacology, material science, and technology, covering coordination chemistry, synthetic methodologies, and structural characterization. Relevant direct applications in nanomaterial preparation, organic synthesis catalysis, photocatalytic hydrogen production, and oxygen activation are also discussed.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Spartak S. Yarovoy, Irina Mirzaeva, Yuri Mironov, Natalia Pervukhina, Konstantin A. Brylev
Summary: Azide cluster complexes were obtained by reacting Re3X9 with sodium azide. These complexes represent the first case of metal cluster polyazide complexes and exhibit high explosiveness.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
Chandrabhan Verma, Abhinay Thakur, Richika Ganjoo, Shveta Sharma, Humira Assad, Ashish Kumar, M. A. Quraishi, Akram Alfantazi
Summary: Heterocyclic compounds containing nitrogen atoms have excellent corrosion inhibition potential and are frequently used to prevent corrosion in extreme circumstances. These compounds can effectively adsorb on the metal's surface and form chelating complexes to protect metallic species from corrosive environments. Azoles and triazines, as well as other N-heterocyclic compounds with multiple nitrogen atoms, are particularly efficient in reducing corrosive effects in aqueous electrolytes. This review discusses the coordination and bonding characteristics of N-based heterocyclic compounds and their ability to prevent corrosion.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
P. Rafael Donnarumma, Sahara Frojmovic, Paola Marino, Hudson A. Bicalho, Hatem M. Titi, Ashlee J. Howarth
Summary: For the first time, rare-earth (RE) analogues of UiO-66 with non-functionalised 1,4-benzenedicarboxylate linkers have been synthesized, and a series of synthetic approaches provided to troubleshoot the synthesis. These RE-UiO-66 analogues are fully characterized and exhibit high crystallinity, high surface area, and thermal stability, consistent with the UiO-66 archetype.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Bertold Rasche, Laura C. Straub, Matthias Adlung, Claudia Wickleder, Mathias S. Wickleder
Summary: In this work, a variety of divalent europium complexes containing bidentate 1,10-phenanthroline ligands were systematically investigated. Different structures of complexes were formed depending on the Eu/Phen ratio. These complexes showed remarkable optical properties based on a partial electron transfer from the EuII center to the Phen ligand. Electrochemistry studies further described the intermediate valence of the Eu center.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Matthew A. Johnson, Max M. Martin, Kevin Cocq, Norbert Jux, Michael J. Ferguson, Rik R. Tykwinski
Summary: The Friedel-Crafts acylation of hexaphenylbenzene selectively produces monoacylated products. The resulting ketones are used as precursors for the synthesis of [5]cumulenes, with one of the derivatives exhibiting significant stability due to the presence of a sterically demanding group. The rotational barrier for diethynyl[5]cumulenes is estimated using VT NMR studies.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Connor M. Simon, Samantha L. Dudra, Ryan T. McGuire, Michael J. Ferguson, Erin R. Johnson, Mark Stradiotto
Summary: This study reveals a new reductive elimination pathway for nickel-catalyzed C-N cross-coupling, involving a bifurcated pathway and a base-promoted pathway for C-N reductive elimination.
Article
Chemistry, Physical
Dylan J. Hale, Michael J. Ferguson, Laura Turculet
Summary: The study presents a novel Ni-based pre-catalyst for the (E)-selective semihydrogenation of alkynes, exhibiting high selectivity under mild conditions through facile alkyne insertion and subsequent alkene isomerization.
Article
Chemistry, Multidisciplinary
Bozheng Sun, Meagan S. Oakley, Kota Yoshida, Yanwen Yang, Matteo Tommasini, Chiara Zanchi, Andrea Lucotti, Michael J. Ferguson, Frank Hampel, Mariusz Klobukowski, Rik R. Tykwinski
Summary: Cyclic tetraaryl[5]cumulenes were synthesized and studied to understand the effects of increasing ring strain. Analysis through X-ray crystallography and DFT calculations showed that while there were observable trends in C-13 NMR, UV-vis, and Raman spectra associated with ring strain, the HOMO-LUMO gap was not significantly affected by the bending of the [5]cumulene framework.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Ian C. Watson, Yuqiao Zhou, Michael J. Ferguson, Eric Rivard
Summary: Anionic N-heterocyclic olefin (aNHO)-supported Group 4 metal complexes were synthesized through salt metathesis reactions, and a ligand-activated bis-aNHO Zr(II) complex was obtained and structurally characterized.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Physical
Roman G. Belli, Jin Yang, Erick Nunez Bahena, Robert McDonald, Lisa Rosenberg
Summary: This study provides a thorough experimental examination of the mechanisms involved in the catalytic hydrophosphination reaction using a series of half-sandwich Ru indenyl complexes. The results highlight the importance of ancillary ligands in the design of active and robust catalysts for this reaction, and reveal the complexity that can arise from simple mechanistic premises.
Article
Chemistry, Multidisciplinary
Brandon L. L. Frenette, Jonathan Trach, Michael J. J. Ferguson, Eric Rivard
Summary: We report the stabilization of phosphinidenes (PR) by an intramolecular frustrated Lewis pair (FLP) chelate. Our new adducts, including PH accessed through thermolysis of coordinated HPCO, act as a starting point for other phosphorus-containing compounds. These adducts participate in thermal- or light-induced phosphinidene elimination, transfer P-2 units to an organic substrate, and yield the semiconductor InP at only 110 degrees C from solution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Samuel R. Baird, Emanuel Hupf, Ian C. Watson, Michael J. Ferguson, Eric Rivard
Summary: A tetramer shaped indium(I) organometallic compound supported by anionic N-heterocyclic olefin ligands is reported. The monomeric unit of this compound shows both Lewis acidic and basic properties at indium, and the steric profile of the N-heterocyclic olefin ligand enables the isolation of a rare monomeric imide.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Alvaro A. Omana, Brandon L. Frenette, Eike Dornsiepen, Ryo Kobayashi, Michael J. Ferguson, Takeaki Iwamoto, Eric Rivard
Summary: The reactivity of [PB{SiX2}] adducts was studied, focusing on reduction attempts to access [PB{E}](x) species. Only free PB ligand was formed as the product in all cases. Computational analysis was performed to evaluate the energy penalty associated with EX2 dissociation from the PB chelates. The reactivity of the formal methylene adduct [PB{CH2}] and its heavier element congeners of [PB{EH2}] was compared. New phosphine-borane frustrated Lewis pair (FLP) chelates were introduced and their coordination chemistry was explored.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Janelle Bykowski, Jocelyn Sinclair, Jonathan Trach, Michael J. Ferguson, Eric Rivard
Summary: We present mild deposition methods for producing crystalline films of elemental tin, achieved through the formation and decomposition of unstable tin(ii) hydrides. By utilizing efficient (OBu)-Bu-t/H metathesis with Sn(ii) alkoxide precursors and pinacolborane (HBpin) as the hydride source, as well as -N(SiMe3)(2)/H exchange, elemental tin was successfully obtained as an insoluble product.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Zachary W. Schroeder, Robert McDonald, Michael J. Ferguson, Wesley A. Chalifoux, Rik R. Tykwinski, Dan Lehnherr
Summary: A general method for the synthesis of ethynylated pentacene ketones is reported, and key noncovalent interactions contributing to their crystallization are revealed by X-ray crystallography.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Matthias T. Ackermann, Michael Seidl, Riccardo Grande, Yuqiao Zhou, Michael J. Ferguson, Alexey Y. Timoshkin, Eric Rivard, Manfred Scheer
Summary: The study reports the formation of novel cationic mixed main group compounds composed of elements from groups 13, 14, and 15. Reactions between pnictogenylboranes and the NHC-stabilized compound IDipp center dot GeH2BH2OTf resulted in the formation of cationic mixed group 13/14/15 compounds through the nucleophilic substitution of the triflate group. The products were characterized by NMR spectroscopy, mass spectrometry, and X-ray structure analysis.
Article
Chemistry, Inorganic & Nuclear
Hannah J. J. Dokken, Brandon L. L. Frenette, Michael J. J. Ferguson, Eric Rivard
Summary: We report the synthesis and reactivity of a geminal-linked fluorene-derived frustrated Lewis pair (FLP), (Pr2P)-Pr-i(C13H8)BCy2 (1). Compound 1 displays anomalous behavior towards small molecules, acting as a masked FLP. This behavior is attributed to significant polarization of the B-C(fluorene) bond in 1, as determined by density functional theory (DFT) computations. We show the exploitation of this B-C bond polarity through reactions with PhPCl2, H3N center dot BH3, and (PrNH2)-Pr-i, leading to P-Cl and N-H bond activation, respectively.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Henrik Gotfredsen, Dominik Thiel, Phillip M. Greibel, Lan Chen, Marcel Krug, Ilias Papadopoulos, Michael J. Ferguson, Mogens Brondsted Nielsen, Tomas Torres, Timothy Clark, Dirk M. Guldi, Rik R. Tykwinski
Summary: This study investigates the influence of sensitizer-chromophore geometry on the separation of singlet excited states into triplet excited states. Two conjugates with different arrangements were synthesized and compared. The results show that the energy transfer rate is 26 times faster in the peripheral arrangement, even though the chromophores are farther apart. This rate acceleration is attributed to the more favorable relative orientation of the transition dipole moments in the peripheral structure. These findings are of significant importance for solar energy research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Rasmus Ringstrom, Fredrik Edhborg, Zachary W. Schroeder, Lan Chen, Michael J. Ferguson, Rik R. Tykwinski, Bo Albinsson
Summary: Three pentacene dimers have been synthesized to study the effect of molecular rotation and rotational conformations on singlet fission. The results show that different conformers exhibit varying SF rates and triplet-pair recombination rates, and that viscosity affects the SF rate and triplet pair lifetime.
