Article
Chemistry, Multidisciplinary
Enrico Bergamaschi, Danijela Lunic, Liam A. McLean, Melissa Hohenadel, Yi-Kai Chen, Christopher J. Teskey
Summary: This study demonstrates, for the first time, the ability to use light to distinguish between ketones and carboxylic acids in more complex molecules. By utilizing different activation modes, a single catalytic system can be used for hydroboration, with chemoselectivity dictated solely by the presence or absence of visible light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Kai Gao, Jerrik Mielby, Soren Kegnaes
Summary: The study demonstrates that Zn-containing MFI zeolites are highly active and selective catalysts for the catalytic dehydrogenation of ethanol. The best catalyst, comprising 5 wt % Zn on Silicalite-1 zeolite, achieves a selectivity of 94.5% towards acetaldehyde at 400 degrees C.
Article
Chemistry, Physical
Arun Dixith Reddy Shada, Alexander J. M. Miller, Thomas J. Emge, Alan S. Goldman
Summary: The method of alkane dehydrogenation using iridium complexes achieves up to 97% yield and up to 15 catalytic turnovers, utilizing proton-coupled electron transfer. This approach offers a promising way to selectively dehydrogenate alkanes with practical implications.
Review
Chemistry, Multidisciplinary
Atanu Bera, Sourajit Bera, Debasis Banerjee
Summary: This article summarizes the recent advances in the dehydrogenation of N-heteroaromatics, discussing different catalysis approaches and reaction conditions such as precious metal and non-precious metal catalysis, photocatalysis, electrocatalysis, and organo-catalysis.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Srabani Nandi, Ishani Borthakur, Kasturi Ganguli, Sabuj Kundu
Summary: A series of phosphine-free Mn(I) complexes with benzimidazole and pyridine ligands were synthesized. The Mn1 complex with a 2-hydroxypyridine-appended benzimidazole ligand showed high effectiveness in the synthesis of N-heterocycles using alcohols. By using a significantly lower catalyst loading (0.05 mol %), several substituted pyrimidines and quinolines were successfully synthesized. The lactim-lactamacid-base equilibrium of the 2-hydroxypyridine fragment, the role of the countercation of the base, and the effect of externally added ligands were investigated, and a probable catalytic cycle was proposed based on control experiments and kinetic studies.
Article
Chemistry, Multidisciplinary
Mitsuki Onoda, Ken-ichi Fujita
Summary: Esters and ethers are commonly used compounds in modern organic synthesis. The dehydrogenative coupling of primary alcohols for ester synthesis has recently been proposed as an environmentally friendly process. In this study, a new catalytic function switching system was successfully developed using a single iridium catalyst, enabling both dehydrogenative esterification and dehydrative etherification under environmentally friendly conditions.
Review
Chemistry, Multidisciplinary
Maria Batuecas, Nikolaus Gorgas, Mark R. Crimmin
Summary: This passage discusses the importance of C-H functionalization, particularly the fast-developing field of C-H borylation. It focuses on palladium- and calcium-catalyzed methods for C-H metalation, revealing new reaction pathways and mechanisms.
Article
Chemistry, Inorganic & Nuclear
Alexey V. Polukeev
Summary: This study presents the synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand. Metalation of POC-H with [Ir(COD)Cl]2 yielded a mixture of (POC)(POC-H)IrHCl and (POC)(COD)IrHCl, which were further converted to (POC)(L)IrHCl complexes through ligand exchange. The compounds were tested in acceptorless and transfer dehydrogenation reactions and compared with pincer complexes. A dimeric complex was obtained from one of the complexes, explaining its low activity. DFT studies shed light on the metalation mechanism.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yan-Cheng Hu, Xiang -Ting Min, Ding -Wei Ji, Qing-An Chen
Summary: Prenylated and reverse-prenylated aromatics are commonly found in natural terpenoids and have diverse pharmaceutical activities. Recent advances in chemical catalysis have successfully emulated the biosynthetic process, using strategies such as Friedel-Crafts reaction, cross-coupling, C-H activation, and others. This review highlights these advancements and discusses regioselectivity issues, aiming to further expand the applications and promote the development of this field.
TRENDS IN CHEMISTRY
(2022)
Article
Chemistry, Physical
Siuli Das, Rakesh Mondal, Gargi Chakraborty, Amit Kumar Guin, Abhishek Das, Nanda D. Paul
Summary: The study presented a ligand-centered redox-controlled approach using a Zn(II)-stabilized azo-anion radical complex as a catalyst for efficient dehydrogenation of various N-heterocycles. The catalyst was found to be compatible with the cascade synthesis of N-heterocycles through dehydrogenative coupling of alcohols with other suitable coupling partners. Mechanistic investigation revealed that the dehydrogenation reactions proceed via a one-electron hydrogen atom transfer pathway and involve exclusive involvement of ligand-centered redox events with zinc acting only as the template.
Article
Chemistry, Physical
Isaac Daniel, Bohyeon Kim, Mark Douthwaite, Samuel Pattisson, Richard Lewis, Joseph Cline, David Morgan, Donald Bethell, Christopher Kiely, Steven Mcintosh, Graham Hutchings
Summary: The cooperative redox enhancement effects in Au-Pd systems play a crucial role in promoting bimetallic catalysis in thermochemical oxidation. The electrochemical polarization of two disparate catalytic sites leads to an observed activity enhancement in thermochemical systems, increasing the driving force of each of the composite half reactions in oxidative dehydrogenation.
Article
Chemistry, Physical
Bolun Yu, Denan Li, Qianqian Zhu, Shufan Yao, Lifeng Zhang, Yanshuo Li, Zhenxin Zhang
Summary: This study successfully improved the catalytic activity of a zeolitic octahedral metal oxide by incorporating a single zinc species into its micropore. The zinc incorporation achieved a high ethane conversion rate and ethylene selectivity. Mechanism study showed that the isolated zinc site played a crucial role in activating oxygen and ethane, as well as stabilizing intermediates and transition states.
APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY
(2024)
Article
Chemistry, Physical
Fang Li, Qian Zhang, Jing Liu, Nan Cui, Guoqing Guan, Wei Huang
Summary: The direct conversion of syngas to higher alcohols can be improved by electronically-modulated ZnO semiconductor with Cu doping, which increases the proportion of higher alcohols in the product. The Cu doping facilitates donor reactions and CO adsorption, leading to higher selectivity. However, excessive Cu doping results in a decrease in higher alcohols proportion.
GREEN ENERGY & ENVIRONMENT
(2022)
Article
Chemistry, Inorganic & Nuclear
Eva Guillamon, Ivan Sorribes, Vicent S. Safont, Andres G. Algarra, M. Jesus Fernandez-Trujillo, Elena Pedrajas, Rosa Llusar, Manuel G. Basallote
Summary: By using a cuboidal [Mo3S4H3(dmpe)(3)](+) hydride cluster as the catalyst, formic acid (FA) can be transformed into hydrogen gas and CO2 without the need for any additives. Compared to other molybdenum compounds, our catalyst has shown higher activity and selectivity. Kinetic studies, reaction monitoring, and DFT calculations have revealed the mechanism of FA dehydrogenation, which involves the formation of a dihydrogen-bonded species and subsequent release of hydrogen gas and coordination of formate. The complete cycle, including the release of CO2 and closure of the catalytic cycle, occurs at higher temperatures.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Sinval F. Sousa, Mehmed Z. Ertem, Leandro A. Faustino, Antonio Eduardo H. Machado, Javier J. Concepcion, Pedro I. S. Maia, Antonio Otavio T. Patrocinio
Summary: A new ruthenium polypyridyl complex was synthesized and characterized, showing instability and oxidation under aerobic conditions. The reaction provides insights into C-H activation with important implications for catalysis. Theoretical and experimental investigations suggest a two-step aerobic oxidative transformation with the formation of a diruthenium mu-peroxo intermediate as an alternative pathway for C-H activation.
DALTON TRANSACTIONS
(2021)
Article
Nanoscience & Nanotechnology
Sreetosh Goswami, Santi P. Rath, Damien Thompson, Svante Hedstrom, Meenakshi Annamalai, Rajib Pramanick, B. Robert Ilic, Soumya Sarkar, Sonu Hooda, Christian A. Nijhuis, Jens Martin, R. Stanley Williams, Sreebrata Goswami, T. Venkatesan
NATURE NANOTECHNOLOGY
(2020)
Article
Chemistry, Inorganic & Nuclear
Meaghan M. Deegan, Rameswar Bhattacharjee, Stavros Caratzoulas, Eric D. Bloch
Summary: This study presents novel approaches to preparing porous molecular structures by metalating nonporous organic cages, resulting in materials with significant structural rigidity. The hybrid metal-organic cages obtained through this method combine characteristics of both porous organic cages and porous coordination cages, potentially offering a new direction for designing and developing porous molecular materials with tunability in various properties.
INORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Sreetosh Goswami, Rajib Pramanick, Abhijeet Patra, Santi Prasad Rath, Martin Foltin, A. Ariando, Damien Thompson, T. Venkatesan, Sreebrata Goswami, R. Stanley Williams
Summary: The profuse dendritic-synaptic interconnections among neurons in the neocortex enable sophisticated decision-making abilities that vastly outperform any artificial electronic analogues. The brain's dynamically reconfigurable network provides flexibility and adaptability to changing environments, in contrast to the hard-wired threshold switches of state-of-the-art semiconductor logic circuits. By re-imagining fundamental electronic circuit elements and expressing complex logic in nanometre-scale material properties, the study demonstrates voltage-driven conditional logic interconnectivity among distinct molecular redox states to embed decision trees within a single memristor, allowing for non-volatile switching transitions between conductance levels in a single sweep cycle. Multiple redox transitions in a molecular memristor can be utilized to undertake complex and reconfigurable logic operations in a single time step.
Article
Chemistry, Inorganic & Nuclear
Rameswar Bhattacharjee, Pere Miro
Summary: This research investigates the speciation chemical structures of hexachloride tetravalent uranium, neptunium, and plutonium species in aqueous media using density functional theory. The study shows that the properties of mixed-ligand complexes in solution are controlled by the concentration of free ligands, and a low chloride concentration can drive the speciation away from the highly thermodynamically stable hexachloride species. Furthermore, the formation of dimeric species is influenced by the number of water ligands.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Rameswar Bhattacharjee, Ethan T. Hare, Pere Miro
Summary: This study provides a computational analysis of the structure, properties, and reactivity of two tetrameric zirconium and hafnium clusters, revealing their characteristic electronic structure and favored incorporation of zirconium into hafnium clusters. Additionally, the study indicates the thermodynamic favorability of incorporating up to four peroxide ligands, while the absence of rich peroxide species with three or more peroxides is attributed to their thermal degradation. The mechanism for peroxide incorporation involves partial dissociation of the cluster.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Thomas M. Rayder, Filip Formalik, Simon M. Vornholt, Hilliary Frank, Seryeong Lee, Maytham Alzayer, Zhihengyu Chen, Debabrata Sengupta, Timur Islamoglu, Francesco Paesani, Karena W. Chapman, Randall Q. Snurr, Omar K. Farha
Summary: Carbon capture, storage, and utilization (CCSU) is an opportunity to reduce carbon emissions and combat global climate change. Metal-organic frameworks (MOFs) have shown great potential as effective CO2 sorbents in CCSU through gas adsorption. Understanding the properties of MOF pores and their dynamic behavior during sorption can lead to the development of more efficient CCSU materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Saptasree Bose, Debabrata Sengupta, Thomas M. Rayder, Xiaoliang Wang, Kent O. Kirlikovali, Ali K. Sekizkardes, Timur Islamoglu, Omar K. Farha
Summary: Direct air capture of CO2 is a promising strategy to address global climate challenges, and metal-organic frameworks show great potential as adsorbents. However, improvements in adsorption efficiency and cost-effectiveness are needed for widespread deployment in DAC.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Megan E. Mccormack, Rameswar Bhattacharjee, Henry Jervis, Zheng Wei, Miklos Kertesz, Marina A. Petrukhina
Summary: A cationic perylene salt was synthesized and characterized. The study revealed a 1D column stacking of perylene molecules, forming dimer structures. Density functional theory calculations showed that pancake bonding contributed significantly to the stability of the perylene dimer, and solid-state packing effects played a critical role in achieving a higher degree of overlap between perylene monomers.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Debabrata Sengupta, Patrick Melix, Saptasree Bose, Joshua Duncan, Xingjie Wang, Mohammad Rasel Mian, Kent O. Kirlikovali, Faramarz Joodaki, Timur Islamoglu, Taner Yildirim, Randall Q. Snurr, Omar K. Farha
Summary: By synthesizing a new air-stable Cu(I)-based material called NU-2100, hydrogen can be stored at ambient temperatures. NU-2100 exhibits good hydrogen storage capability with a density of 10.4 g/L under ambient conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Nanoscience & Nanotechnology
Sreetosh Goswami, Santi P. Rath, Damien Thompson, Svante Hedstrom, Meenakshi Annamalai, Rajib Pramanick, B. Robert Ilic, Soumya Sarkar, Sonu Hooda, Christian A. Nijhuis, Jens Martin, R. Stanley Williams, Sreebrata Goswami, T. Venkatesan
NATURE NANOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Saptasree Bose, Debabrata Sengupta, Christos D. Malliakas, Karam B. Idrees, Haomiao Xie, Xiaoliang Wang, Michael L. Barsoum, Nathaniel M. Barker, Vinayak P. Dravid, Timur Islamoglu, Omar K. Farha
Summary: The increase in atmospheric carbon dioxide level poses a significant threat to our planet, making the selective removal of CO2 from the air a global concern. Metal-organic frameworks (MOFs) show promising potential as adsorbents for CO2 capture due to their high surface area and tunable properties. Among these technologies, direct air capture (DAC) using MOFs is a promising strategy for actively reducing atmospheric CO2 concentration to safer levels and achieving climate targets.
Article
Chemistry, Inorganic & Nuclear
Zhenwei Ni, Rosa Padilla, Rajib Pramanick, Mike S. B. Jorgensen, Martin Nielsen
Summary: A base-free, acceptorless dehydrogenative coupling of ethanol to ethyl acetate is achieved using a pincer complex ((PNP)-P-Ph)RuH(BH4)(CO) (0.25 mol%) and m-xylene as the co-solvent. The catalysis shows excellent conversion and yield of >99% after 24 h at 120 degrees C. The scaled-up reaction is also effective under similar conditions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Gerard P. Van Trieste, Joseph H. Reibenspies, Yu-Sheng Chen, Debabrata Sengupta, Richard R. Thompson, David C. Powers
Summary: In this work, we report the synthesis and oxygen-atom transfer (OAT) photochemistry of [Cu(tpa)BrO3]ClO4. In situ spectroscopy and in crystallo experiments reveal that OAT occurs from a Cu-O fragment, which is generated by sequential Cu-O bond cleavage and OAT from BrOx to [Cu(tpa)](+). These findings highlight synthetic opportunities in M-O photochemistry and demonstrate the usefulness of in crystallo experiments in evaluating photochemical reaction mechanisms.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sibao Liu, Rameswar Bhattacharjee, Sha Li, Andrew Danielson, Tobias Mazal, Basudeb Saha, Dionisios G. Vlachos
Article
Chemistry, Multidisciplinary
Debabrata Sengupta, Sreetosh Goswami, Rajdeep Banerjee, Matthew J. Guberman-Pfeffer, Abhijeet Patra, Anirban Dutta, Rajib Pramanick, Shobhana Narasimhan, Narayan Pradhan, Victor Batista, T. Venkatesan, Sreebrata Goswami
