@article{60600, abstract = {{In the search for noble metal free photocatalytic systems, iron is the dream candidate. To increase excited state lifetimes of iron complexes, the multichromophoric approach is promising, combining organic chromophores with photoactive iron complexes, potentially enabling a reservoir effect. We present a series of chromophore-functionalized complexes based on the parental FeIII complex [Fe(ImP)2][PF6] (HImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazole-2-ylidene)). The four organic chromophores benzene, naphthalene, anthracene, and pyrene are attached to the ImP-ligand in para-position to the coordination site to systematically investigate the influence of the steric demand and electronic properties of the chromophore on charge transfer lifetimes as well as photodynamics. A thorough ground state characterization was conducted in addition to investigations of the excited state dynamics by transient absorption spectroscopy and streak camera emission measurements. The conclusions drawn are supported by extensive DFT calculations. The emission coefficients could be significantly improved by the addition of chromophores. After excitation of the complexes with larger chromophores, coplanarization of the backbone and complex motif occurs to stabilize the formal charge. This results in population of a superligand state that exhibits a much faster radiationless relaxation to the ground state compared to the parent complex, hindering a reservoir effect.}}, author = {{Schmitz, Lennart and Argüello Cordero, Miguel A. and Al-Marri, Mohammed J. and Schoch, Roland and Egold, Hans and Neuba, Adam and Steube, Jakob and Bracht, Bastian Johannes and Bokareva, Olga S. and Lochbrunner, Stefan and Bauer, Matthias}}, issn = {{0020-1669}}, journal = {{Inorganic Chemistry}}, keywords = {{Photo}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Chromophore Induced Effects in Iron(III) Complexes}}}, doi = {{10.1021/acs.inorgchem.5c00526}}, year = {{2025}}, } @article{58180, abstract = {{A series of CoIII complexes [Co(RImP)2][PF6], with HMeImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazole-2-ylidene)) and R = Me, Et, iPr, nBu, is presented in this work. The influence of the strong donor ligand on the ground and excited-state photophysical properties was investigated in the context of different alkyl substituents at the imidazole nitrogen. X-ray diffraction revealed no significant alterations of the structures and all differences in the series emerge from the electronic structures. These were probed via cyclic voltammetry and UV–vis spectroscopy, detailing the influence of the different alkyl substituents on the ground-state properties. All complexes are emissive at 77 K from a 3MC state, which exhibits lifetimes in the range of 1–5 ns at room temperature, depending on the alkyl substituent. Therefore, it is clearly shown that even small differences in the electronic structure have a large impact on the details of the excited state landscape. The observed behavior was rationalized by a detailed DFT analysis, which shows that the minimum-energy crossing point to the ground-state is located only slightly above the MC energy: Consequently, nonradiative decay to the ground state at room temperature is enabled, while at 77 K this path is prohibited, leading to low-temperature 3MC emission.}}, author = {{Krishna, Athul and Fritsch, Lorena and Steube, Jakob and Argüello Cordero, Miguel A. and Schoch, Roland and Neuba, Adam and Lochbrunner, Stefan and Bauer, Matthias}}, issn = {{0020-1669}}, journal = {{Inorganic Chemistry}}, keywords = {{Photo}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Low Temperature Emissive Cyclometalated Cobalt(III) Complexes}}}, doi = {{10.1021/acs.inorgchem.4c04479}}, year = {{2025}}, } @article{52541, abstract = {{AbstractWe conducted an investigation into the palladium‐catalyzed carbon‐sulfur cross‐coupling reaction involving a 2‐bromothiophene derivative and potassium thioacetate as a substitute for hydrogen sulfide. This investigation utilized kinetic and computational methods. We synthesized two palladium complexes supported by the bisphosphane ligands bis(diphenylphosphino)ferrocene (DPPF) and bis(diisopropylphosphino)ferrocene (DiPPF), as well as their tentative intermediates in the catalytic cycle. Reaction rates were measured and then compared to computational predictions.}}, author = {{Peschtrich, Sebastian and Schoch, Roland and Kuckling, Dirk and Paradies, Jan}}, issn = {{1434-193X}}, journal = {{European Journal of Organic Chemistry}}, keywords = {{Organic Chemistry, Physical and Theoretical Chemistry}}, number = {{8}}, publisher = {{Wiley}}, title = {{{A Comparative Kinetic and Computational Investigation of the Carbon‐Sulfur Cross Coupling of Potassium Thioacetate and 2‐Bromo Thiophene Using Palladium/Bisphosphine Complexes}}}, doi = {{10.1002/ejoc.202301207}}, volume = {{27}}, year = {{2024}}, } @article{52572, abstract = {{A series of substituted ferrocenyl boron derivatives was synthesized. The oxidation of the ferrocenyl unit resulted in a significant increase of the boron‐centered Lewis acidity. The neutral and cationic Lewis acids were characterized by NMR‐spectroscopy, crystal structure analysis and by computational methods. The new Lewis acids were then applied in the Meinwald rearrangement of epoxides, predominantly furnishing aldehydes as the kinetic products.}}, author = {{Köring, Laura and Birenheide, Bernhard and Krämer, Felix and Wenzel, Jonas O. and Schoch, Roland and Brehm, Martin and Breher, Frank and Paradies, Jan}}, issn = {{1434-1948}}, journal = {{European Journal of Inorganic Chemistry}}, keywords = {{Inorganic Chemistry}}, publisher = {{Wiley}}, title = {{{Synthesis of Ferrocenyl Boranes and their Application as Lewis Acids in Epoxide Rearrangements}}}, doi = {{10.1002/ejic.202400057}}, year = {{2024}}, } @article{56075, abstract = {{An isostructural series of FeII, FeIII, and Fe(IV)complexes [Fe(ImP)2]0/+/2+ utilizing the ImP 1,1′-(1,3-phenylene)-bis(3-methyl-1-imidazol-2-ylidene) ligand, combining N-heterocy-clic carbenes and cyclometalating functions, is presented. The strong donor motif stabilizes the high-valent Fe(IV) oxidation state yet keeps the FeII oxidation state accessible from the parent Fe(III)compound. Chemical oxidation of [Fe(ImP)2]+ yields stable [FeIV(ImP)2]2+. In contrast, [FeII(ImP)2]0, obtained by reduction,is highly sensitive toward oxygen. Exhaustive ground state characterization by single-crystal X-ray diffraction, 1H NMR,Mössbauer spectroscopy, temperature-dependent magnetic measurements, a combination of X-ray absorption near edge structureand valence-to-core, as well as core-to-core X-ray emission spectroscopy, complemented by detailed density functional theory (DFT) analysis, reveals that the three complexes[Fe(ImP)2]0/+/2+ can be unequivocally attributed to low-spin d6, d5, and d4 complexes. The excited state landscape of the Fe(II) and Fe(IV) complexes is characterized by short-lived 3MLCT and 3LMCT states, with lifetimes of 5.1 and 1.4 ps, respectively. In the FeII-compound, an energetically low-lying MC state leads to fast deactivation of the MLCT state. The distorted square-pyramidal state, where one carbene is dissociated, can not only relax into the ground state, but also into a singlet dissociated state. Its formation was investigated with time-dependent optical spectroscopy, while insights into its structure were gained by NMR spectroscopy.}}, author = {{Steube, Jakob and Fritsch, Lorena and Kruse, Ayla and Bokareva, Olga S. and Demeshko, Serhiy and Elgabarty, Hossam and Schoch, Roland and Alaraby, Mohammad and Egold, Hans and Bracht, Bastian Johannes and Schmitz, Lennart and Hohloch, Stephan and Kühne, Thomas D. and Meyer, Franc and Kühn, Oliver and Lochbrunner, Stefan and Bauer, Matthias}}, issn = {{0020-1669}}, journal = {{Inorganic Chemistry}}, keywords = {{Photo}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States}}}, doi = {{10.1021/acs.inorgchem.4c02576}}, year = {{2024}}, } @article{52346, abstract = {{Promising cathode materials for fluoride-ion batteries (FIBs) are 3d transition metal containing oxides with Ruddlesden-Popper-type structure. So far, multi-elemental compositions were not investigated, but could alternate electrochemical performance similar to what has been found for cathode materials for lithium-ion batteries. Within this study, we investigate RP type La2Ni0.75Co0.25O4.08 as an intercalation-based active cathode material for all-solid-state FIBs. We determine the structural changes of La2Ni0.75Co0.25O4.08 during fluoride intercalation / de-intercalation by ex-situ X-ray diffraction, which showed that F- insertion leads to transformation of the parent phase to three different phases. Changes in Ni and Co oxidation states and coordination environment were examined by X-ray absorption spectroscopy and magnetic measurements in order to understand the complex reaction behaviour of the phases in detail, showing that the two transition metals behave differently in the charging and discharging process. Under optimized operating conditions, a cycle life of 120 cycles at a critical cut-off capacity of 40 mAh g-1 against Pb/PbF2 was obtained, which is one of the highest observed for intercalation electrode materials in FIBs so far. The average Coulombic efficiencies ranged from 85% to 90%. Thus, La2Ni0.75Co0.25O4.08 could be a promising candidate for cycling-stable high-energy cathode materials for all-solid-state FIBs}}, author = {{Vanita, Vanita and Waidha, Aamir Iqbal and Vasala, Sami and Puphal, Pascal and Schoch, Roland and Glatzel, Pieter and Bauer, Matthias and Clemens, Oliver}}, issn = {{2050-7488}}, journal = {{Journal of Materials Chemistry A}}, keywords = {{Xray}}, number = {{12}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Insights into the First Multi-Transition-Metal Containing Ruddlesden Popper-Type Cathode for all-solid-state Fluoride Ion Batteries}}}, doi = {{10.1039/d4ta00704b}}, year = {{2024}}, } @article{54969, abstract = {{This work presents a new and facile route for the preparation of iron oxide-based catalysts supported on alumina, which enables the targeted synthesis of catalysts with an increased amount of isolated tetrahedrally coordinated iron centers compared to a conventional impregnation procedure, and therefore leads to an increase in activity for CO oxidation reaction. By a multi-step impregnation–calcination protocol, the catalysts were synthesized with iron loadings of between 1 and 10 wt%, and their catalytic activity was then compared with a 10 wt% loaded catalyst prepared by conventional single impregnation. With a loading of 8 wt%, the presented catalysts showed an improved catalytic activity regarding light-off and full conversion temperatures compared to this reference. Through the application of several analytical methods (PXRD, PDF, DRUVS, SEM, XAFS), the improved catalytic activity can be correlated with an increased amount of isolated iron centers and a significantly reduced fraction of agglomerates or particles.}}, author = {{Schlicher, Steffen and Schoch, Roland and Prinz, Nils and Zobel, Mirijam and Bauer, Matthias}}, issn = {{2073-4344}}, journal = {{Catalysts}}, keywords = {{Catalysis}}, number = {{7}}, publisher = {{MDPI AG}}, title = {{{New and Facile Preparation Method for Highly Active Iron Oxide Catalysts for CO Oxidation}}}, doi = {{10.3390/catal14070416}}, volume = {{14}}, year = {{2024}}, } @article{52345, abstract = {{Photoactive chromium(III) complexes saw a conceptual breakthrough with the discovery of the prototypical molecular ruby mer-[Cr(ddpd)2]3+ (ddpd = N,N′-dimethyl-N,N′-dipyridin-2-ylpyridine-2,6-diamine), which shows intense long-lived near-infrared (NIR) phosphorescence from metal-centered spin-flip states. In contrast to the numerous studies on chromium(III) photophysics, only 10 luminescent molybdenum(III) complexes have been reported so far. Here, we present the synthesis and characterization of mer-MoX3(ddpd) (1, X = Cl; 2, X = Br) and cisfac-[Mo(ddpd)2]3+ (cisfac-[3]3+), an isomeric heavy homologue of the prototypical molecular ruby. For cisfac-[3]3+, we found strong zero-field splitting using magnetic susceptibility measurements and electron paramagnetic resonance spectroscopy. Electronic spectra covering the spin-forbidden transitions show that the spin-flip states in mer-1, mer-2, and cisfac-[3]3+ are much lower in energy than those in comparable chromium(III) compounds. While all three complexes show weak spin-flip phosphorescence in NIR-II, the emission of cisfac-[3]3+ peaking at 1550 nm is particularly low in energy. Femtosecond transient absorption spectroscopy reveals a short excited-state lifetime of 1.4 ns, 6 orders of magnitude shorter than that of mer-[Cr(ddpd)2]3+. Using density functional theory and ab initio multireference calculations, we break down the reasons for this disparity and derive principles for the design of future stable photoactive molybdenum(III) complexes.}}, author = {{Kitzmann, Winald R. and Hunger, David and Reponen, Antti-Pekka M. and Förster, Christoph and Schoch, Roland and Bauer, Matthias and Feldmann, Sascha and van Slageren, Joris and Heinze, Katja}}, issn = {{0020-1669}}, journal = {{Inorganic Chemistry}}, keywords = {{Inorganic Chemistry, Physical and Theoretical Chemistry}}, number = {{39}}, pages = {{15797--15808}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby}}}, doi = {{10.1021/acs.inorgchem.3c02186}}, volume = {{62}}, year = {{2023}}, } @article{46481, abstract = {{AbstractAlthough iron is a dream candidate to substitute noble metals in photoactive complexes, realization of emissive and photoactive iron compounds is demanding due to the fast deactivation of their charge-transfer states. Emissive iron compounds are scarce and dual emission has not been observed before. Here we report the FeIII complex [Fe(ImP)2][PF6] (HImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene)), showing a Janus-type dual emission from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. This behaviour is achieved by a ligand design that combines four N-heterocyclic carbenes with two cyclometalating aryl units. The low-lying π* levels of the cyclometalating units lead to energetically accessible MLCT states that cannot evolve into LMCT states. With a lifetime of 4.6 ns, the strongly reducing and oxidizing MLCT-dominated state can initiate electron transfer reactions, which could constitute a basis for future applications of iron in photoredox catalysis.}}, author = {{Steube, Jakob and Kruse, Ayla and Bokareva, Olga S. and Reuter, Thomas and Demeshko, Serhiy and Schoch, Roland and Argüello Cordero, Miguel A. and Krishna, Athul and Hohloch, Stephan and Meyer, Franc and Heinze, Katja and Kühn, Oliver and Lochbrunner, Stefan and Bauer, Matthias}}, issn = {{1755-4330}}, journal = {{Nature Chemistry}}, keywords = {{General Chemical Engineering, General Chemistry}}, number = {{4}}, pages = {{468--474}}, publisher = {{Springer Science and Business Media LLC}}, title = {{{Janus-type emission from a cyclometalated iron(iii) complex}}}, doi = {{10.1038/s41557-023-01137-w}}, volume = {{15}}, year = {{2023}}, } @article{40981, abstract = {{Room temperature sodium-sulfur (RT Na-S) batteries are considered potential candidates for stationary power storage applications due to their low cost, broad active material availability and low toxicity. Challenges, such as high volume expansion of the S-cathode upon discharge, low electronic conductivity of S as active material and herewith limited rate capability as well as the shuttling of polysulfides (PSs) as intermediates often impede the cycle stability and practical application of Na-S batteries. Sulfurized poly(acrylonitrile) (SPAN) inherently inhibits the shuttling of PSs and shows compatibility with carbonate-based electrolytes, however, its exact redox mechanism remained unclear to date. Herein, we implement a commercially available and simple electrolyte into the Na-SPAN cell chemistry and demonstrate its high rate and cycle stability. Through the application of in situ techniques utilizing electronic impedance spectroscopy (EIS) and X-ray absorption spectroscopy (XAS) at different depths of charge and discharge, an insight into SPAN’s redox chemistry is obtained.}}, author = {{Kappler, Julian and Tonbul, Güldeniz and Schoch, Roland and Murugan, Saravanakumar and Nowakowski, Michał and Lange, Pia Lena and Klostermann, Sina Vanessa and Bauer, Matthias and Schleid, Thomas and Kästner, Johannes and Buchmeiser, Michael Rudolf}}, issn = {{0013-4651}}, journal = {{Journal of The Electrochemical Society}}, keywords = {{Materials Chemistry, Electrochemistry, Surfaces, Coatings and Films, Condensed Matter Physics, Renewable Energy, Sustainability and the Environment, Electronic, Optical and Magnetic Materials}}, number = {{1}}, publisher = {{The Electrochemical Society}}, title = {{{Understanding the Redox Mechanism of Sulfurized Poly(acrylonitrile) as Highly Rate and Cycle Stable Cathode Material for Sodium-Sulfur Batteries}}}, doi = {{10.1149/1945-7111/acb2fa}}, volume = {{170}}, year = {{2023}}, } @article{52343, abstract = {{Improved enantioselectivity in the 1,2-addition was observed for chiral Rh norbornadiene catalysts immobilized on ordered mesoporous silica with small pores. Confinement effects were rationalized by experimental and computational studies.}}, author = {{Kirchhof, Manuel and Gugeler, Katrin and Beurer, Ann-Katrin and Fischer, Felix Richard and Batman, Derman and Bauch, Soeren M. and Kolin, Sofia and Nicholas, Elliot and Schoch, Roland and Vogler, Charlotte and Kousik, Shravan R. and Zens, Anna and Plietker, Bernd and Atanasova, Petia and Naumann, Stefan and Bauer, Matthias and Bruckner, Johanna R. and Traa, Yvonne and Kästner, Johannes and Laschat, Sabine}}, issn = {{2044-4753}}, journal = {{Catalysis Science Technology}}, keywords = {{Catalysis}}, number = {{12}}, pages = {{3709--3724}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Tethering chiral Rh diene complexes inside mesoporous solids: experimental and theoretical study of substituent, pore and linker effects on asymmetric catalysis}}}, doi = {{10.1039/d3cy00381g}}, volume = {{13}}, year = {{2023}}, } @article{49608, abstract = {{The effects of backbone amine functionalization in three new homoleptic C^N^C type ruthenium(II) complexes bearing a tridentate bis‐imidazole‐2‐ylidene pyridine ligand framework are characterized and studied by single crystal diffraction, electrochemistry, optical spectroscopy and transient absorption spectroscopy in combination with ab initio DFT calculations. Functionalization by dimethylamine groups in 4‐position of the pyridine backbone significantly influences the properties of the complexes as revealed by comparison with the unfunctionalized references. As a result of the amine functionalization, a higher molar absorption coefficient of the MLCT bands, a decreased photoluminescence quantum yield at room temperature together with a shortened excited state lifetime but an improved photostability is observed. Introduction of electron donating and withdrawing groups at the NHC unit modifies the electronic and optical properties, such as the oxidation potential, absorption and emission properties, and the lifetimes of the excited states.}}, author = {{Fritsch, Lorena and Vukadinovic, Yannik and Lang, Moritz and Naumann, Robert and Bertrams, Maria-Sophie and Kruse, Ayla and Schoch, Roland and Müller, Patrick and Neuba, Adam and Dierks, Philipp and Lochbrunner, Stefan and Kerzig, Christoph and Heinze, Katja and Bauer, Matthias}}, issn = {{2367-0932}}, journal = {{ChemPhotoChem}}, keywords = {{Photo}}, publisher = {{Wiley}}, title = {{{Chemical and photophysical properties of amine functionalized bis‐NHC‐pyridine‐Ru(II) complexes}}}, doi = {{10.1002/cptc.202300281}}, year = {{2023}}, } @article{46548, abstract = {{The use of iron as a replacement for noble metals in photochemical and photophysical applications is challenging due to the typically fast deactivation of short-lived catalytically active states. Recent success of a cyclometalated iron(III) complex utilizing a bis-tridentate ligand motif inspired the use of phenyl-1H-pyrazole as a bidentate ligand. Five complexes using the tris(1-phenylpyrazolato-N,C2)iron(III) complex scaffold are presented. In addition to the parent complex, four derivatives with functionalization in the meta-position of the phenyl ring are thoroughly investigated by single crystal diffractometry, UV-Vis-spectroscopy, and cyclic voltammetry. Advanced X-ray spectroscopy in the form of X-ray absorption and emission spectroscopy allows unique insights into the electronic structure as well as DFT calculations. The ligand design leads to overlapping MLCT and LMCT absorption bands, and emissive behavior is suppressed by low-lying MC states.}}, author = {{Hirschhausen, Tanja and Fritsch, Lorena and Lux, Franziska and Steube, Jakob and Schoch, Roland and Neuba, Adam and Egold, Hans and Bauer, Matthias}}, issn = {{2304-6740}}, journal = {{Inorganics}}, keywords = {{Photo}}, number = {{7}}, publisher = {{MDPI AG}}, title = {{{Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands}}}, doi = {{10.3390/inorganics11070282}}, volume = {{11}}, year = {{2023}}, } @article{48167, abstract = {{AbstractA new approach for the characterization of CO2 methanation catalysts prepared by thermal decomposition of a nickel MOF by hard X‐ray photon‐in/photon‐out spectroscopy in form of high energy resolution fluorescence detected X‐ray absorption near edge structure spectroscopy (HERFD‐XANES) and valence‐to‐core X‐ray emission (VtC‐XES) is presented. In contrast to conventional X‐ray absorption spectroscopy, the increased resolution of both methods allows a more precise phase determination of the final catalyst, which is influenced by the conditions during MOF decomposition.}}, author = {{Strübbe, Sven and Nowakowski, Michał and Schoch, Roland and Bauer, Matthias}}, issn = {{1439-4235}}, journal = {{ChemPhysChem}}, keywords = {{Catalysis}}, publisher = {{Wiley}}, title = {{{High‐Resolution X‐ray Absorption and Emission Spectroscopy for Detailed Analysis of New CO2 Methanation Catalysts}}}, doi = {{10.1002/cphc.202300113}}, year = {{2023}}, } @article{40993, abstract = {{Understanding high-temperature unconventional superconductivity has become a long-lasting problem in which the cuprates stand as central reference materials. Given this impasse, the recent discovery of superconductivity in analogous nickelate thin films represents a fundamental breakthrough calling for the identification of additional materials in this class. In particular, thermodynamically more robust systems are required to “upgrade” nickelate superconductors from thin films to bulk samples. Here, we contribute in this direction by reporting the synthesis of the new single-layer T′ Pr2NiO3F compound, assessing this synthesis in relation to the only previous T′ nickelate La2NiO3F, and analyzing the electronic properties across the R2NiO3F series (R = La–Lu) via first-principles calculations. We find that these mixed anion systems have a comparatively high degree of stability and their synthesis enables a fine-tuning of their composition as inferred from their characterization. Furthermore, we find that these unprecedented square-planar nickelates hold great promise as prospective superconductors due to their exceptional electronic structure.}}, author = {{Wissel, Kerstin and Bernardini, Fabio and Oh, Heesu and Vasala, Sami and Schoch, Roland and Blaschkowski, Björn and Glatzel, Pieter and Bauer, Matthias and Clemens, Oliver and Cano, Andrés}}, issn = {{0897-4756}}, journal = {{Chemistry of Materials}}, keywords = {{Materials Chemistry, General Chemical Engineering, General Chemistry}}, number = {{16}}, pages = {{7201--7209}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Single-Layer T′ Nickelates: Synthesis of the La and Pr Members and Electronic Properties across the Rare-Earth Series}}}, doi = {{10.1021/acs.chemmater.2c00726}}, volume = {{34}}, year = {{2022}}, } @article{40987, abstract = {{ii) complexes by chelate ring expansion}}}, doi = {{10.1039/d1cc02173g}}, volume = {{57}}, year = {{2021}}, } @article{41000, abstract = {{Metal-catalyzed C−H activations are environmentally and economically attractive synthetic strategies for the construction of functional molecules as they obviate the need for pre-functionalized substrates and minimize waste generation. Great challenges reside in the control of selectivities, the utilization of unbiased hydrocarbons, and the operation of atom-economical dehydrocoupling mechanisms. An especially mild borylation of benzylic CH bonds was developed with the ligand-free pre-catalyst Co[N(SiMe3)2]2 and the bench-stable and inexpensive borylation reagent B2pin2 that produces H2 as the only by-product. A full set of kinetic, spectroscopic, and preparative mechanistic studies are indicative of a tandem catalysis mechanism of CH-borylation and dehydrocoupling via molecular CoI catalysts.}}, author = {{Ghosh, Pradip and Schoch, Roland and Bauer, Matthias and Jacobi von Wangelin, Axel}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{1}}, publisher = {{Wiley}}, title = {{{Selective Benzylic CH‐Borylations by Tandem Cobalt Catalysis}}}, doi = {{10.1002/anie.202110821}}, volume = {{61}}, year = {{2021}}, } @article{41013, abstract = {{Within this article, it is shown that an electrochemical defluorination and additional fluorination of Ruddlesden–Popper-type La2NiO3F2 is possible within all-solid-state fluoride-ion batteries. Structural changes within the reduced and oxidized phases have been examined by X-ray diffraction studies at different states of charging and discharging. The synthesis of the oxidized phase La2NiO3F2+x proved to be successful by structural analysis using both X-ray powder diffraction and automated electron diffraction tomography techniques. The structural reversibility on re-fluorinating and re-defluorinating is also demonstrated. Moreover, the influence of different sequences of consecutive reduction and oxidation steps on the formed phases has been investigated. The observed structural changes have been compared to changes in phases obtained via other topochemical modification approaches such as hydride-based reduction and oxidative fluorination using F2 gas, highlighting the potential of such electrochemical reactions as alternative synthesis routes. Furthermore, the electrochemical routes represent safe and controllable synthesis approaches for novel phases, which cannot be synthesized via other topochemical methods. Additionally, side reactions, occurring alongside the desired electrochemical reactions, have been addressed and the cycling performance has been studied.}}, author = {{Wissel, Kerstin and Schoch, Roland and Vogel, Tobias and Donzelli, Manuel and Matveeva, Galina and Kolb, Ute and Bauer, Matthias and Slater, Peter R. and Clemens, Oliver}}, issn = {{0897-4756}}, journal = {{Chemistry of Materials}}, keywords = {{Materials Chemistry, General Chemical Engineering, General Chemistry}}, number = {{2}}, pages = {{499--512}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Electrochemical Reduction and Oxidation of Ruddlesden–Popper-Type La2NiO3F2 within Fluoride-Ion Batteries}}}, doi = {{10.1021/acs.chemmater.0c01762}}, volume = {{33}}, year = {{2021}}, }