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
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, Multidisciplinary
Jessica Rodriguez, Maxime Boudjelel, Leonard J. Mueller, Richard R. Schrock, Matthew P. Conley
Summary: This passage describes the reaction of W(NAr) ((C4H8)-C-13) (OSiPh3)(2) (1) with partially dehydroxylated silica at 700 degrees C. The results show that the reaction outcome is highly influenced by the reaction conditions. Different compounds are formed as products, and their formation is affected by light and heating treatment.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Benjamin A. Suslick, Aliza N. Yazdani, Morgan M. Cencer, Justine E. Paul, Nil A. Parikh, Katherine J. Stawiasz, Isabel P. S. Qamar, Nancy R. Sottos, Jeffrey S. Moore
Summary: Frontal ring-opening metathesis polymerization (FROMP) catalyzed by Grubbs-type Ru complexes allows for the rapid and energy-efficient synthesis of high-performance structural plastics. By using a thermally latent bis-N-heterocyclic carbene complex and Cu-I coreagents, the system can be primed for rapid reactivity after thermal initiation, leading to the formation of robust resins with enhanced stability. Additionally, controlling the Cu to Ru ratio significantly impacts the reaction velocity and temperature, as well as the glass-transition temperature of the resulting polymers.
Article
Chemistry, Organic
Zhen Yu, Li Wang, Li Liu, Meng Wang, Hong Yang
Summary: This Account summarizes our research efforts and achievements in the field of olefin metathesis polymerization over the past decade, with a particular focus on acyclic diene metathesis (ADMET) polymerization and ring-opening metathesis polymerization (ROMP) strategies. The merits and limitations of these methods are also demonstrated, and our recently developed sequence-controlled ROMP strategy is highlighted.
Editorial Material
Chemistry, Multidisciplinary
Catherine S. J. Cazin
Summary: The seminal paper by Chauvin and Herisson on alkene metathesis mechanism is elegant, simple, and insightful, deserving admiration even after more than 50 years of its publication.
NATURE REVIEWS CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Iris Elser, Roman Schowner, Laura Stoehr, Katharina Herz, Mathis J. Benedikter, Suman Sen, Wolfgang Frey, Dongren Wang, Michael R. Buchmeiser
Summary: This article presents the extension of a library of molybdenum imido alkylidene N-heterocyclic carbene complexes with unsymmetrical ligands. Substitution of one triflate in these complexes with an alkoxide or a phenoxide led to the synthesis of new complexes with modified ligands. The structures of these complexes were analyzed using NMR and X-ray data.
Article
Chemistry, Multidisciplinary
Stella A. Gonsales, Zoe C. Mueller, Fengyue Zhao, Paulo H. S. Paioti, Lydia Karmazin, Jing Wan, Fang Liu, K. N. Houk, Amir H. Hoveyda
Summary: The study reveals that phosphine-free Ru-CAAC complexes have the steric and electronic attributes to be highly effective in generating allenes, paving the way for the development of additional olefin metathesis reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Kosuke Ono, Satoru Onodera, Hidetoshi Kawai
Summary: A novel synthetic strategy using boroxine formation for large macrocyclic molecules has been developed. This strategy utilizes the boroxine moiety as a covalent template to produce macrocyclic compounds through reactions with alkenyl chains. This method eliminates the need for template molecules and simplifies the synthetic procedure.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Laura Stohr, Christian Fajman, Roman Schowner, Iris Elser, Andreas Fuchs, Philipp M. Hauser, Somnath Bhattacharya, Dongren Wang, Michael R. Buchmeiser
Summary: This study determined the interconversion rates of the syn- and anti-isomers of neutral molybdenum and tungsten imido alkylidene N-heterocyclic carbene complexes and found that they were significantly lower than in tetracoordinated Schrock catalysts. NMR investigations suggest that higher transition state Gibbs free energy values are due to the dissociation of an anionic ligand from a neutral pentacoordinated catalyst. The anti-isomer showed higher reactivity and productivity in both ring-opening metathesis polymerization and ring-closing metathesis reactions.
Article
Chemistry, Multidisciplinary
Ting-Wei Hsu, Samuel J. Kempel, Alyssa P. Felix Thayne, Quentin Michaudel
Summary: In this study, a stereoretentive acyclic diene metathesis polymerization method was developed to control the cis/trans geometry of polyalkenamers. This method exhibited low catalyst loadings and tolerance towards trans impurities, enabling the synthesis of various polymers with predictable cis:trans ratios. The impact of the stereochemistry of the repeating alkenes on the thermal properties was clearly demonstrated.
Article
Polymer Science
Henry L. Cater, Iana Balynska, Marshall J. Allen, Benny D. Freeman, Zachariah A. Page
Summary: This paper presents a systematic study on ROMP with endo-norbornene monomers using stable chelated Ru-alkylidene initiators. The study shows that ROMP with endo-norbornene monomers is versatile and robust, providing access to polymers with excellent molecular weight control, low dispersities, good functional group tolerance, and high chain-end fidelity. The process is oxygen-tolerant and can be performed under ambient conditions, allowing for the synthesis of mechanically robust thermoplastics with high glass transition and decomposition temperatures.
Article
Polymer Science
Janis V. Musso, Paul Gebel, Vincent Gramm, Wolfgang Frey, Michael R. Buchmeiser
Summary: A system for visible-light-controlled ring-opening metathesis polymerization (ROMP) was developed by combining thermally latent group 6 olefin metathesis initiators with a photoredox catalyst. This system can be applied to two-dimensional (2D) photolithography, and it exhibits high activity and stability without the need for thermal or UV post-curing.
Article
Chemistry, Organic
Xia-Lin Wang, Nicholas Yiching Chiang, Jian-Jhih Peng, Lei Yu, Li-Jun Xu, Hau-Ren Yang, Bih-Yaw Jin, Pinglu Zhang, Yu-Ying Lai, Ze Li, Guo-Qiao Lai, Tien-Yau Luh
Summary: The Grubbs G-I or G-II catalyst forms a ruthenium ethoxy carbene complex, which catalyzes the ring-opening cross metathesis reaction to produce a diene with an ethoxy substituent. Various hydrocarbons can smoothly undergo this reaction, while tertiary amines, N-alkylimides, esters, and aryl or alkyl bromides remain intact.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Narumi Miyasako, Shin-ichi Matsuoka, Masato Suzuki
Summary: New ester-functionalized bicyclic aliphatic polymers were successfully synthesized through ring-opening metathesis polymerization (ROMP) of various norbornene lactones and their analogues, followed by hydrogenation. The comparison and discussion of polymerizability and thermal properties between different monomers before and after hydrogenation were conducted. The obtained polymers showed excellent thermal stability and processing deformation suitable for transparent resin materials.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Juliane Heitkaemper, Sergio Posada-Perez, Silvia Escayola, Miquel Sola, Johannes Kaestner, Albert Poater
Summary: For decades, efforts have been made to reduce the amount of metal reagents used in the synthesis of secondary alcohols. In 2021, Newman and collaborators pioneered a synthesis method using metals as catalytic engines rather than reactants. This paper presents a description of the process using Density Functional Theory calculations and attempts to shed light on the mechanism behind the attainment of secondary alcohols, emphasizing the debate on whether the catalytically active species is Ni(0) or if they take shortcuts following the course of Ni(II). Effective Orbital analyses provide a clear picture. Furthermore, this paper provides insight into both the nature of the ligands of the metal catalyst and the role of the base.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Lole Jurado, Jerome Esvan, Ligia A. A. Luque-Alvarez, Luis F. F. Bobadilla, Jose A. Odriozola, Sergio Posada-Perez, Albert Poater, Aleix Comas-Vives, M. Rosa Axet
Summary: Rhodium-catalysed hydroformylation is an effective tool for both bulk and fine-chemical synthesis, but its major drawbacks are metal leaching and catalyst recycling. Single-atom catalysts have emerged as a powerful solution to combine the advantages of homogeneous and heterogeneous catalysts. In this study, we demonstrate that Rh atoms anchored on graphitic carbon nitride are robust catalysts for the hydroformylation reaction of styrene.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Organic
Roger Monreal-Corona, Miquel Sola, Anna Pla-Quintana, Albert Poater
Summary: The mechanism for the stereospecific synthesis of cyclobutanes is revealed using density functional theory (DFT) calculations. The rate-determining step involves the release of N2 from the 1,1-diazene intermediate to form an open-shell singlet 1,4-biradical. The formation of the stereo-retentive product is explained by the barrierless collapse of this open-shell singlet 1,4-biradical. The methodology could potentially be used for the synthesis of [2]-ladderanes and bicyclic cyclobutanes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Mostafa Ahmadi, Albert Poater, Sebastian Seiffert
Summary: Advances in self-sorting mechanisms have led to the development of well-defined supra-molecular coordination complexes (SCCs) with unprecedented geometries. However, these advances have been rarely applied to the design of metallo-supramolecular polymer networks (MSPNs). To address this gap, steric hindrance was used as a self-sorting mechanism to construct MSPNs based on the formation of heteroleptic complexes. These results open up a promising interface between polymer science and coordination chemistry.
Article
Chemistry, Physical
P. Hima, M. Vageesh, Michele Tomasini, Albert Poater, Raju Dey
Summary: A transition metal-free synthesis of quinazoline derivatives from 2-aminobenzyl alcohols and aryl amides using a potassium tertiary butoxide-promoted alcohol dehydrogenation strategy is reported. Control experiments were conducted to identify reaction intermediates and the role of the K+ ion. DFT calculations uncovered the reaction mechanism, focusing on the rate-determining state. This method tolerates various functional groups, providing easy access to diversely substituted quinazolines.
MOLECULAR CATALYSIS
(2023)
Review
Chemistry, Inorganic & Nuclear
Jesus Antonio Luque-Urrutia, Thalia Ortiz-Garcia, Miquel Sola, Albert Poater
Summary: In this review, the author discusses how the burning of fossil fuels is driving the need for green energy. The overuse of non-renewable resources and the lack of recycling efforts have created an unsustainable situation that is leading to climate change. The article explores various methods, such as catalysts for using water or alcohols as energy sources, the recycling of gases like CO2 and N2O, and non-catalytic means of generating energy through solar cell production.
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sergio Posada-Perez, Anna Vidal-Lopez, Miquel Sola, Albert Poater
Summary: In this study, the performance of Cu, Ag, and Au single-atom particles dispersed on a two-dimensional carbon nitride support for CO2 reduction reaction was explored. It was found that the deposition of single metal atoms enhances the catalytic activity of the system, with the first proton-electron transfer being favored in terms of energy. However, strong binding energies were found for CO adsorption on Cu and Au single atoms, leading to the favorable competitive H2 generation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Tharinee Theerathanagorn, Anna Vidal-Lopez, Aleix Comas-Vives, Albert Poater, Valerio D'Elia
Summary: The study demonstrates that water-soluble organocatalysts can efficiently synthesize cyclic carbonates from CO2 and various epoxides in water-organic biphasic systems. The addition of simple inorganic salts accelerates the reaction rates and seawater is particularly effective as the aqueous layer. Control experiments and DFT calculations provide insights into the heterogeneous catalytic process at the interface between water droplets and the epoxide phase.
Article
Polymer Science
Mohammadreza Mehdizadeh, Fereshteh Karkhaneh, Mehdi Nekoomanesh, Samahe Sadjadi, Mehrsa Emami, HamidReza Teimoury, Mehrdad Salimi, Miquel Sola, Albert Poater, Naeimeh Bahri-Laleh, Sergio Posada-Perez
Summary: The influence of ethanol content in adducts on the catalytic behavior of Ziegler-Natta catalysts in propylene homo- and copolymerizations was investigated. The results showed that higher ethanol content in the adducts led to increased catalyst activity, particularly in homopolymerization reactions in the absence of H2. Additionally, the catalyst with the highest ethanol content produced a copolymer with lower isotacticity index and more uniform distribution of comonomer. These findings highlight the importance of controlling ethanol content in catalyst/support during the preparation process. Molecular simulation was also utilized to explain the iso-specificity of the polypropylene produced by the synthesized catalysts.
Article
Chemistry, Physical
Mostafa Ahmadi, Cora Sprenger, Gerard Pareras, Albert Poater, Sebastian Seiffert
Summary: Nature utilizes spontaneous self-organization of supramolecular bonds to create complex matter capable of adaptation and self-healing. In this study, the self-sorting of unlike ligands in a mixed ligand system was used to form stimuli-responsive polymer networks with various geometries. By studying the coordination preferences of different metal ions, the researchers achieved the formation of heteroleptic complexes in polymer networks, resulting in enhanced strength and stability compared to individual components. The findings offer new opportunities for the development of topology-switching polymer networks.
Article
Chemistry, Physical
Arshia Dehghani, S. Sadra Mohammad Nafari, Naeimeh Bahri-Laleh, Leila Moballegh, Samahe Sadjadi, Mehrsa Emami, Montserrat Rodriguez-Pizarro, Albert Poater
Summary: In this research, nano-scaled halloysite-supported imidazolium based dicationic ionic liquids (ILs) with different electronic features were prepared and used in the oligomerization of 1-octene monomer. The resulting polyalphaolefins (PAOs) showed lower molar masses but comparable performance to commercial counterparts, indicating a more sustainable and greener polymerization procedure.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Physical
Mostafa Ahmadi, Cora Sprenger, Gerard Pareras, Albert Poater, Sebastian Seiffert
Summary: This study reports the formation of topology-switching polymer networks based on spontaneous self-organization of heteroleptic complexes. The results show that various network structures can be achieved by adjusting the coordination geometry preference of the metal ion, indicating the potential for stimuli-responsive properties.