Review
Chemistry, Physical
Augustin Nouaille, Jan Lorkowski, Xavier Pannecoucke, Marc Mauduit, Thomas Poisson, Samuel Couve-Bonnaire
Summary: This article presents a review of the challenges in using fluoroalkenes in ring-closing metathesis and cross-metathesis, highlighting the major developments in this field in recent years.
Article
Chemistry, Organic
Laurence N. Rohde, Therese H. Wild, Steven T. Diver
Summary: In this study, a variety of ene-yne cross metathesis reactions were carried out using unsaturated phosphonate and phosphate reagents, resulting in the phosphorylated 1,3-diene products in good to excellent yields. The challenging ene-yne metatheses were facilitated by a Grubbs catalyst with a cyclic amino alkyl carbene ligand, allowing for the transformation of terminal alkynes of varying substitution into conjugated diene products with high yields. The resulting dienes were further modified through Horner-type Wittig reactions and a Diels-Alder cycloaddition.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
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, Organic
Jennifer A. Nguyen, David C. Cabanero, Tomislav Rovis
Summary: A system for electrochemically controlling ruthenium-catalyzed olefin metathesis has been developed. This system, catalyzed by a commercially-available bis-NHC Ru complex, exhibits a wide substrate scope with short reaction times, and achieves excellent temporal control over metathesis using only electricity as a stimulus.
Article
Chemistry, Physical
Or Eivgi, Anna Vaisman, N. Gabriel Lemcoff
Summary: The ligand shell that surrounds an active metal center plays a crucial role in determining the reactivity and properties. This study presents new ruthenium indenylidene complexes with a combination of phosphite olefin metathesis precatalysts and cyclic alkyl amino carbene (CAAC) ligands, which show efficient photoactivity and robust stability. These catalysts exhibit formidable latency at ambient temperatures, allowing for a wide range of olefin metathesis reactions and efficient recycling for multiple reaction cycles under air.
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
Multidisciplinary Sciences
Ru Jiang, Lu Ding, Chao Zheng, Shu-Li You
Summary: The study introduces iridium-catalyzed asymmetric allylic substitution reactions that can preserve the Z-olefin geometries while establishing adjacent quaternary stereocenters. This method shows promise for the preparation of chiral Z-olefinic compounds.
Article
Chemistry, Multidisciplinary
Kerlane A. Fernandes, Aline Aparecida C. Franca, Ana Karina B. Costa, Eliada A. da Silva, Benedito dos S. Lima-Neto, Nouga C. Batista, Jose Luiz S. Sa
Summary: LN-1 and LN-2, as Ru(II) complexes coordinated to phosphine and amines simultaneously, were tested as initiators for piperine self-metathesis olefin for the first time. The experiments showed that olefin metathesis products from piperine were observed at 50 degrees C for 72 h, with LN-1 yielding approximately 29% of product and LN-2 yielding approximately 39%. There was no product formation in experiments with a catalyst:substrate ratio of 1:10 mol. The results were discussed in terms of the electronic and steric properties of the ancillary ligands of LN1 and LN-2.
Article
Chemistry, Applied
Adrian Sytniczuk, Pawel Malecki, Anna Kajetanowicz, Karol Grela
Summary: The activity of new indenylidene complexes with two unsymmetrical N-heterocyclic carbene (NHC) ligands was investigated. They were found to be effective in both straightforward olefin metathesis reactions and more demanding processes.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Benedikt W. Grau, Alexander Neuhauser, Sadig Aghazada, Karsten Meyer, Svetlana B. Tsogoeva
Summary: Metathesis reaction is an important tool in synthetic chemistry that transforms hydrocarbon molecules through exchange of molecular fragments. There have been many modifications and improvements, including the use of iron as a catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Ravindra S. Phatake, Noy B. Nechmad, Ofer Reany, N. Gabriel Lemcoff
Summary: A selective ring-closing metathesis (RCM) reaction using latent sulfur chelated ruthenium iodide benzylidenes as catalysts, activated by thermal and photochemical stimuli, has been reported. This method enables the formation of large macrocycles with high yields, especially for dienes with one terminal alkene and one internal double bond. For substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Leonildo A. Ferreira, Josiane T. Silva, Raissa G. Alves, Kelley C. B. Oliveira, Eduardo N. dos Santos
Summary: In this study, the cross metathesis of estragole and methyl sorbate was investigated to produce methyl 6-(4-methoxyphenyl)hexa-2,4-dienoate with good conversion and selectivity using ruthenium-based metathesis catalysts at low catalyst loadings as 50 ppm (0.005 mol%) and minimal solvent. This demonstrates the importance of catalyst selection and reaction conditions in achieving the desired product conversion and selectivity.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Physical
Seongwook Park, Seunghwan Byun, Huijeoung Ryu, Hyungwoo Hahm, Junseong Lee, Sukwon Hong
Summary: Novel ruthenium catalysts bearing azobenzene groups were developed for olefin metathesis reactions, demonstrating an on-off switching ability in ring-closing metathesis reactions depending on UV irradiation. Various types of olefin metathesis reactions, such as ring-opening metathesis, cross-metathesis, and ethenolysis, exhibited photoswitching phenomena. The reversible feature of photoswitching was confirmed by observing the photoisomerization of azobenzene-bearing cyclic(alkyl)(amino)carbene ligands and the corresponding ruthenium catalysts using UV-vis spectroscopy.
Article
Chemistry, Organic
Somsuvra Banerjee, Takafumi Kobayashi, Kazuhiko Takai, Sobi Asako, Laurean Ilies
Summary: In the presence of triphenylphosphine as a mild reductant, the use of catalytic amounts of Mo(CO)6 and an ortho-quinone ligand enables the intermolecular reductive coupling of aromatic aldehydes and the intramolecular coupling of aromatic ketones to produce functionalized alkenes. Diaryl-and diheteroaryl alkenes are synthesized with high (E)-selectivity and a tolerance toward bromide, iodide, and steric hindrance. Intramolecular coupling of dicarbonyl compounds under similar conditions affords mono-and disubstituted phenanthrenes.
Article
Chemistry, Physical
Peng Ma, Jiaren Zhang, Xiaqian Wu, Jianhui Wang
Summary: Phosphine-free ruthenium benzylidene complexes with imidazole ligands have been reported. These catalysts are effective for high-temperature ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, unlike the commonly used phosphine-containing N-heterocyclic carbene-based ruthenium catalysts which exhibit side reactions. This discovery paves the way for the development of more selective ruthenium metathesis catalysts for reactions requiring harsh conditions.
Article
Chemistry, Organic
Francois Mazars, Madalina Hrubaru, Nikolay Tumanov, Johan Wouters, Lionel Delaude
Summary: A total of twelve imidazolium-, imidazolinium-, or benzimidazolium-2-dithiocarboxylate zwitterions were synthesized in high yields, including four new unsymmetrical derivatives. The novel synthesis method employed a weak base and mild aerobic conditions, showcasing potential advantages over previous approaches.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Koffi Senam Etse, Guillermo Zaragoza
Summary: In this study, a novel compound was synthesized and characterized, with its crystal structure confirmed as the (R,S)-stereoisomer by X-ray diffraction analysis. Spectroscopic analysis revealed the unique molecular shape and crystal structure of the compound. Computational investigations suggested that the compound may have potential pharmacological activity as a promising BCRP inhibitor.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Physical
Koffi Senam Etse, Albert Demonceau, Guillermo Zaragoza, Didier Serteyn, Ange Mouithys-Mickalad
Summary: This paper reports the design, synthesis, and biochemical evaluation of a benzodioxole material derived from cheap and available vanillin, which shows promising precursor properties for natural derivatives. The compounds exhibit good biochemical properties, antioxidant activities, and inhibition of peroxidase activity. Molecular docking exploration further confirms the mechanism of peroxidase activity inhibition, suggesting compound 9 as a potential drug candidate with low cytotoxicity.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Inorganic & Nuclear
Sandra Fernandez-Farina, Luis M. Gonzalez-Barcia, Maria J. Romero, Javier Garcia-Tojal, Marcelino Maneiro, Jose M. Seco, Guillermo Zaragoza, Miguel Martinez-Calvo, Ana M. Gonzalez-Noya, Rosa Pedrido
Summary: This study presents the first example of a silver double-tetranuclear cluster helicate obtained from a bisthiosemicarbazone ligand using electrochemical synthesis. The cluster helicate undergoes a rare desulfurization process in chloroform, giving rise to a cationic silver dihelicate, which represents the first silver-mediated desulfurization reaction.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Sandra Fernandez-Farina, Miguel Martinez-Calvo, Marcelino Maneiro, Jose M. Seco, Guillermo Zaragoza, Ana M. Gonzalez-Noya, Rosa Pedrido
Summary: We report two different approaches to isolate neutral and cationic mesocate-type metallosupramolecular architectures derived from coinage monovalent ions. By using a thiocarbohydrazone ligand, we successfully prepared a series of neutral and cationic dinuclear mesocates and analyzed their crystal structures, revealing the influence of synthetic methodology and counterions on the mesocates' structures.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Guillermo Zaragoza, Lionel Delaude
Summary: The alkylation of caffeine with methyl iodide led to the synthesis of a new compound. Three complexes were obtained through multiple steps and were found to be highly active catalysts for the Suzuki-Miyaura cross-coupling reaction. The reaction showed high yields and could be carried out in a green solvent with low catalyst loading and in the presence of air.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Koffi Senam Etse, Guillermo Zaragoza, Albert Demonceau
Summary: Two novel palladium(II) complexes were prepared using 2-iodo-N-ethylbenzenesulfonamide and 2-iodo-N-isopropylbenzenesulfonamide as starting materials. The complexes were fully characterized and their molecular structures were confirmed by various spectroscopic techniques. The crystal packing and short interactions of these complexes were investigated. The catalytic activities of the complexes in a cyclopropanation reaction and polymerization reaction were evaluated.
Article
Chemistry, Physical
Koffi Senam Etse, Kodjo Djidjole Etse, Guillermo Zaragoza, Ange Mouithys-Mickalad
Summary: This research presents the synthesis and characterization of a new compound, N-cyclohexyl-N-tosylformamide (10). Its thermal stability was explored through thermogravimetric analysis, and its molecular structure was obtained using X-ray diffraction analysis. The compound exhibited good crystal stability and showed moderate antioxidant activity and interesting potential for inhibiting HRP peroxidase activity.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Lionel Delaude
Summary: By using natural and renewable methylxanthine alkaloids such as caffeine or theophylline, two ruthenium-arene complexes with the formula [RuCl2(p-cymene)(NHC)] were successfully obtained. The synthesis of these complexes required different steps and yielded compounds with different catalytic activity and dynamic behavior.
Article
Chemistry, Multidisciplinary
Nedra Touj, Jerwin Jay Taping, Nikolay Tumanov, Johan Wouters, Lionel Delaude
Summary: The hydrolysis of imidazolinium chlorides occurs readily in a basic water/dichloromethane biphasic mixture at room temperature. Substrates with alkyl or aryl substituents on their nitrogen atoms led to high yields of gamma-aminoformamides. Bulky alkyl or aryl groups on the formamide moiety resulted in high stereoisomeric purity of the (E)-isomer. The presence of bulky aromatic substituents on the nitrogen atoms slowed down the hydrolysis of certain imidazolinium chlorides. The counteranion was found to have a critical influence on the reactivity of imidazolinium cations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Guillermo Zaragoza, Lionel Delaude
Summary: A series of unsymmetrical imidazolium chlorides were synthesized and used to prepare novel palladium complexes. These complexes showed excellent catalytic activity in the Suzuki-Miyaura cross-coupling reaction.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Koffi Senam Etse, Guillermo Zaragoza, Lionel Delaude
Summary: The activity of three Pd-PEPPSI catalyst precursors with N-heterocyclic carbene (NHC) ligands derived from caffeine and theophylline in Mizoroki-Heck reactions was tested. The results showed that the catalysts achieved high conversions and yields, especially in the presence of electron-withdrawing substituents.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Francois Mazars, Guillermo Zaragoza, Lionel Delaude
Summary: This study demonstrates that the alkylation or iodination of imidazol(in)ium salts can readily take place at their C2 or C2 alpha position in the presence of Cs2CO3, extending the chemistry of NHCs and weak bases to their NHO analogues.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sandra Fernandez-Farina, Miguel Martinez-Calvo, Maria J. Romero, Jose M. Seco, Guillermo Zaragoza, Rosa Pedrido, Ana M. Gonzalez-Noya
Summary: The mechanism of carbamate activation promoted by different metal ions has been investigated, revealing that the reaction between carbamate ligand H2L and chloride metal salts leads to hydrolysis and release of products.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Vaibhav Bedi, Dipendu Mandal, Zahid Hussain, Shi-Ming Chen, Yile Wu, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: The reaction of (tBuO(2)CN)(2) with 9-BBN leads to the formation of a bicyclic heterocyclic compound, while its reactions with BF3 or [Et3Si][B(C6F5)(4)] result in the isolation of different compounds. Computational studies reveal that the steric and electronic properties of the Lewis acid are important in the formation of one of the compounds.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Chisa Itoh, Haruka Yoshino, Taku Kitayama, Wataru Kosaka, Hitoshi Miyasaka
Summary: A new synthetic route for constructing functional paddlewheel diruthenium(II,II) complexes was developed, utilizing Schiff base condensation reactions. The attached Schiff base groups significantly affected the electronic states of the resulting complexes, as revealed by cyclic voltammetry and DFT calculations.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Danrui Ni, Haozhe Wang, Xianghan Xu, Weiwei Xie, Robert J. Cava
Summary: A layered rhombohedral polymorph of indium(iii) triiodide is synthesized at high pressure and temperature. It has an orange color, which is different from ambient pressure InI3, which has a monoclinic molecular structure and a light-yellow color.
DALTON TRANSACTIONS
(2024)
Review
Chemistry, Inorganic & Nuclear
Juan Carlos Perez-Sanchez, Raquel P. Herrera, M. Concepcion Gimeno
Summary: Gold(II) complexes have been less utilized in catalysis compared to their gold(I) and gold(III) counterparts. However, gold(II) complexes offer potential in homo-coupling and cross-coupling reactions, as they are more easily accessible through simplified oxidation and reduction processes. Gold(II) exhibits characteristics of both soft acid gold(I) and hard acid gold(III). This review explores the unique reactivity and potential applications of gold(II) species, highlighting their significance in catalytic transformations.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Nighat Yousuf, Yanping Ma, Qaiser Mahmood, Wenjuan Zhang, Yizhou Wang, Hassan Saeed, Wen-Hua Sun
Summary: In this study, a series of structurally rigid cyclooctyl-fused iminopyridine iron complexes were synthesized and used with methylaluminoxane for isoprene polymerization. The extent of steric hindrance of the ligand framework was found to significantly affect catalytic performance, with less hindrance leading to better activity and stability.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Chenghao Song, Huiwei Du, Menglei Xu, Jie Yang, Xinyu Zhang, Jungan Wang, Yuanfang Zhang, Chengjun Gu, Rui Li, Tao Hong, Jingji Zhang, Jiangying Wang, Yongchun Ye
Summary: This study improves the performance of perovskite solar cells by using a dual-hole transport layer strategy. This strategy enhances the charge transfer efficiency of the transport layer, reduces charge recombination, and improves the quality of the perovskite film layer. Ultimately, the stability of the device is enhanced.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Mahender Singh, Aakash Yadav, Ranjit Singh, Chullikkattil P. Pradeep
Summary: A new aryl selenonium polyoxometalate hybrid was developed and compared with an aryl sulfonium polyoxometalate hybrid in terms of their photocatalytic properties. It was found that the aryl selenonium hybrid exhibited better catalytic performance, which could be attributed to the larger atomic radii of selenium stabilizing the photogenerated electron-hole pair more efficiently. Additionally, the generation of elemental selenium through cleavage of C-Se bonds during catalysis was observed.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Yuhan Xie, Boyu Dong, Xuemin Wang, Siyuan Wang, Jinxi Chen, Yongbing Lou
Summary: This study successfully fabricated visible-light-responsive three-dimensional core-shell CoSe2/ZnIn2S4 heterostructures and achieved attractive activity in photocatalytic hydrogen evolution. The presence of CoSe2 improved light absorption and accelerated charge transfer kinetics. The strong interaction between CoSe2 and ZnIn2S4 reduced charge recombination, further enhancing photocatalytic activity for hydrogen evolution.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Andre L. de O. Batista, Joao Marcos T. Palheta, Mauricio J. Piotrowski, Celso R. C. Rego, Diego Guedes-Sobrinho, Alexandre C. Dias
Summary: This study presents a simulation protocol that provides a solid foundation for exploring two-dimensional materials. Using the TiBr2 2H monolayer as an example, the study reveals its promising properties for optoelectronic and valleytronic applications, including its stability, spin-orbit coupling effects, and optical helicity selection rule.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Jiang Jiang, Zi-Wei Li, Zhi-Zhuan Zhang, Bin Tan, Zhao-Feng Wu, Xiao-Ying Huang
Summary: In this work, two metal organic frameworks (MOFs) containing {Cu2I2} clusters, Eu-CuI-INA and Sr-K-CuI-INA, were synthesized and characterized. Both materials have a three-dimensional structure with {Cu2I2} clusters coordinated by INA(-) ligands and Eu3+ or Sr2+ ions. The Sr-K-CuI-INA material exhibited sensitive fluorescence sensing behaviors towards cysteine and nitro-bearing molecules, showing potential applications in bio and explosive molecule sensing. This work provides a good reference for designing fluorescent MOF probes containing CuI molecules.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Zhiya Lin, Jiasheng Wu, Qianwen Ye, Yulong Chen, Hai Jia, Xiaohui Huang, Shaoming Ying
Summary: Na-ion batteries (NIBs) have attracted great interest as a potential technology for grid-scale energy storage due to the wide distribution, low cost, and environmental friendliness of sodium resources. However, their implementation is hindered by low rate capability and cycling stability caused by the large ionic size of Na+. In this study, a three-dimensional nanoarchitectured coral-like CoSe2@N-doped carbon (CL-CoSe2@NC) was synthesized, and it exhibited improved sodium storage properties with better electrode kinetics and a stable SEI film.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Ya-Qiong Zhang, Yu Zhang, Guoping Zeng, Rong-Zhen Liao, Man Li
Summary: The mechanism and selectivity of CO2 reduction under visible light were investigated using density functional calculations. The results showed that a tetradentate PNNP-type Iridium(III) complex exhibited high activity and selectivity in the reaction.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Sanyukta Ghosh, Shubhanth Jain, Soumya Ranjan Mishra, Gerda Rogl, Peter Rogl, Ernst Bauer, B. S. Murty, A. Govindaraj, Ramesh Chandra Mallik
Summary: In this study, reduced graphene oxide (rGO) was uniformly dispersed in the In0.5Co4Sb12 bulk material by ultrasonication, which effectively reduced the lattice thermal conductivity and improved the thermoelectric efficiency.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Mika Takeuchi, Yutaka Amao
Summary: This study developed an effective visible-light driven system for fumaric acid production using renewable resources such as biomass derivatives, providing an alternative to the current petroleum-based synthesis methods.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Juan Jian, Meiting Wang, Zhuo Wang, Jingwen Meng, Yuqin Yang, Limin Chang
Summary: Developing low-cost and self-supported bifunctional catalysts is crucial for highly efficient water splitting devices. In this study, nano-NiFe2O4 was directly grown onto iron foil surface and Sn4+ was introduced into the NiFe2O4. The resulting Sn-NiFe2O4/IF showed low overpotentials and high current densities during oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), making it a promising catalyst for large-scale hydrogen production.
DALTON TRANSACTIONS
(2024)