Review
Chemistry, Multidisciplinary
Shyam Basak, Laura Winfrey, Betty A. Kustiana, Rebecca L. Melen, Louis C. Morrill, Alexander P. Pulis
Summary: Boranes have the ability to mediate hydride abstraction from amino C-H bonds, resulting in the generation of reactive iminium hydridoborate salts that can participate in various stoichiometric and catalytic processes. These reactions include manipulation of amino scaffolds and the use of amine-based reagents for reactions such as transfer hydrogenation and alkylation.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Ivan V. Lapshin, Anton V. Cherkasov, Konstantin A. Lyssenko, Georgy K. Fukin, Alexander A. Trifonov
Summary: A series of NHC-stabilized amido compounds showed remarkable catalytic efficiency in the addition of PhPH and PH3 to alkenes. The sigma-donor capacity of NHCs was found to have an effect on catalytic activity. The complex (NHG)(2)Sm[N(SiMe3)(2)] (5Sm) was identified as the most efficient catalyst.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Danila O. Zakharov, Konstantin Chernichenko, Kristina Sorochkina, Shengjun Yang, Ville-Veikko Telkki, Timo Repo, Vladimir V. Zhivonitko
Summary: In this study, we report the nuclear spin hyperpolarization of various alkenes achieved through alkyne hydrogenations with a metal-free hydroborane catalyst. The specific spin dynamics in catalytic intermediates leads to the hyperpolarization of one hydrogen in the alkene, allowing for advanced characterization of the catalytic process.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Joseph P. Gillions, Salma A. Elsherbeni, Laura Winfrey, Lei Yun, Rebecca L. Melen, Louis C. Morrill, Alexander P. Pulis
Summary: C-H functionalization is an important area in synthetic methodology, and electron-deficient organoboranes have great potential in mediating hydride abstraction from alpha-amino C-H bonds. This review covers recent advances in organoborane-mediated hydride abstraction, focusing on their catalytic applications in alpha- or beta-functionalization, alpha,beta-difunctionalization, and amine dehydrogenation.
Article
Materials Science, Ceramics
Nathaniel S. S. Olson, Frances I. I. Hurwitz, Jamesa L. L. Stokes, Haiquan Guo, Richard B. B. Rogers, Jessica A. A. Krogstad
Summary: The high porosities and low densities of ceramic aerogels offer excellent insulation performance in weight-sensitive applications. However, the high surface area-to-volume ratios and specific surface areas lead to rapid densification of the pore structure at elevated temperatures, limiting their use in high-temperature applications.
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Santanu Ghosh, Johannes Eike Erchinger, Rajat Maji, Benjamin List
Summary: A catalytic enantioselective Diels-Alder reaction has been developed for the synthesis of spirocycles containing highly congested quaternary stereogenic centers. The obtained products are utilized in the concise total and formal syntheses of several sesquiterpenes. The selectivity and regioselectivity of the reaction are controlled by strongly acidic and confined imidodiphosphorimidate catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Andie R. Delaney, Asja A. Kroeger, Michelle L. Coote, Annie L. Colebatch
Summary: This study investigates the bimetallic beta-hydride elimination reaction in nickel complexes, providing further understanding of bimetallic elementary reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Xinzi Pan, Maria Talavera, Thomas Braun
Summary: Dehydrofluorination reactions of fluoroalkanes were catalyzed by nanoscopic aluminum chlorofluoride (ACF, AlClxF3-x, x approximate to 0.05-0.3) in the presence of HSnBu3. Mechanistic studies suggest an initial interaction of ACF with the tin hydride instead of the fluoroalkane.
JOURNAL OF FLUORINE CHEMISTRY
(2022)
Article
Chemistry, Physical
Arron C. Deacy, Christopher B. Durr, Ryan W. F. Kerr, Charlotte K. Williams
Summary: Anhydride and epoxide ring opening copolymerisation can produce aliphatic, semi-aromatic, and functionalised polyesters through the use of heterodinuclear catalysts. These catalysts show high efficiency in forming ester linkages, but exhibit lower activity compared to certain previously reported catalysts. Further exploration of factors influencing synergic heterometallic combinations is needed.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Daniel Duvinage, Lorraine A. Malaspina, Simon Grabowsky, Stefan Mebs, Jens Beckmann
Summary: In this study, the molecular and electronic structures of five divalent bis(m-terphenyl)element cations were investigated using experimental and computational methods. The preparation and characterization of some of these cations have been previously reported, while one was prepared and characterized for the first time. Quantum chemical calculations were used to analyze their electronic structures and compare them to a similar group of compounds previously studied. The results showed that these compounds have high fluoride ion affinities, classifying them as Lewis superacids.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Freya M. M. Harvey, Alexandra H. H. Heidecker, Christian Merten, Thorsten Bach
Summary: Allenes with different substituents at their terminal carbon atom exhibit axial chirality and can be obtained in enantiopure form through a photochemical deracemization protocol. This study investigates the conditions under which allenoic acid derivatives undergo a Diels-Alder reaction with 1,3-cyclopentadienes and the resulting products. Cyclic derivatives (lactams, lactones) exhibited an exo-selective reaction catalyzed by the Lewis acid Eu(fod)(3), while acyclic derivatives mainly produced endo-products (with EtAlCl2 as the preferred Lewis acid). The exocyclic double bond exhibited excellent diastereoselectivity and achieved near-perfect chirality transfer. The method was successfully applied to the synthesis of sesquiterpenes beta-santalol (1) and 10(E)-beta-santalic acid (13).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Organic
Sudheesh T. T. Sivanandan, Mukkath J. J. Jesline, Divya K. K. Nair, Tarun Kumar
Summary: Organic transformations using visible light-mediated photoredox reactions have gained significant attention in recent years. Nitroalkenes have emerged as excellent coupling partners in these reactions, and various methodologies have been reported to achieve different types of alkenes and heterocycles. This review provides a summary of the synthetic potential of nitroalkenes under visible light photoredox catalysis, as a focused review on this topic has not yet appeared.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yuuri Tanaka, Shu-hei Kobayashi, Yasunao Hattori, Atsushi Kawamura, Hidefumi Makabe
Summary: This study investigated the Lewis acid mediated self-condensation of epicatechin gallate derivative. It was found that Yb(OTf)3 provided a good yield of dimeric epicatechin gallate derivative, which was then used for the synthesis of procyanidin B2 3,3''-digallate.
Article
Chemistry, Inorganic & Nuclear
Anran Zhou, Xuanyu Cao, Huanhuan Chen, Dongru Sun, Yufen Zhao, Wonwoo Nam, Yong Wang
Summary: This study reveals the performance of cobalt complexes in reactions through calculated results, finding that the oxygen species of cobalt ions may have different electronic structures and reaction mechanisms under different coordination and reaction conditions. These theoretical findings are of great significance for understanding biomimetic metal-oxygen chemistry.
DALTON TRANSACTIONS
(2022)
Article
Materials Science, Ceramics
Eeshani Godbole, Anette von der Handt, David Poerschke
Summary: This study investigates the influence of rare earth ion radius on the stability and extent of the garnet solid solution phase. Results show a reduction in stability of silicate garnet with increasing rare earth ion radius. Different rare earth systems exhibit varied phases formation, but the extent of the garnet solid solution only slightly increases compared to apatite stability.
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Naresh Eedugurala, Zhuoran Wang, Uddhav Kanbur, Arkady Ellern, Marek Pruski, Aaron D. Sadow
Summary: This study presented the synthesis and characterization of To(M) copper complexes, as well as the attempt to synthesize monomeric copper(II) hydride. Through experiments and analyses, the structures and properties of these copper(II) compounds were determined, providing a reference for further research in the field of organometallic chemistry.
HELVETICA CHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Smita Patnaik, Uddhav Kanbur, Arkady Ellern, Aaron D. Sadow
Summary: The study revealed that the (BOXZnR)-B-Ph-Zn-Me2 catalyst can efficiently catalyze the synthesis of silyl ethers and hydrogen under solvent-free conditions. The catalyst adapts its mechanism to achieve the most efficient conversion by adjusting the rate law and experimental rate constants based on reactant concentrations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Uddhav Kanbur, Guiyan Zang, Alexander L. Paterson, Puranjan Chatterjee, Ryan A. Hackler, Massimiliano Delferro, Igor I. Slowing, Frederic A. Perras, Pingping Sun, Aaron D. Sadow
Summary: This study introduces a new catalytic method that converts polyolefins in discarded plastics into high-value compounds, overcoming the limitations of traditional carbon-carbon bond cleavage methods. Economic analysis shows that this method is cost-effective and has the potential to address the plastic-waste crisis.
Article
Chemistry, Multidisciplinary
Yuting Li, Uddhav Kanbur, Jinlei Cui, Guocang Wang, Takeshi Kobayashi, Aaron D. Sadow, Long Qi
Summary: The zeolite-supported lanthanide La(BH4)(x)-HY30 is capable of catalyzing the C-H borylation of benzene with pinacolborane, providing a complementary approach to precious, late transition metal-catalyzed borylations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Frederic A. Perras, Uddhav Kanbur, Alexander L. Paterson, Puranjan Chatterjee, Igor I. Slowing, Aaron D. Sadow
Summary: The immobilization of molecularly precise metal complexes on substrates, such as silica, provides a platform for designing active sites in heterogeneous catalysts. NMR-based surface-to-complex interatomic distances can be used to solve the three-dimensional structures of metal complexes on silica, revealing unexpected features. This approach is robust and easily applicable to most single-site catalysts with little extra effort.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xun Wu, Akalanka Tennakoon, Ryan Yappert, Michaela Esveld, Magali S. Ferrandon, Ryan A. Hackler, Anne M. LaPointe, Andreas Heyden, Massimiliano Delferro, Baron Peters, Aaron D. Sadow, Wenyu Huang
Summary: This study investigates the effects of Pt nanoparticle size on the activity and selectivity of polyethylene hydrogenolysis. The results show that the smallest Pt nanoparticles exhibit the highest activity, while the three different-sized Pt nanoparticles have equivalent selectivity. Furthermore, the study also reveals that the mesoporous pores template the formation of a C 23 -centered distribution of hydrocarbons. These findings provide a framework for catalyst design by separating the carbon-carbon bond cleavage activity from the selectivity for chain lengths of the products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Yang-Yun Chu, Annabelle Lolinco, Naresh Eedugurala, Arkady Ellern, Theresa L. Windus, Aaron D. Sadow
Summary: The study investigates the reactions of proligands C(5)H(5)CMe(2)CHPhOx(R) (R = Me-2, CHMe2, and CMe3) with M(NMe2)(4) (M = Ti, Zr, and Hf), and identifies different reaction products under different conditions and with different ligands and metal centers. The results highlight the importance of the oxazoline ligand in the reaction and its effects on the proton transfer.
Article
Chemistry, Physical
Kevin Basemann, Bradley M. Schmidt, Aaron D. Sadow
Summary: The study of reaction conditions for ruthenium-catalyzed ene-yne metathesis has shown that substituents and functional groups on the terminal alkyne reactant play a significant role in affecting the outcomes. Utilizing different methods and optimized conditions can lead to high turnovers and yields. Various research approaches and reaction conditions can improve the efficiency and conversion rates of the reactions.
Article
Chemistry, Physical
Puranjan Chatterjee, Hsin Wang, J. Sebastian Manzano, Uddhav Kanbur, Aaron D. Sadow, Igor I. Slowing
Summary: The study reports an improved catalytic activity for the aerobic alpha-oxidation of amines using silica-supported Au nanoparticles by tethering pyridyl ligands to the support. The research indicates that ligands affect the electronic properties of the Au nanoparticles, which in turn determine their ability to activate O-2 and mediate C-H cleavage in the substrate.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Rick W. Dorn, Alexander L. Paterson, Ivan Hung, Peter L. Gor'kov, Austin J. Thompson, Aaron D. Sadow, Zhehong Gan, Aaron J. Rossini
Summary: This study investigated pulse sequences for magic-angle spinning solid-state NMR experiments to probe the vicinity of quadrupolar spins. The experiments and numerical simulations allowed estimation of isotopic enrichment. Moreover, the practical application of these heteronuclear correlation experiments in probing structural connectivity between two quadrupolar spins was demonstrated.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Uddhav Kanbur, Alexander L. Paterson, Jessica Rodriguez, Andrew L. Kocen, Ryan Yappert, Ryan A. Hackler, Yi-Yu Wang, Baron Peters, Massimiliano Delferro, Anne M. LaPointe, Geoffrey W. Coates, Frederic A. Perras, Aaron D. Sadow
Summary: The C-H/Et-Al exchange reaction of saturated hydrocarbons and AlEt3 using zirconium catalysts produces versatile organoaluminum compounds and ethane. The grafting of commercially available Zr(OtBu)(4) on silica/alumina provides monopodal SiO-Zr(OtBu)(3) surface pre-catalyst sites that can be activated by ligand exchange with AlEt3. This selective methyl group alumination enables the C-H alumination of various hydrocarbon substrates without significant chain deconstruction. Additionally, methane can undergo selective mono-alumination under solvent-free catalytic conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Katherine E. McCullough, Ian L. Peczak, Robert M. Kennedy, Yi-Yu Wang, James Lin, Xun Wu, Alexander L. Paterson, Frederic A. Perras, Jacklyn Hall, A. Jeremy Kropf, Ryan A. Hackler, Youngho Shin, Jens Niklas, Oleg G. Poluektov, Jianguo Wen, Wenyu Huang, Aaron D. Sadow, Kenneth R. Poeppelmeier, Massimiliano Delferro, Magali S. Ferrandon
Summary: This study presents a scalable synthesis method for Pt/STO by surface organometallic chemistry (SOMC) techniques using Pt(ii) acetylacetonate or trimethyl(methylcyclopentadienyl)platinum. The Pt/STO catalysts effectively hydrogenolyzed polyolefins into hydrocarbon oils, offering a promising approach for upcycling plastic waste. This new synthesis method overcomes the cost and resource-intensive issues associated with the previous atomic layer deposition (ALD) technique.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Shaojiang Chen, Akalanka Tennakoon, Kyung-Eun You, Alexander L. L. Paterson, Ryan Yappert, Selim Alayoglu, Lingzhe Fang, Xun Wu, Tommy Yunpu Zhao, Michelle P. P. Lapak, Mukunth Saravanan, Ryan A. A. Hackler, Yi-Yu Wang, Long Qi, Massimiliano Delferro, Tao Li, Byeongdu Lee, Baron Peters, Kenneth R. R. Poeppelmeier, Salai C. C. Ammal, Clifford R. R. Bowers, Frederic A. Perras, Andreas Heyden, Aaron D. D. Sadow, Wenyu Huang
Summary: Non-reducible zirconia catalysts can efficiently hydrogenolytically cleave polyolefins, achieving similar activity as precious metal nanoparticles.
Article
Chemistry, Inorganic & Nuclear
Yang-Yun Chu, Andres Garcia Alejo, Sergey L. Bud'ko, Kasuni Boteju, Smita Patnaik, Arkady Ellern, Marilu Perez Garcia, Aaron D. Sadow
Summary: The magnetic properties of 4f organometallic compounds stabilized by secondary Ln-H-Si and benzylic interactions were investigated. The compounds without a benzyl group have a larger ligand field splitting energy manifold. Doping DyR3 into LaR3 results in the crystal structure of the latter compound, and the resulting material shows hysteresis in magnetic measurements.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Max Meirow, Akalanka Tennakoon, Xun Wu, Jarod Willmon, Daniel Howell, Wenyu Huang, Aaron D. Sadow, Erik Luijten
Summary: Due to the plastic waste crisis, selective chemical upcycling of polyolefins into value-added products has attracted great interest. A recent study has synthesized a catalytic architecture that can control the product chain lengths by manipulating the pore length, and uncovered the dynamic phenomenon responsible for the pore-length dependence of the cleavage products.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
