TY - JOUR AB - 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. AU - Ghosh, Pradip AU - Schoch, Roland AU - Bauer, Matthias AU - Jacobi von Wangelin, Axel ID - 41000 IS - 1 JF - Angewandte Chemie International Edition KW - General Chemistry KW - Catalysis SN - 1433-7851 TI - Selective Benzylic CH‐Borylations by Tandem Cobalt Catalysis VL - 61 ER - TY - JOUR AB - 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. AU - Wissel, Kerstin AU - Schoch, Roland AU - Vogel, Tobias AU - Donzelli, Manuel AU - Matveeva, Galina AU - Kolb, Ute AU - Bauer, Matthias AU - Slater, Peter R. AU - Clemens, Oliver ID - 41013 IS - 2 JF - Chemistry of Materials KW - Materials Chemistry KW - General Chemical Engineering KW - General Chemistry SN - 0897-4756 TI - Electrochemical Reduction and Oxidation of Ruddlesden–Popper-Type La2NiO3F2 within Fluoride-Ion Batteries VL - 33 ER - TY - JOUR AB - We present the η3-coordination of the 2-phosphaethynthiolate anion in the complex (PN)2La(SCP) (2) [PN=N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate-bridged (PN)2La(μ-1,3-SCN)2La(PN)2 (3) and azide-bridged (PN)2La(μ-1,3-N3)2La(PN)2 (4) complexes indicates that the [SCP]− coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*-orbital of the [SCP]− ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP]− anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]− ligand to form the first CAAC stabilized group 15–group 16 fulminate-type complexes (PN)2La{SPC(RCAAC)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP-to-SPC isomerization is proposed based on DFT calculations. AU - Watt, Fabian A. AU - Burkhardt, Lukas AU - Schoch, Roland AU - Mitzinger, Stefan AU - Bauer, Matthias AU - Weigend, Florian AU - Goicoechea, Jose M. AU - Tambornino, Frank AU - Hohloch, Stephan ID - 41010 IS - 17 JF - Angewandte Chemie International Edition KW - General Chemistry KW - Catalysis SN - 1433-7851 TI - η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)** VL - 60 ER - TY - JOUR AB - Here we explore the electronic structure of the diiron complex [(dppf)Fe(CO)3]0/+ [10/+; dppf = 1,1′-bis(diphenylphosphino)ferrocene] in two oxidation states by an advanced multitechnique experimental approach. A combination of magnetic circular dichroism, X-ray absorption and emission, high-frequency electron paramagnetic resonance (EPR), and Mössbauer spectroscopies is used to establish that oxidation of 10 occurs on the carbonyl iron ion, resulting in a low-spin iron(I) ion. It is shown that an unequivocal result is obtained by combining several methods. Compound 1+ displays slow spin dynamics, which is used here to study its geometric structure by means of pulsed EPR methods. Surprisingly, these data show an association of the tetrakis[3,5-bis(trifluoromethylphenyl)]borate counterion with 1+. AU - Winkler, Mario AU - Schnierle, Marc AU - Ehrlich, Felix AU - Mehnert, Kim-Isabelle AU - Hunger, David AU - Sheveleva, Alena M. AU - Burkhardt, Lukas AU - Bauer, Matthias AU - Tuna, Floriana AU - Ringenberg, Mark R. AU - van Slageren, Joris ID - 41012 IS - 5 JF - Inorganic Chemistry KW - Inorganic Chemistry KW - Physical and Theoretical Chemistry SN - 0020-1669 TI - Electronic Structure of a Diiron Complex: A Multitechnique Experimental Study of [(dppf)Fe(CO) 3]+/0 VL - 60 ER - TY - JOUR AB - Platinum hydride species catalyze a number of interesting organic reactions. However, their reactions typically involve the use of high loadings of noble metal and are difficult to recycle, making them somewhat unsustainable. We have synthesized surface-immobilized Pt–H species via oxidative addition of surface OH groups to Pt(PtBu3)2 (1), a rarely used immobilization technique in surface organometallic chemistry. The hydride species thus made were characterized by infrared, magic-angle spinning nuclear magnetic resonance, and X-ray absorption spectroscopies and catalyzed both olefin isomerization and cycloisomerization of a 1,6 enyne (5) with a high selectivity and low Pt loading. AU - Maier, Sarah AU - Cronin, Steve P. AU - Vu Dinh, Manh-Anh AU - Li, Zheng AU - Dyballa, Michael AU - Nowakowski, Michal AU - Bauer, Matthias AU - Estes, Deven P. ID - 41009 IS - 11 JF - Organometallics KW - Inorganic Chemistry KW - Organic Chemistry KW - Physical and Theoretical Chemistry SN - 0276-7333 TI - Immobilized Platinum Hydride Species as Catalysts for Olefin Isomerizations and Enyne Cycloisomerizations VL - 40 ER - TY - JOUR AB - The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe4, Fe6, and Fe7 nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles. AU - Chakraborty, Uttam AU - Bügel, Patrick AU - Fritsch, Lorena AU - Weigend, Florian AU - Bauer, Matthias AU - Jacobi von Wangelin, Axel ID - 41011 IS - 2 JF - ChemistryOpen KW - General Chemistry SN - 2191-1363 TI - Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles VL - 10 ER - TY - BOOK ED - Standke, Jan ED - Topalovic, Elvira ID - 40920 KW - General Earth and Planetary Sciences KW - General Environmental Science SN - 0418-9426 TI - In Krisen erzählen – von Krisen erzählen. Sprachliche, literarische und mediale Dimensionen. VL - 68 ER - TY - CHAP AU - Sackel, Johanna AU - Wöbse, Anna-Katharina ED - Torma, Franziska ID - 40494 SN - 9781474299107 T2 - A Cultural History of the Sea in the Global Age TI - Networks VL - 6 ER - TY - BOOK ED - Plien, Christian ED - Topalovic, Elvira ID - 37092 KW - General Earth and Planetary Sciences KW - General Environmental Science SN - 0418-9426 TI - Mehrdeutigkeiten VL - 68 ER - TY - CONF AU - Adelt, Peer AU - Koppelmann, Bastian AU - Müller, Wolfgang AU - Scheytt, Christoph ID - 23992 T2 - Workshop Methoden und Beschreibungssprachen zur Modellierung und Verifikation von Schaltungen und Systemen (MBMV 2021) TI - Register and Instruction Coverage Analysis for Different RISC-V ISA Modules ER -