Article
Chemistry, Multidisciplinary
Jana-Alina Zur, Michelle Schmidt, Kai-Stephan Feichtner, Prakash Duari, Julian Loffler, Thorsten Scherpf, Viktoria H. Gessner
Summary: This study reports the formation of stable PH ylides and their ability to promote the formation of carbanionic phosphines with strong donor abilities and high basicities. Additionally, they can form zwitterionic complexes and be used for catalytic hydroamination reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Katharina Dilchert, Michelle Schmidt, Angela Grossjohann, Kai-Stephan Feichtner, Robert E. Mulvey, Viktoria H. Gessner
Summary: s-Block metal carbenoids are carbene synthons used in a variety of organic transformations. While sodium and potassium chloride carbenoids exhibit high stabilities in all solvents, the stability of lithium carbenoid varies depending on the solvent.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Lukas Brieger, Christian Unkelbach, Carsten Strohmann
Summary: The formation of THF-solvated alkali metal benzyl compounds [PhCH2M . (thf)(n)] (M=Na, Rb, Cs) was successfully achieved through deprotonation of toluene with a bimetallic mixture and selective crystallization. These compounds can serve as alkali metal mediating reagents and have shown to be convenient for deprotonating acidic C-H as well as N-H compounds for aminometalation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Keith Izod, Atheer M. Madlool, Alex Craig, Paul G. Waddell
Summary: Different phosphido-borane complexes were synthesized using different solvents and reactants. Crystal structure analysis showed that some of these complexes formed polymer structures.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Jan Klett
Summary: Lochmann-Schlosser superbases (LSB) are standard reagents in synthetic chemistry for exchanging protons on organic frameworks with alkali metal cations, which can then be replaced by various electrophilic groups. Recent research, mainly based on new soluble compounds, has provided structural evidence for the nature of the reactive species in LSB mixtures, leading to advanced and detailed conclusions about the interplay of the components involved.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Duo Fu, Changmeng Xi, Jiaxi Xu
Summary: alpha-Halo-alpha-methylthio-beta-ketosulfones with a quaternary halocarbon stereocenter were synthesized in moderate to excellent yields (39 examples; up to 98%) through selective demethyl oxidative halogenations of diacyl dimethylsulfonium methylides. The current protocols provide a direct and efficient approach to introduce a halogen atom into organic compounds with high functional group tolerance under metal-free conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Sachin A. Nalawade, Manjeet Singh, DRGKoppalu R. Puneeth R. Kumar, Sanjit Dey, Hosahudya N. Gopi
Summary: Utilization of the Wittig reaction to synthesize conjugative multiple double bonds is rare. We examined the utility of the Wittig reaction to construct conjugative two and three carbon-carbon double bonds on the N-protected amino acid backbone. The ethyl esters of N-Boc amino acids with multiple carbon-carbon double bonds in the backbone were isolated in excellent yields with exceptional E-selectivity of the double bonds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Srikanth Balijapelly, Prashanth Sandineni, Amit Adhikary, Nikolay N. Gerasimchuk, Aleksandr V. Chernatynskiy, Amitava Choudhury
Summary: Two new ternary thiogallates were synthesized via gas passing and high temperature solid state routes, exhibiting different crystal structures and ionic conductivities. Experimental and theoretical studies provided insights into their structural parameters and band gaps, shedding light on the mechanisms of ionic conduction in these compounds.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Kwangnam Kim, Yiliang Li, Ping-Chun Tsai, Fei Wang, Seoung-Bum Son, Yet-Ming Chiang, Donald J. Siegel
Summary: The development of solid-state batteries has been hindered by limited understanding of ion mobility control in solid electrolytes (SEs). However, the present study combines theory and experiments to explore the synthesizability of marginally stable anti-perovskite (AP) SEs, which are predicted to exhibit high ionic mobility for Li+, Na+, and K+. The study finds a linear correlation between lattice distortion and stabilization temperature, indicating that APs with the highest ionic mobility require the highest synthesis temperature. The experimental results align well with the computational predictions, suggesting that a compound's zero K decomposition energy is an efficient descriptor for synthesizing new SEs.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Natalia L. Bazyakina, Mikhail Moskalev, Anton Cherkasov, Valentin M. Makarov, Igor L. Fedushkin
Summary: Treatment of toluene solutions with 4,4'-bipyridine affords coordination polymers with different dimensional structures.
Article
Agricultural Engineering
Anfu Hu, Qian Xia, Jun Wang, Tan Li, Kaige Wang, Jian Wu, Guojun Zhou, Jian Jiang
Summary: This study reveals the effects of alkali and alkali earth metals on the pyrolysis behavior of tobacco. The addition of these metals increases the content of ketones, acids, nitrogen-containing compounds, and esters, while inhibiting the formation of anhydro sugars and aldehydes. The presence of alkali and alkali earth metal ions enhances the generation of solid residues and promotes the conversion of anhydro sugars to ketones.
INDUSTRIAL CROPS AND PRODUCTS
(2023)
Article
Chemistry, Physical
Miao Yu, Ming-Wen Chang, Nikolay Kosinov, Emiel J. M. Hensen
Summary: Alkali metals can enhance the synthesis of methanethiol, and alkali sulfides themselves are found to be the active sites. This study presents the first example of using hydrogen sulfide as a hydrogen donor for the formation of thiol counterpart.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Alex Von Gunten, Kunal Velinkar, Eranda Nikolla, Jeffrey Greeley
Summary: Sodium-containing batteries have the potential to improve energy storage devices. However, the development of Na-O-2 batteries is hindered by poor cell lifespans caused by parasitic reactions involving the NaO2 discharge products. In this study, a molecular-level mechanistic understanding of the surface chemistry of the NaO2 discharge product is elucidated through density functional theory calculations and experimental observations.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Wenli Zhang, Minglei Sun, Jian Yin, Edy Abou-Hamad, Udo Schwingenschlogl, Pedro M. F. J. Costa, Husam N. Alshareef
Summary: Organic anodes, particularly cyclized polyacrylonitrile (cPAN), have shown excellent potential for alkali metal ion batteries, achieving high reversible capacity and displaying unique potential-dependent solid electrolyte interphase formation. The hexagonal carbon ring, piperidine ring, and pyridine nitrogen in ladder cPAN are identified as the main active sites for lithium-ion storage. Additionally, cPAN demonstrates decent performance as an anode in SIBs and PIBs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Yaoyao Lian, Ya Li, Ruyan Lv, Lifeng Wang, Wenfei Xiong
Summary: This study found that alkali concentration has a significant impact on the gel formation of rice protein, with higher concentration leading to faster gel formation. Heating can accelerate the gel formation rate, but prolonged heat treatment causes gel liquefaction. Alkali can cause depolymerization of glutelin and form a gel network, while higher alkali concentration contributes to the gel network mainly through the formation of disulfide bonds.
FOOD HYDROCOLLOIDS
(2024)
Review
Chemistry, Multidisciplinary
Sebastien Lapointe, Abir Sarbajna, Viktoria H. Gessner
Summary: Phosphines are important ligands in homogeneous catalysis, and YPhos ligands, with their strong donor abilities and high tunability, have shown remarkable activities and selectivity in gold and palladium catalyzed reactions. They have been used in a variety of transformations with high efficiency, making them suitable for medium- to large-scale applications.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Tobias Stalder, Felix Krischer, Henning Steinert, Philipp Neigenfind, Viktoria H. Gessner
Summary: In this study, the preparation, structural and coordination properties of ylide-substituted phosphonium cations were investigated. The results revealed that the ylide systems exhibited stronger electron-donating properties compared to N-heterocyclic phosphenium ions, and the mono-ylide substituted cations showed more pronounced electrophilic behavior. These findings suggest the tunability of ylide-functionalized phosphorus cations and their potential applications in coordination chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Philipp Neigenfind, Daniel Knyszek, Jens Handelmann, Viktoria H. Gessner
Summary: This study successfully synthesized bulky, ortho-substituted triarylamines using ylide-substituted phosphines (YPhos) with high yields at low temperatures, providing a convenient and mild method for the synthesis of organic electronic materials.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Jana-Alina Zur, Michelle Schmidt, Kai-Stephan Feichtner, Prakash Duari, Julian Loffler, Thorsten Scherpf, Viktoria H. Gessner
Summary: This study reports the formation of stable PH ylides and their ability to promote the formation of carbanionic phosphines with strong donor abilities and high basicities. Additionally, they can form zwitterionic complexes and be used for catalytic hydroamination reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jonas F. Goebel, Julian Loeffler, Zhongyi Zeng, Jens Handelmann, Albert Hermann, Ilja Rodstein, Tobias Gensch, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium-catalyzed couplings of silicon enolates with aryl electrophiles are limited to expensive bromide substrates. However, a study using ylide functionalized phosphines (YPhos) showed promising results in coupling inexpensive aryl chlorides with alpha-trimethylsilyl alkylnitriles. A statistical model was developed to predict catalyst structures with superior performance, leading to the synthesis of pharmaceutically significant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Mike Joerges, Felix Krischer, Viktoria H. Gessner
Summary: The ability of transition metals to convert carbon monoxide into useful compounds is crucial for many chemical processes. However, only a few s- and p-block elements can bind and activate CO. This study reports a new method using metalated phosphorus ylides to generate stable ketenyl anions, offering a new pathway for the synthesis of ketenes and related compounds.
Article
Chemistry, Multidisciplinary
V. S. V. S. N. Swamy, Felix Krischer, Christopher Schwarz, Henning Steinert, Bert Mallick, Viktoria H. Gessner
Summary: Due to the strong electron-donating ability of ylide substituents, diylidyltetrylenes are usually highly nucleophilic species with strong donor capacities. However, we demonstrate that their electronic properties can be effectively tuned through variation of the substituent in the ylide backbone. Cyano groups are particularly capable in lowering the LUMO energy of diylidyl germylenes and turning them into electrophilic compounds. Experimental studies confirmed this.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Julian Loeffler, Sofie M. P. Vanden Broeck, Catherine S. J. Cazin, Steven P. Nolan, Viktoria H. Gessner
Summary: Ylide-functionalized phosphines (YPhos) have been shown to be highly donating ligands in gold(I)-mediated reactions, with high binding strengths. A calorimetric study of the [Au(YPhos)Cl] system revealed the enthalpies of YPhos-Au bond dissociation, which were found to correlate with the electronic properties of the ligands. Computational methods can be used to conveniently derive the reaction enthalpies, making them easily accessible descriptors for quantifying ligand donor properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Ilja Rodstein, Angelino Doppiu, Viktoria H. Gessner
Summary: In recent years, highly electron-donating ligands have emerged as advantageous for the development of high-performance platinum catalysts for hydrosilylation reactions. This work presents platinum precatalysts based on ylide-substituted phosphines (YPhos) that show stability under ambient conditions and high activities and selectivities in hydrosilylation reactions of alkenes and amides at low catalyst loadings and mild reaction conditions.
Article
Chemistry, Physical
Florian Papp, Daniel Sowa Prendes, Sourav Manna, Ann-Katrin Seitz, Sofiya Kostiukovska, Julian Loeffler, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium complexes with ylide-functionalized phosphine ligands catalyze the arylation of N-protected hydantoins with aryl chlorides, enabling the synthesis of a wide variety of hydantoins, including derivatives of the anticonvulsant drugs phenytoin and mephenytoin. Selective monoarylations, sequential diarylations, and arylation-alkylation sequences have been achieved, along with stepwise deprotection strategies.
Article
Chemistry, Multidisciplinary
Julian Loeffler, Viktoria H. Gessner
Summary: Bulky ylide-substituted phosphines have recently been used as effective ligands in homogeneous catalysis. The attempted synthesis of the ylide-substituted fluorenylphosphine resulted in unexpected elimination reactions and the formation of cyclic phosphonium ylide. Coordination to transition metals resulted in the formation of zwitterionic metal complexes with a neutral phosphide ligand.
Article
Chemistry, Physical
Angela Burhenn, Roberta Bavaro, Viktoria H. Gessner
Summary: In this study, a series of chloro- and polyhalogenated compounds, including polychlorinated biphenyls (PBCs) extracted from construction dust, were successfully dehalogenated under mild reaction conditions using palladium complexes with ylide-substituted phosphines (YPhos) as ligands. Ethanol was used as the hydride source in the reaction, and site-selective deuterations could be achieved by switching to deuteroethanol.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Sebastien Lapointe, Prakash Duari, Viktoria H. Gessner
Summary: Control of metal-ligand interaction by changing the ligand protonation state is crucial for catalytic transformations. We investigated a new pincer ligand with a central ylide that changes from a neutral to an anionic ligand upon deprotonation. The strong donor ability of the ylide was enhanced by deprotonation and exhibited unique interaction with the metal, resulting in activation of strong bonds.
Article
Chemistry, Physical
Svenja Jaeger, Philipp Meyer, Kai-Stephan Feichtner, Stefan Henkel, Gerhard W. Schwaab, Viktoria H. Gessner, Martina Havenith
Summary: The study demonstrates that the reaction of alkali metal amides with water is close to barrierless even at ultra-cold conditions, leading to aggregation induced reaction to form specific products in helium nanodroplets at ultra-low temperatures.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Ilja Rodstein, Leif Kelling, Julian Loffler, Thorsten Scherpf, Abir Sarbajna, Diego M. Andrada, Viktoria H. Gessner
Summary: The use of simple PdCl2 complexes stabilized through a unique bonding motif with ylide-substituted phosphines (YPhos) as efficient precatalysts has improved the efficiency of C-X cross-coupling reactions.
