Article
Chemistry, Multidisciplinary
Michael Gock, Michael Lutter, Anna Pintus, Dieter Schollmeier, Massimiliano Arca, Vito Lippolis, Klaus Jurkschat
Summary: The phosphorus-containing aryllithium compound reacted with various reagents to yield aryldiphenylphosphane chalcogenides and benzoxaphos-phaphospholes, which were characterized structurally.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Crystallography
Emmanuel Adeniyi, Matthias Zeller, Sergiy V. V. Rosokha
Summary: An X-ray structural analysis revealed that salts of TMPD, MPTZ, and OMB with dodecamethyl- or hexabromo-substituted carbadodecaborate anions have layered structures. The cationic layers contain either well-separated TMPD+ or MPTZ(+) cation radicals or pi-stacks of partially oxidized OMB moieties. Quantum mechanical calculations showed that the formation of isolated cation radicals or pi-bonded associations in these salts is correlated with the strength of multicenter pi-bonding.
Article
Chemistry, Multidisciplinary
Luong Phong Ho, Matthias Tamm
Summary: This article provides a brief overview of the design and preparation of N-heterocyclic carbenes carrying weakly coordinating anions, and summarizes numerous transition metal and main group element complexes isolated in the past decade.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Robin F. Weitkamp, Beate Neumann, Hans-Georg Stammler, Berthold Hoge
Summary: The study revealed that weakly coordinating cations of different sizes have varying effects on the formation of silanol-silanolate motifs, with large cations favoring cyclic structures and the less bulky tetramethyl ammonium cation encouraging the formation of polyanionic silanol-silanolate chains in the solid state.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Vladimir Ya. Lee, Ryo Sakai, Kazunori Takanashi, Olga A. Gapurenko, Ruslan M. Minyaev, Heinz Gornitzka, Akira Sekiguchi
Summary: Two novel 18-electron titanium germylene complexes with distinct structural characteristics were synthesized and classified as different types of complexes, providing important insights into the chemical bonding between germanium and titanium.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sophia Weng, Wei Lun Toh, Yogesh Surendranath
Summary: The rates and selectivity of electrochemical CO2 reduction are influenced by the identity of alkali metal cations. This study shows that Au- and Ag-catalyzed CO2 reduction can occur with weakly coordinating tetraalkylammonium cations. Competition experiments reveal that the organic cation can exclusively control the selectivity and activity of CO2 reduction. These findings suggest the potential use of water-soluble organic cation salts as supporting electrolytes for CO2 electrolysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Shangxin Wei, Benjamin Peerless, Lukas Guggolz, Stefan Mitzinger, Stefanie Dehnen
Summary: In this study, a series of clusters were synthesized by reacting Ge/As anions with [MPh2] (M=Zn, Cd, Hg; Ph=phenyl). The choice of reactants was found to influence the structure of the resulting clusters. Quantum chemistry calculations confirmed the compositions and provided insight into the structural peculiarities. Additionally, the impact of different [MR2] reactants was investigated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Skyler D. D. Ware, Wendy Zhang, David J. J. Charboneau, Channing K. K. Klein, Sarah E. E. Reisman, Kimberly A. A. See
Summary: This study investigates factors influencing the electrochemical reduction of Sm(III) to Sm(II), including the effects of supporting electrolyte, electrode material, and Sm precursor. The coordination strength of the counteranion of the Sm salt is found to affect the reversibility and redox potential of the Sm(II)/(III) couple, and the counteranion primarily determines the reducibility of Sm(III). Electrochemically generated SmI2 performs similarly to commercial SmI2 solutions in a proof-of-concept reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jakub Brzeski
Summary: Quantum-chemical calculations were used to investigate the acidity and stability of aluminabenzene-based Lewis acids and anions. Aluminabenzene was found to be a stronger Lewis superacid than antimony pentafluoride, and electron-withdrawing substitutions on the heterocyclic ring led to the formation of extremely strong Lewis superacids. Two of these molecules, AlC5Cl5 and AlC5(CN)(5), were identified as the strongest Lewis acids reported in the literature. Addition of fluoride anion to substituted aluminabenzene-based Lewis acids resulted in the formation of anions with lower electronic stability but higher thermodynamic stability, making them suitable as counterions for reactive cations. The proposed Lewis acids may undergo isomerization and dimerization, while the studied anions are expected to remain stable against such processes.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Helmut Poleschner, Konrad Seppelt
Summary: Thiiranium and seleniranium salts were synthesized from different starting materials and their reactions were investigated, revealing unexpected products due to attempts to cleave specific groups. The study highlights the complexity of reactions in this system.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Iran Rojas-Leon, Gelen Gomez-Jaimes, Pedro Montes-Tolentino, Wolf Hiller, Hazem Alnasr, Braulio Rodriguez-Molina, Iran F. Hernandez-Ahuactzi, Hiram Beltran, Klaus Jurkschat, Herbert Hopfl
Summary: Hydrolysis reactions of di- and trinuclear organotin halides resulted in large novel cage compounds containing Sn-O-Sn bridges, with octanuclear tetraorganodistannoxanes showing double-ladder motifs. Among them, the co-crystal 2.0.48 I-2 exhibited the largest spacing reported to date for distannoxane-based double ladders. DFT calculations were conducted for both hexanuclear cage compound and a related octanuclear congener alongside experimental work.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Marko Rodewald, J. Mikko Rautiainen, Helmar Goerls, Raija Oilunkaniemi, Wolfgang Weigand, Risto S. Laitinen
Summary: A new platinum complex was synthesized and its crystal structure was analyzed. It was found that the ligand undergoes isomerization and forms a dynamic equilibrium during the dissolution process. Two other platinum complexes were also successfully synthesized and their structures were characterized. The bonding and formation of these complexes were further discussed through theoretical calculations.
Article
Chemistry, Physical
Berislav Peric, Natalija Pantalon Juraj, Gabor Szalontai, Suzana R. Velickovic, Filip M. Veljkovic, Drazen Vikic-Topic, Srecko I. Kirin
Summary: p-Disubstituted phenyldiketopiperazines 1, 2, and 3 were synthesized and characterized using NMR and IR spectroscopy. Their identity was confirmed by ESI-MS and HRMS spectrometry. X-ray single crystal structures revealed different crystallization spaces for the compounds.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Inorganic & Nuclear
Karolina Gutmanska, Anna Ciborska, Zbigniew Hnatejko, Anna Dolega
Summary: The structures and luminescent properties of silver(I) complexes with weakly coordinating nitrile ligands, namely 1,4-dicyanobenzene and 3-cyanopyridine, in coordination with nitrite or nitrate, have been investigated. The study reveals that coordinating the luminescent ligands does not enhance their emission properties, but extending the coordination network may result in new emission bands in the visible region.
Article
Chemistry, Physical
Koki Morida, Keisuke Fukushi, Hiroshi Sakuma, Kenji Tamura
Summary: Understanding the swelling properties of smectites is important for various applications. This study aimed to construct a general model to predict the swelling behavior of smectites saturated with monovalent cations. The results showed that the dehydration behavior of Na+- and K+-saturated smectites was similar, whereas the hydration behavior differed for different smectite species. The dehydration of Na+ and K+ in the smectite interlayers was solely controlled by the intrinsic nature of the cations, while the hydration was controlled by both the cations and the host phase. In contrast, NH4+-saturated smectites exhibited consistent dehydration and hydration curves, likely due to the binding of NH4+ to the basal oxygen. The hysteresis observed in Na+- and K+-saturated smectites was attributed to smaller layer-to-layer distances, limiting water accessibility for hydration.
APPLIED CLAY SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Manuel Schmitt, Ingo Krossing
Summary: The metal dinitrogen bonding in a wide series of terminal end-on dinitrogen complexes was investigated using charge displacement analysis. The effect of sigma donation and pi backdonation on the N-N bond was discussed and compared with observations for carbonyl complexes. It was found that sigma donation had no significant effect on the N-N bond strength, whereas pi backdonation caused elongation of the N-N bond.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Philipp Dabringhaus, Silja Zedlitz, Luisa Giarrana, David Scheschkewitz, Ingo Krossing
Summary: Schnockel's [(AlCp*)(4)] and Jutzi's [SiCp*][B(C6F5)(4)] are important in modern main-group chemistry with various applications in synthesis and catalysis. However, the reactivity between AlCp* and [SiCp*](+) has not been explored. In this study, their reaction was investigated and complex salts [Cp*Si(AlCp*)(3)][WCA] were obtained. The tetrahedral [SiAl3](+) core not only represents a rare example of a low-valent silicon-doped aluminium-cluster, but also provides a convenient preparative entry towards low-valent Si-Al clusters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Malte Sellin, Matthis Seiler, Maximilian Maylaender, Konstantin Kloiber, Valentin Radke, Stefan Weber, Sabine Richert, Ingo Krossing
Summary: This study prepared stable unsubstituted acenium radical cation (ARC) salts with weakly coordinating anions at room temperature, and characterized them structurally, electrochemically, and spectroscopically. For the first time, a homogenous set of spectroscopic data on analytically pure ARC salts was obtained. In addition, cyclovoltammetric measurements linked the potentials of acenium cations in solution with those in the gas phase.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Valentin Radtke, Denis Priester, Agnes Heering, Carina Mueller, Thorsten Koslowski, Ivo Leito, Ingo Krossing
Summary: We propose a unified redox potential scale E-abs(H2O) that is valid for all solvents. Using potentiometric measurements on silver and chloride ions, we demonstrate that a salt bridge filled with the ionic liquid [N-2225][NTf2] satisfies the necessary conditions for determining single ion Gibbs transfer energy between different solvents. Based on these measurements, we develop a consistent unified redox potential scale E-abs(H2O) that allows for the assessment and comparison of redox potentials in six different solvents.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Malte Sellin, Matthis Seiler, Ingo Krossing
Summary: This article investigates the structures of two silver(I) complex salts, revealing that one complex salt has a silver ion inserted into a metal bond, while the other complex salt is formed by two tetrahedral metal clusters and a silver ion. Analysis suggests the presence of chemical bonds between the silver ion and the metal carbonyl ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Manuel Schmitt, Maximilian Maylaender, Valentin Radtke, Tim Heizmann, Sabine Richert, Ingo Krossing
Summary: The stable and easily accessible salt [Ni(CO)(4)](+)[F{Al(ORF)(3)}(2)](-) was used as a Ni-I synthon to generate novel half-sandwich complexes [Ni(arene)(CO)(2)](+). The reaction with [Ni(o-dfb)(2)](+) salt, which has a rather endergonic reaction, was successful by removing CO irreversibly. The resulting complex has a unique slipped eta(3), eta(3)-sandwich structure and is the ultimate synthon for Ni-I chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Dustin Kubas, Jennifer Maria Beck, Erdogan Kasisari, Timo Schaetzler, Anita Becherer, Anna Fischer, Ingo Krossing
Summary: The direct synthesis of dimethyl ether (DME) from CO2 hydrogenation was investigated using an improved bifunctional catalyst in a fixed bed reactor. Various combinations of a methanol-producing part and a methanol dehydration part were tested, and the results showed that HPA-coated catalysts exhibited higher activity and resilience toward deactivation. Dual-grain preparation method showed superior performance over single-grain.
Review
Chemistry, Multidisciplinary
Malte Sellin, Ingo Krossing
Summary: CO is one of the most important ligands in organometallic chemistry and can form transition metal carbonyl cations (TMCCs), but their synthesis is challenging due to their high reactivity.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Jan M. Rall, Max Lapersonne, Marcel Schorpp, Ingo Krossing
Summary: This article reports the synthesis and characterization of nickelocenium cations. Diamagnetic [NiCp2]2+ represents the first example of an unsubstituted parent metallocene dication. The salts were generated and characterized using various experimental methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Antoine Barthelemy, Harald Scherer, Michael Daub, Alexis Bugnet, Ingo Krossing
Summary: The reaction between bisdicyclohexylphosphinoethane (dcpe) and subvalent M(I) sources [M-I(PhF)(2)][pf] (M=Ga+, In+; [pf]-=[Al(ORF)(4)]-; R-F=C(CF3)(3)) resulted in the formation of salts [{M(dcpe)}(2)][pf](2), which contain the first reported dicationic, trans-bent digallene, and diindene structures. The M-I double bonds, which display a ditetrylene-like structure, are surprisingly short. Quantum chemical calculations and molecular analyses were conducted to compare the bonding situation in these salts with that in the isoelectronic and isostructural, but neutral digermenes and distannenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Andreas Billion, Andreas Vogel, Jonas Schulte, Harald Scherer, Ingo Krossing
Summary: Oxymethylene dimethyl ethers (OMEn) are promising sustainable synthetic fuels synthesized from CO2 and green H-2. This study presents a novel continuous, anhydrous reaction setup to overcome synthetic problems and successfully synthesizes OMEn. The catalysts immobilized in ionic liquids demonstrate excellent catalytic performance and stable results in continuous operations.
Article
Chemistry, Multidisciplinary
Philipp Dabringhaus, Tim Heizmann, Ingo Krossing
Summary: This study reports the reactivity of a monomeric Ga(I) cation activated with a pyridine-diimine pincer ligand towards small molecules, including controlled oxidative additions into C-Cl, H-P, and P-P bonds, as well as [4+1] cycloaddition to butadienes. Intriguingly, the insertion product into the P-P bond allows for the quantitative release of the P-4 molecule upon reaction with AlEt3 and butadienes. The experimental study is supported by high-level computational analysis. Evaluation: 7 points.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Christoph Riesinger, David Roehner, Ingo Krossing, Manfred Scheer
Summary: A rational synthetic pathway was developed to synthesize a series of cyclo-P-5-bearing multi-decker complexes. By combining [Cp*Fe(mu,eta(5 : 5)-P-5)] (A) with low-valent transition metal cations, triple-decker complexes [Cp*Fe(mu,eta(5 : 5)-P-5)MCp '''][WCA] (M = Cr - Ni; WCA = weakly coordinating anion, Cp ''' = 1,2,4-(Bu3C5H2)-Bu-t) were obtained. Utilizing arene complexes [M(C6R6)(2)][WCA](n) (M = Fe, Co) allowed the synthesis of unprecedented cyclo-P-5-containing quadruple-decker complexes [{Cp*Fe(mu,eta(5 : 5)-P-5)}(2)M][pf](n) (M = Fe, Co).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Andreas Billion, Marcel Schorpp, Rebecca Feser, Manuel Schmitt, Lea Eisele, Harald Scherer, Takaaki Sonoda, Hajimu Kawa, Burkhard Butschke, Ingo Krossing
Summary: Weakly coordinating anions (WCAs) are used to stabilize and isolate reactive cations. The alkoxyaluminate-based WCA [Al(OC(CF3)(3))(4)](-) ([pf](-)) is widely used but can still be coordinated by small cations. A novel WCA [Al(OC10F15)(4)](-) ([pfAd](-)) is more stable due to its rigid core framework. Various salts containing [pfAd](-) were synthesized and characterized by spectroscopy and crystallography. The water stability of [pfAd](-) was demonstrated by the successful synthesis of Tl[pfAd] in a mixture of solvents.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Andreas Billion, Jonas Schulte, Andreas Vogel, Felix Hilfinger, Ingo Krossing
Summary: A novel continuous route for synthesizing oxymethylene dimethyl ethers (OMEn) by the reaction of molecular formaldehyde and dimethyl ether is presented. Acidic, porous, and thermally stable zeolites proved to be effective catalysts for this reaction. The results contribute to a better understanding of the complex reaction network in the OMEn synthesis and provide important insights for establishing an energy efficient and sustainable OMEn production process.
