Article
Chemistry, Multidisciplinary
Kelsie E. Wentz, Andrew Molino, Sarah L. Weisflog, Aishvaryadeep Kaur, Diane A. Dickie, David J. D. Wilson, Robert J. Gilliard
Summary: The study explores the synthesis of carbene-stabilized monoanionic borafluorenes as a new platform for constructing high-value boracyclic materials, demonstrating their potential for forming novel boron-containing compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Tobias Bischof, Xueying Guo, Ivo Krummenacher, Lukas Bessler, Zhenyang Lin, Maik Finze, Holger Braunschweig
Summary: This article describes the synthesis of 9-borafluorene with an electron-withdrawing o-carboranyl substituent and its reactions with a series of alkenes. The experimental results show that the carboranyl-substituted derivative has superior insertion reactivity.
Review
Polymer Science
Jiaxi Xu, Nikos Hadjichristidis
Summary: The incorporation of heteroatom-containing weak bonds along polymer backbones has become a popular tool to accelerate degradation. Many methods have been reported for the synthesis of degradable heteroatom-containing polymers based on step-growth polymerization and chain-growth ring-opening polymerization. Ring-opening metathesis polymerization has emerged as an approach for the synthesis of various types of degradable polymers. This review covers the synthesis of different heteroatom-containing degradable polymers via ring-opening metathesis polymerization and their degradation mechanisms under different conditions.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Xing Chen, Guoyun Meng, Guanming Liao, Florian Rauch, Jiang He, Alexandra Friedrich, Todd B. Marder, Nan Wang, Pangkuan Chen, Suning Wang, Xiaodong Yin
Summary: A series of 9-borafluorene derivatives functionalized with electron-donating groups were synthesized, some of which showed strong yellowish emission. The new compounds exhibited enhanced stability towards the atmosphere and excellent thermal stability, demonstrating great potential for applications in materials science. Organic light-emitting diode (OLED) devices fabricated with two of the highly emissive compounds displayed strong yellow-greenish electroluminescence, reaching a maximum luminance intensity of over 22,000 cd m(-2).
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Polymer Science
Mohammad Yasir, Andreas F. M. Kilbinger
Summary: Norbornene and cyclohexene show different polymerization behaviors using Grubbs' catalysts due to their varying ring strain energy levels; a sequence-selective cascade polymerization of a monomer containing both rings resulted in polymers with moderate molecular weight dispersities and good control over molecular weight.
Article
Chemistry, Multidisciplinary
Tobias Bischof, Lukas Bessler, Ivo Krummenacher, Leon Erhard, Holger Braunschweig, Maik Finze
Summary: Direct insertion of unsaturated substrates into a five-membered borole ring can produce valuable heterocycles with three-coordinate boron atoms. A highly Lewis acidic 9-o-carboranyl-9-borafluorene can react with a wide range of unsaturated molecules to form larger boraheterocyclic products. The ring expansion reactions of the central borole ring proceed rapidly at room temperature, with the o-carboranyl substituent enhancing the insertion reactivity of 9-borafluorenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Kelsie E. Wentz, Andrew Molino, Lucas A. Freeman, Diane A. Dickie, David J. D. Wilson, Robert J. Gilliard
Summary: The impact of the spatial arrangement of the alkali metal on the electronic properties of 9-carbene-9-borafluorene monoanions has been evaluated, leading to the isolation of a series of [K][9-CAAC-9-borafluorene] complexes. These complexes show potential for controlling the nucleophilic and electron transfer properties of the monoanions, with the formation of new air-stable spirocycles that display fluorescence properties under UV light.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jan Adamek, Paulina H. Marek-Urban, Krzysztof Wozniak, Krzysztof Durka, Sergiusz Lulinski
Summary: The synthesis and characterization of two fluorinated 3,6-diaza-9-hydroxy-9-borafluorene oxonium acids with improved hydrolytic stability and strong electron-deficient character are reported. These compounds were used as precursors for fluorescent spiro-type complexes with specific properties such as delayed emission, white light emission, and photocatalytic performance.
Article
Chemistry, Multidisciplinary
Johannes Krebs, Alena Haefner, Sonja Fuchs, Xueying Guo, Florian Rauch, Antonius Eichhorn, Ivo Krummenacher, Alexandra Friedrich, Lei Ji, Maik Finze, Zhenyang Lin, Holger Braunschweig, Todd B. Marder
Summary: The choice of backbone linker has a significant impact on the reactivity of the compounds and the location of the LUMO. This study focuses on the rearrangement of two ortho-bis-(9-borafluorene)s and the synthesis of dibora-benzo[a]fluoroanthene isomers. The compounds were fully characterized using various techniques and theoretical calculations.
Article
Polymer Science
James McQuade, Mya I. Serrano, Frieder Jakle
Summary: The incorporation of main group elements into polymers enables the synthesis of functional materials with unique molecular structures and chemical properties. Ring-opening metathesis polymerization (ROMP) is a versatile method for generating new main group element-functionalized materials.
Article
Chemistry, Inorganic & Nuclear
Yijie Li, Yu-Hsuan Shen, Alec M. M. Esper, John R. R. Tidwell, Adam S. S. Veige, Caleb D. D. Martin
Summary: The reaction of Ph3PAuN3 with 9-Ph-9-borafluorene resulted in the complexation of azide to boron, while a gold acetylide reacted with 9-Ph-9-borafluorene to insert the acetylide carbon and form a six-membered boracycle with an exocyclic double bond.
DALTON TRANSACTIONS
(2023)
Review
Polymer Science
Jiaxi Xu, Xin Wang, Jingjing Liu, Xiaoshuang Feng, Yves Gnanou, Nikos Hadjichristidis
Summary: Ring-opening polymerization (ROP) is a prevalent and convenient method for synthesizing well-defined polymers with initiators/catalysts. One of the challenges faced by ROP catalysts is the selective activation of functional groups or linkages of the monomer without those carried out in the polymer chains, especially at high conversion. H-bonding organocatalysts can offer precise selectivity for ROP in a wide range of monomers.
PROGRESS IN POLYMER SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert
Summary: The ring-opening metathesis polymerization of cyclopropenes using hydrazonium initiators was investigated. The initiators, formed by condensing 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers through a sequence of [3+2] cycloaddition and cycloreversion reactions. The study showed that the monomer to initiator ratio had a positive correlation with the degree of polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Zhunxuan Li, Rui Chen, Ying Wang, Linlin Zhu, Wenyi Luo, Zhen Zhang, Nikos Hadjichristidis
Summary: An efficient synthetic methodology was developed for the modification of hyperbranched polyethyleneimines (PEI) using N-sulfonyl aziridines, resulting in materials with unique fluorescence properties and the ability to remove hazardous metals.
Review
Chemistry, Applied
Nina Guy, Olivia Giani, Sebastien Blanquer, Julien Pinaud, Jean-Jacques Robin
Summary: Photopolymerization is gaining interest in both industrial and academic fields due to its high reaction kinetics, low emissions of organic solvents, and reduced shrinking stress. This method has mainly been developed for radical polymerization of vinyl monomers and to a lesser extent for ring-opening polymerization (ROP). With the emergence of new initiating systems, the photopolymerization of various cyclic monomers has expanded beyond epoxides, which were the first monomers polymerized by cationic ring-opening polymerization (CROP).
PROGRESS IN ORGANIC COATINGS
(2021)
Article
Chemistry, Applied
D. E. Dusmatova, Kh. M. Bobakulov, K. K. Turgunov, R. F. Mukhamatkhanova, V. V. Uzbekov, H. Gildenast, U. Englert, I. D. Sham'yanov, B. Tashkhojaev, V. P. Bruskov, N. D. Abdullaev
Summary: This study conducted a phytochemical research on Karatanolide(1), 11,13β-dihydrokaratanolide(2), and 11,13α-dihydrokaratanolide(3) and made significant findings.
NATURAL PRODUCT RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Lukas Alig, Kim A. Eisenlohr, Yaroslava Zelenkova, Sven Rosendahl, Regine Herbst-Irmer, Serhiy Demeshko, Max C. Holthausen, Sven Schneider
Summary: In this study, a Re-IV pincer platform is reported to mediate N-2 splitting with unprecedented yield through chemical reduction or electrolysis. The resulting Re-V nitrides from N-2 undergo facile nitrogen atom transfer to nitric oxide, giving nitrous oxide nearly quantitatively. Experimental and computational results suggest that outer-sphere ReN/NO radical coupling is facilitated by the activation of the nitride via initial coordination of NO.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hans Gildenast, Felix Garg, Ulli Englert
Summary: Tris(2-(trimethylsilyl)phenyl)phosphine, P(o-TMSC6H4)(3), was synthesized and characterized. The compound shows air stability due to its large steric bulk, and can undergo protonation, oxidation, and complexation to Au-I. However, complexation reactions with other metal cations were unsuccessful. In addition, the compound exhibits reversible electrochemical oxidation, making it a model compound for studying the electronic properties of sterically unencumbered phosphines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Spectroscopy
Sherzod Zhurakulov, Khayrulla Bobakulov, Akmaljon Tojiboev, Ulli Englert, Ruimin Wang, Irmgard Kalf, Valentina Vinogradova, Bakhodir Tashkhodjaev
Summary: The structure of 3-(3,4-dimethoxyphenylethylamino)-methylidene-1,2,3,9-tetrahydropyrrolo[2,1-b]-quinazolin-9-one hydrochloride has been determined by single-crystal X-ray diffraction at 100 K. The crystallographic study revealed the molecular structure, configuration of the bond, and space group of the crystal.
SPECTROSCOPY LETTERS
(2022)
Article
Crystallography
Damian Mroz, Ruimin Wang, Carsten Paulmann, Ulli Englert, Richard Dronskowski
Summary: In this study, anisotropic displacement parameters (ADPs) of an organopalladium complex were obtained from synchrotron diffraction data and compared with first-principles calculations. The results show that the harmonic approximation underestimates the amplitudes of atomic motion by approximately 20%. By calculating the ADPs at a temperature 20 K higher than the actual diffraction temperature, the systematic underestimation of the harmonic theory can be accounted for. The findings highlight the importance of using high-quality experimental benchmarks and provide insights for the application of quasi-harmonic approximation in larger systems.
Article
Crystallography
Steven van Terwingen, Noah Nachtigall, Ulli Englert
Summary: The ligand 3-(4-(1,3,5-trimethyl-1H-pyrazol-4-yl)phenyl)acetylacetone (1) shows different coordination modes when coordinated to different metal ions, and comparison with a related ligand reveals a larger rotational degree of freedom in the ligand 1, allowing for richer architectures in emerging coordination polymers.
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-CRYSTALLINE MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander G. Sturm, Tobias Santowski, Thorsten Felder, Kenrick M. Lewis, Max C. Holthausen, Norbert Auner
Summary: A convenient single-step process for the synthesis of bifunctional hydridochlorosilane Me2SiHCl has been developed, utilizing in situ H/Cl exchange and redistribution reactions. The reaction temperature and byproduct handling steps have been optimized to achieve high yields.
Article
Crystallography
Steven van Terwingen, Ben Ebel, Noah Nachtigall, Ulli Englert
Summary: The heteroditopic molecule HacacMePz combines a Pearson hard acetylacetone donor site with a softer trimethylpyrazole and shows site selectivity towards the coinage metal cations. It was found that the ligand coordinates with Ag-I and Au-I, leading to linear coordination about the metal cations. Furthermore, the ligand's ability for the synthesis of bimetallic coordination polymers was demonstrated.
Article
Chemistry, Multidisciplinary
Alexander G. Sturm, Uhut S. Karaca, Myron Heinz, Thorsten Felder, Kenrick M. Lewis, Norbert Auner, Max C. Holthausen
Summary: In this study, an energetically and environmentally benign synthetic protocol for the highly selective conversion of SiCl4 to HSiCl3 was reported. The protocol utilized organohydridosilanes as recyclable hydrogen transfer reagents and onium chlorides as efficient catalysts. This same protocol was also used for the quantitative conversion of higher oligosilane residues generated from Siemens processes.
Article
Chemistry, Inorganic & Nuclear
Thomas Hoellerhage, Thomas P. Spaniol, Ulli Englert, Jun Okuda
Summary: In this study, the synthesis of a hydride cation in the presence of Me(6)HACO was attempted, and the hydrogenolysis of the benzyl cation was investigated. The results showed that the benzyl cation undergoes hydrogenolysis to form toluene and a hydride species.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Ze-Jie Lv, Philipp D. Engel, Lukas Alig, Sandipan Maji, Max C. Holthausen, Sven Schneider
Summary: The synthesis and characterization of isolable complexes with a doubly deprotonated diazomethane (CNN2-) ligand are reported, providing new fleeting intermediates for nitrogen transfer reactions. The bonding within the allenic dimetallanitrilimine core was investigated through the oxidation of the bridging ligand. Enhanced reactivity towards [3 + 2]-cycloaddition with CO2 was observed. Photofragmentation experiments favor the cleavage of the N-NC bond to generate cyanide and a transient metallonitrene complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hendrik Verplancke, Martin Diefenbach, Jonas N. Lienert, Mihkel Ugandi, Marios-Petros Kitsaras, Michael Roemelt, Stella Stopkowicz, Max C. Holthausen
Summary: We present a dramatic failure of CCSD(T) theory due to the multi-reference character of a key intermediate in the benzaldehyde amidation reaction studied experimentally and theoretically. By using a minimal model system, we show that broken-symmetry or Kohn-Sham orbital references improve the accuracy of CCSD(T) results. The revised reaction pathway energetics provide a mechanistic rationale for the experimental observations.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Annalena Gaertner, Uhut S. Karaca, Maximilian Rang, Myron Heinz, Philipp D. Engel, Ivo Krummenacher, Merle Arrowsmith, Alexander Hermann, Alexander Matler, Anna Rempel, Robert Witte, Holger Braunschweig, Max C. Holthausen, Marc-Andre Legare
Summary: We present a comprehensive study on the fixation and reductive coupling of dinitrogen with low-valent boron compounds, combining computational and experimental approaches. The results demonstrate that the selectivity of nitrogen fixation or coupling can be controlled by steric bulk or reaction conditions, enabling the synthesis of nitrogen chains as needed. Furthermore, we elucidate the electronic structure and magnetic properties of intermediates and products of the reaction using high-level computational methods.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Tushar S. Basu Baul, Avishek Khatiwara, Maheswara Rao Addepalli, Bietlaichhai Hlychho, Andrew Duthie, Hans Gildenast, Ulli Englert, Abdallah G. Mahmoud, M. Fatima C. Guedes da Silva
Summary: Three stable diorganotin(IV) complexes were synthesized and their solution and solid-state structures were studied. The thermal stability of the complexes was determined by thermogravimetric analysis. The application of one of the complexes in a catalytic reaction was investigated, and the effects of different reaction parameters were studied.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Hans Gildenast, Lukas Gruszien, Felix Friedt, Ulli Englert
Summary: Phosphasilatriptycene provides a unique scaffold for TRIP-Py, and its P and N donor sites selectively coordinate metal cations of different properties. TRIP-Py can act as a ditopic linker to form discrete mixed-metal complexes when both hard Zn-II and soft Au-I cations are available for coordination.
DALTON TRANSACTIONS
(2022)