Review
Chemistry, Multidisciplinary
Antonio Del Vecchio, Harry R. Smallman, Jennifer Morvan, Tom McBride, Duncan L. Browne, Marc Mauduit
Summary: This article introduces the versatility of olefin metathesis and its successful applications in natural product synthesis and the valorization of renewable feedstocks. In addition, flow chemistry has gained significant interest as a valuable alternative to traditional batch chemistry and has paved the way for new transformations. The article highlights the promising application of continuous-flow methods in olefin metathesis, addressing typical issues such as undesired self-reactions and ethylene-mediated catalyst deactivation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Augustin Nouaille, Xavier Pannecoucke, Thomas Poisson, Samuel Couve-Bonnaire
Summary: This study presents an efficient ruthenium-catalyzed CM reaction method, successfully allowing various alkenes to react with methyl 2-fluoroacrylate to obtain trisubstituted fluoroalkenes for the first time. Additionally, an unprecedented TON value for the CM reaction involving fluoroalkenes was achieved, demonstrating good tolerance and effectiveness with a wide range of olefin partners.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Andre Both, Thomas Roider, Felix Ziegler, Xiulan Xie, Michael R. Buchmeiser, Ulrich Tallarek
Summary: In this study, a 2(nd)-generation Grubbs-Hoveyda type catalyst was immobilized in mesoporous silica and used in the ring-closing metathesis (RCM) of an alpha,omega-diene to a large macro(mono)cycle. The relationship between substrate concentration, reaction time, and overall experiment time on the rate of isomerization under spatial confinement with continuous-flow microreactors was investigated. The results showed that higher substrate concentrations and longer reaction times increased the isomerization rate, while prolonged overall experiment times led to a decline in the isomerization rate.
Article
Chemistry, Inorganic & Nuclear
Michal Patrzalek, Adam Zielinski, George Pasparakis, Maria Vamvakaki, Anna Ruszczynska, Ewa Bulska, Anna Kajetanowicz, Karol Grela
Summary: This study investigates purification methods for aqueous media olefin metathesis reactions to address the challenge of removing the catalyst from the reaction products. The addition of thiocyanate ions successfully removes the catalyst from water, but the methodology does not provide satisfactory results for reactions performed in water/alcohol mixtures.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Felix Ziegler, Thomas Roider, Markus Pyschik, Christian P. Haas, Dongren Wang, Ulrich Tallarek, Michael R. Buchmeiser
Summary: The study demonstrates the efficient use of a 2(nd)-generation Hoveyda-Grubbs-type catalyst immobilized inside mesoporous silica for selective macro(mono)cyclization (MMC) of an alpha,omega-diene under spatially confined and continuous-flow conditions. By analyzing reaction mixtures through NMR and MALDI-TOF-MS, the study identifies the effects of confinement on olefin metathesis pathways and determines conditions for achieving high MMC selectivity. The research also highlights the preference for ring-closing metathesis of monomers and backbiting from dimers and trimers under confinement, leading to a high MMC selectivity of 60%.
Article
Chemistry, Physical
Didier Astruc, Guy Bertrand, Mohamed Eddaoudi, Yu Han, Kuo-Wei Huang, Johannes Lercher, Catherine Santini, Kazuhiro Takanabe, Mostafa Taoufik, Luigi Cavallo
Summary: This article discusses the contributions of Jean-Marie Basset in the field of catalysis. He introduced the approach of molecular organometallic chemistry to the study of supported catalysts, established the field of surface organometallic chemistry, and significantly improved numerous known reactions while also discovering new ones.
Article
Chemistry, Multidisciplinary
Xiaohua Hou, Xiaojian Chen, Xiang Gao, Lei Xu, Hui Zou, Li Zhou, Zong-Quan Wu
Summary: The binuclear vanadium alkylidene showed higher activity in ROMP of norbornene, leading to the formation of cyclic polymers. The size of the polymer ring could be adjusted by the vanadium catalyst structure and polymerization temperature. Similar results were also observed in the ROMP of cyclopentene.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Jesus A. Avendano-Villarreal, Fabio G. Delolo, Artur V. Granato, Elena V. Gusevskaya, Eduardo N. dos Santos
Summary: A new and efficient method was developed to transform naturally occurring 1-propenylbenzenes into 2-arylpropylamines. This method involved a one-pot ethenolysis/hydroaminomethylation reaction and required careful selection of reaction conditions to achieve high yields. By adjusting the molar ratio of the catalysts, the interference between ethenolysis and hydroaminomethylation catalysts was avoided, resulting in the synthesis of nine 2-arylpropylamines with yields ranging from 75-93%.
Article
Biochemistry & Molecular Biology
Stefan Czarnocki, Louis Monsigny, Michal Sienkiewicz, Anna Kajetanowicz, Karol Grela
Summary: A modular and flexible strategy for synthesizing N-heterocyclic carbene (NHC) ligands bearing Bronsted base tags has been proposed and used to prepare two tagged NHC ligands with different acid residues. These tagged NHC ligands serve as an attractive starting point for the synthesis of olefin metathesis ruthenium catalysts with non-dissociating ligands. The impact of the Bronsted base tags on the activity of the obtained olefin metathesis catalysts has been investigated.
Article
Chemistry, Multidisciplinary
Jana Hatzfeld, Steffen Skowaisa, Elisabeth Jackel, Julia Kaufmann, Edgar Haak
Summary: Various triaminocyclopentadienyl ruthenium complexes were synthesized from Ru-3(CO)(12) and tested for their ability to catalyze cascade conversions of propargyl alcohols. The substrate scope of catalytic cycloadditions was extended to terpenoid-derived propargyl alcohols containing an internal alkyne moiety, resulting in a wide range of cyclic terpenoid and phloroglucinol adducts obtained by complementary application of both types of catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Haoyu Wang, Haitao Yu, Dong Bai, Dan Yao, Yongjun Han, Yichao Shi, Zhiqun Wang
Summary: A ruthenium olefin metathesis catalyst (C1-H) with a novel NHC ligand tethered by an ethoxy-pyridyl arm was synthesized and compared with its methylated derivative (C1-Me). The study showed profound variations in initiation rate, kinetics, metathesis activity, and decomposition behavior between these two catalysts. The remote torsional strain was found to have a considerable influence on the catalytic activity and decomposition behavior of this ligand class.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Hea Ji Kim, Go Bong Choi, Jae-Hyung Wee, Seungki Hong, Jieun Park, Yoong Ahm Kim, Hyungwoo Kim
Summary: This study explores the design of functional carbon materials from microporous organic polymers, demonstrating the potential for simultaneous elemental engineering of carbonaceous materials during thermal carbonization. Incorporation of heteroatoms during this process can enhance the catalytic performance of carbon materials.
Article
Chemistry, Multidisciplinary
Jully Patel, Gabriel Bury, Alireza K. Ravari, Roman Ezhov, Yulia Pushkar
Summary: This study investigates the descriptors correlated with catalytic activity through the synthesis and characterization of two catalysts. The results show that the introduction of an ethoxy group can enhance the catalytic activity in chemically driven and photocatalytic water oxidation, and it is related to the configuration of the Ru-oxo unit.
Article
Chemistry, Applied
Eva Pump, Albert Poater, Naeimeh Bahri-Laleh, Raffaele Credendino, Luigi Serra, Vittorio Scarano, Luigi Cavallo
Summary: This study computationally investigates the origin of chemo-, regio- and stereoselectivity in cross metathesis reactions leading to the desired product. By comparing the relative stabilities of intermediates and products, as well as transition states, the probability for each pathway is linked. The transition states in each reaction play a crucial role in tuning the regio- and stereoselectivity by defining the energy barriers needed to form the final product. The research findings provide valuable insights for understanding the selectivity in new olefin metathesis reactions and a web-server is developed to support future predictive catalysis.
Article
Chemistry, Physical
Antonio Del Vecchio, Jakub Talcik, Sophie Colombel-Rouen, Jan Lorkowski, Melinda R. Serrato, Thierry Roisnel, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit
Summary: New Blechert-type ruthenium complexes with cyclic(alkyl)(amino)carbene (CAAC) ligands show remarkable thermal stability in solution and excellent catalytic performances in various metathesis reactions. They exhibit high catalytic activity at low loading and can achieve high enantiomeric excess in asymmetric metathesis reactions.
Article
Mineralogy
Mateusz P. P. Sek, Adam Wlodek, Marcin Stachowicz, Krzysztof Wozniak, Adam Pieczka
Summary: Two tourmaline samples from quartz veinlets in the Karkonosze Mountains, SW Poland, were analyzed using microprobe and single crystal X-ray diffraction. The core sample is composed of dravite-oxy-dravite, while the rim sample is composed of magnesio-lucchesiite. Both tourmalines have similar compositions and crystallized from B-bearing metamorphic fluids. The Budniki camp is the third documented occurrence of magnesio-lucchesiite worldwide.
MINERALOGICAL MAGAZINE
(2023)
Article
Chemistry, Inorganic & Nuclear
Joanna Skiba, Aleksandra Kowalczyk, Aleksander Gorski, Natalia Dutkiewicz, Magdalena Gapinska, Jozef Strozek, Krzysztof Wozniak, Damian Trzybinski, Konrad Kowalski
Summary: The synthesis of luminescent dinucleoside phosphate analogs with a [Re-2(mu-Cl)(2)(CO)(6)(mu-pyridazine)] click linker as a replacement for the natural phosphate group is reported. These compounds exhibited orange emission and showed no toxicity to human cancer cells in vitro. Additionally, they showed moderate antibacterial activity against Staphylococcus aureus and Escherichia coli strains.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Paulina H. Marek-Urban, Karolina A. Urbanowicz, Karolina Wrochna, Piotr Pander, Agata Blacha-Grzechnik, Simone T. Hauer, Henning R. V. Berens, Krzysztof Wozniak, Thomas J. J. Mueller, Krzysztof Durka
Summary: A synthetic approach to two regioisomeric pi-electron extended [1,4]thiaborins annulated with two benzothiophene units has been developed. The obtained boracycles exhibit different electronic properties reflected in their aromatic characters, boron Lewis acidity, and UV-vis spectroscopic behavior. The spiro thiaborin-BODIPY complexes show excellent photocatalytic performance as singlet oxygen photosensitizers with high singlet oxygen quantum yields and full conversion of organic substrates.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Katarzyna Gajda, Adrian Sytniczuk, Laure Vendier, Bartosz Trzaskowski, Noel Lugan, Anna Kajetanowicz, Stephanie Bastin, Karol Grela, Vincent Cesar
Summary: Three Hoveyda-Grubbs complexes supported by N-(9-alkylfluorenyl)imidazol-2-ylidene ligands were synthesized. The C(sp(3))-H activation of the dangling alkyl group was studied for generating cyclometalated (C,C-NHC) ruthenium complexes for Z-selective olefin metathesis. The methyl derivative led to the expected cyclometalated complex, while no C(sp(2))-H activation of the fluorenyl moiety and no evolution/transformation were observed for the ethyl and benzyl derivatives, respectively. The cyclometalated complex exhibited Z/E stereoselectivity up to 94/6, despite its fragility under catalytic conditions. An unprecedented insertion of the alkylidene moiety into the Ru-C-NHC bond leading to ruthenium N-heterocyclic olefin complexes was also observed and supported by calculations of the corresponding reaction pathway.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Malgorzata Wierzbicka, Agnieszka Abratowska, Olga Bemowska-Kalabun, Dorota Panufnik-Medrzycka, Pawel Wasowicz, Monika Wrobel, Damian Trzybinski, Krzysztof Wozniak
Summary: Armeria maritima (Mill.) Wild is a plant species capable of tolerating high levels of heavy metals in unfavorable environments. It exhibits morphological variations and different levels of tolerance to heavy metals compared to individuals in non-metalliferous areas. A. maritima shows adaptations at the organismal, tissue, and cellular levels, and physiological and biochemical responses to heavy metals. This review focuses on A. maritima's adaptations and genetic variation in zinc-lead waste heaps, highlighting its role as a model for microevolution processes in plants in anthropogenically changed areas.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Magdalena Woinska, Sylwia Pawledzio, Michal L. Chodkiewicz, Krzysztof Wozniak
Summary: The study demonstrates that using aspherical atomic scattering factors for Hirshfeld atom refinement (HAR) can systematically elongate metal-hydrogen bonds in metal-organic complexes. High-quality experimental data is crucial in obtaining significant improvements in transition metal-hydrogen bond lengths. Different refinement strategies can result in significant differences in hydrogen positions.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Biochemistry & Molecular Biology
Marcin Witkowski, Damian Trzybinski, Sylwia Pawledzio, Krzysztof Wozniak, Wojciech Dzwolak, Agata Krolikowska
Summary: Cyclic dipeptides with a six-membered 2,5-diketopiperazine ring, such as cyclo(l-Cys-d-Cys), have attracted attention for their biological and chemical properties. This study characterizes cyclo(l-Cys-d-Cys) structurally with X-ray diffraction and vibration spectroscopy with the aid of density functional theory (DFT). The optimized computational model based on crystallographic structure enhances the correspondence between theoretical and experimental vibrational spectra.
Article
Chemistry, Multidisciplinary
Yizhi Xu, Michal L. Chodkiewicz, Magdalena Woinska, Damian Trzybinski, Ivana Brekalo, Filip Topic, Krzysztof Wozniak, Mihails Arhangelskis
Summary: The application of Hirshfeld atom refinement (HAR) fragmentation is shown to be effective in refining metal-organic framework (MOF) crystal structures. This method allows anisotropic refinement of imidazolate hydrogen atoms and complex analysis of solvent disorder within MOF pores. The study demonstrates that high quality structural analysis of MOFs can now be achieved using standard resolution in-house single crystal X-ray diffraction measurements, eliminating the need for neutron or synchrotron facilities.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Adrian Sytniczuk, Filip Struzik, Vishal Purohit, Karol Grela, Anna Kajetanowicz
Summary: The synthesis of inexpensive 2-isopropyl-6-methylaniline analogues was achieved through the employment of aza-Claisen rearrangement and subsequent reduction of anilines, overcoming the issue of high price and low availability. The obtained aniline derivatives were utilized in the synthesis of lipophilic Hoveyda-Grubbs-type complexes, serving as efficient catalysts in ethenolysis reactions. The complexes with bulky sec-butyl substituent exhibited superior performance compared to the leading catalyst based on 2-isopropyl-6-methylaniline, making them valuable candidates for large-scale industrial production with a TON of up to 192,000.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Pratikkumar Lakhani, Darshil Chodvadiya, Prafulla K. Jha, Vivek Kumar Gupta, Damian Trzybinski, Krzysztof Wozniak, Krzysztof Kurzydlowski, U. K. Goutam, Himanshu Srivastava, Chetan K. Modi
Summary: A Cu(ii)-salen complex encapsulated in MWW-framework was developed as an efficient chiral organocatalyst for synthesizing 3,4-dihydropyrimidin-2-(1H)-one (DHPMs) derivatives asymmetrically. Various techniques were used to confirm its structural properties. The Cu(ii)-salen complex was optimized to fit into the MWW support while maintaining its chirality through computer-assisted DFT calculations. This organocatalyst exhibited potent catalytic activity and could be reused multiple times without significant loss of activity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Magdalena Woin, Sylwia Pawledzio, Michal L. Chodkiewicz, Krzysztof Wozniak
Summary: Hydrogen positions in hydrides play a key role in hydrogen storage materials and high-temperature superconductors. Our study shows that using aspherical atomic scattering factors for Hirshfeld atom refinement (HAR) can result in longer metal-hydrogen bond lengths compared to using spherical scattering factors with the Independent Atom Model (IAM). By comparing X-ray and neutron data of metal-organic complexes, we find that the quality of experimental data is crucial for significant improvement in transition metal-hydrogen bond lengths from HAR.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Adrian Sytniczuk, Mariusz Milewski, Michal Dabrowski, Karol Grela, Anna Kajetanowicz
Summary: A set of macrocyclic unsaturated musk compounds were obtained through a high-concentration RCM process, achieved by forming oligomers and then undergoing backbiting metathesis reaction. The process exhibited high selectivity and yielded pure macrocyclic musk products. The reaction conditions were user-friendly and environmentally friendly, using commercially available catalyst and bio-sourced oleic acid substrates.
Article
Chemistry, Multidisciplinary
Krzysztof Durka, Adam Zuba, Paulina H. Marek-Urban, Krzysztof Nowicki, Jakub Drapala, Krzysztof Wozniak, Sergiusz Lulinski
Summary: Crystal structures of a series of functionalized 3-hydroxybenzo[c][1,2,3]siloxaboroles were compared, taking into account the electronic and steric effects of substituents at the aromatic ring on the hydrogen-bond motifs involving B-OH groups. The supramolecular assemblies of these compounds show strong variation depending on the substituents. DFT calculations revealed similar stabilization energies for all observed hydrogen-bond motifs, explaining the diversification of structures.
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
Adrian Sytniczuk, Filip Struzik, Karol Grela, Anna Kajetanowicz
Summary: A series of tunable CAAC-based ruthenium benzylidene complexes with increased lipophilicity derived from a key substrate for the drug ibuprofen were obtained and tested in various olefin metathesis transformations. The size of the N-aryl moiety was found to be a decisive factor, offering tunability for selecting the best catalyst for specific reactions.
