Article
Chemistry, Physical
Dilip K. Pandey, Eugene Khaskin, Shrinwantu Pal, Robert R. Fayzullin, Julia R. Khusnutdinova
Summary: We describe an efficient semihydrogenation of terminal alkynes using a modified tetramethylated PNP pincer Fe hydride complex. The modified complex shows different reactivity compared to a classical PNP Fe hydride complex with CH2 arms, which predominantly catalyzes terminal alkyne dimerization even in the presence of H-2. The modified PNP ligand allows for selective alkene formation, eliminating dimerization side products and minimizing overreduction.
Article
Chemistry, Organic
Andrea Nicola Paparella, Francesco Messa, Serena Perrone, Antonio Salomone
Summary: Treatment of internal alkynes with Al powder, Pd/C, and basic water in a methyltriphenylphosphonium bromide/ethylene glycol eutectic mixture yields highly chemoselective formation of (Z)-alkenes, with yields up to 99% and Z/E stereoselectivity ranging from 63/37 to 99/1. The unusual catalytic activity of Pd/C is believed to be modulated by the in situ formation of a phosphine ligand.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shuaishuai Song, Yunfei Lai, Zekun Tuo, Jianming Zhong, Wang Zhou
Summary: A rhodium(III)-catalyzed oxidative cyclization of chalcones with internal alkynes is reported, resulting in the formation of biologically important 3,3-disubstituted 1-indanones and reusable aromatic aldehydes. This transformation exhibits a unique (4+1) reaction mode, excellent regioselectivity, broad substrate scope, ability to construct quaternary carbon centers, and scalability. Steric hindrance from the substrate and ligand likely controls the chemoselectivity of this carbocyclization. Importantly, this discovery enables a practical two-step protocol to switch the overall reaction from a (3+2) to a (4+1) annulation of acetophenones with internal alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Kanchana Chatchaipaiboon, Kotohiro Nomura
Summary: New niobium(V)-alkylidene complexes were prepared and found to exhibit superior catalytic activities for ring-opening metathesis polymerization (ROMP) reactions. One of the complexes also showed Z-specific ROMP activity for cis-cyclooctene at high temperature.
Review
Chemistry, Physical
Maximilian Koy, Peter Bellotti, Mowpriya Das, Frank Glorius
Summary: This review discusses the use of N-heterocyclic carbenes as molecular modifiers for metal surfaces, aiming to improve the reactivity of metal-based heterogeneous catalysts. Combining sophisticated ligand systems from homogeneous catalysis with metal surfaces can enhance parameters such as stability and selectivity of catalysts.
Article
Chemistry, Inorganic & Nuclear
David Decker, Zhihong Wei, Jabor Rabeah, Hans-Joachim Drexler, Angelika Brueckner, Haijun Jiao, Torsten Beweries
Summary: In this study, a Co(ii) PNNH pincer catalyst system was applied for the highly E-selective transfer semihydrogenation of internal diaryl alkynes. The catalyst system showed high activity, short reaction times, and operated under mild conditions.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Xuehua Wang, Xianghu Wang, Tianyu Shi, Yuhan Fang, Alan Meng, Lei Wang, Shaoxiang Li, Guicun Li, Xiao Yu, Zhenjiang Li
Summary: A sulfur-deficient ZnIn2S4/In2Se3 photocatalyst was developed to achieve efficient direct Z-scheme charge transfer, which significantly improved the separation of photocarriers and enhanced the utilization of visible light.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Xiaoming Song, Yingmo Zhang, Yunqiang Li, Xiaowei Zhao, Yanli Yin, Xu Ban, Zhiyong Jiang
Summary: A modular and efficient synthetic approach that enables the enantioselective reductive coupling of imine-containing azaarenes with 1,4-dihydropyridines via cooperative photoredox and chiral Bronsted acid catalysis is reported. The enantioselective radical coupling generates aza-quaternary carbon stereocenters α to azaarenes, offering a promising strategy for the asymmetric synthesis of α-azaaryl-substituted tertiary amines and α-amino acid derivatives.
Article
Thermodynamics
Felipe Bolanos-Chaverri, John Mantzaras, Timothy Griffin, Rolf Bombach, Dieter Winkler
Summary: The catalytic-rich/gaseous-lean combustion concept was studied for syngas fuels, showing that the exothermicity of heterogeneous reactions promoted homogeneous ignition and complete fuel conversion. The catalyst not only initiated gaseous combustion but also reduced potential NOx emissions, while two-sided diffusion flames were advantageous for burner compactness.
PROCEEDINGS OF THE COMBUSTION INSTITUTE
(2021)
Article
Chemistry, Organic
Liu Changjun, Hu Huiling, Liu Chenghong, Zhu Chaojie, Tang Tiandi
Summary: 1,2-dione compounds were synthesized under clean reaction conditions using Pd/METS-10 catalyst. The catalyst demonstrated excellent selectivity and substrate scope, as well as good repetition performance. The reaction mechanism was also proposed.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jiamin Wei, Qing Wang, Mian He, Shuai Li, Yunan Zhang, Yang Yang, Shipeng Luo, Lianshe Fu, Xin Wang, Tinghai Yang
Summary: Researchers have developed a Fe (III) doping modified AgI/NH2-MIL-68(In/Fe) Z-scheme heterojunction composite with unique charge transmission performance. The optimized composite, ANM-50, showed significantly higher photocatalytic activity for tetra-cycline degradation compared to other materials used in the study. The photocatalytic procedure resulted in the generation of Ag nanoparticles, which acted as a charge transfer highway and improved charge transfer efficiency and stability of the heterojunction.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Ahmed M. Fathy, Mahmoud M. Hessien, Mohamed M. Ibrahim, Abd El-Motaleb M. Ramadan
Summary: This study focused on synthesizing and characterizing four naphthaldiimine ligands and their ruthenium(III) complexes. The molecular formulas of the prepared Ru(III) complexes were determined through various analyses. The structural formulas of the complexes were confirmed using X-ray diffraction data and computer program Expo 2014. The catalytic potential of the complexes in hydrogenation reactions was investigated, and a mechanism for the reactions was proposed based on experimental results.
JOURNAL OF COORDINATION CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Erik T. Ouellette, Julian S. Magdalenski, Robert G. Bergman, John Arnold
Summary: Low-valent transition metalates are highly reactive chemical reagents that find applications in organic synthesis, small-molecule activation, transient species stabilization, and M-E bond formation. Recent studies have discovered new types of highly reactive metalates without traditional carbonyl ligands. These metalates display unique reactivity in small-molecule activation, metal-metal bond formation, and heterometallic complex synthesis.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Organic
Savannah M. Stull, Liangyong Mei, Thomas L. Gianetti
Summary: A new organic reaction method has been reported in this study, allowing for the synthesis of a variety of organic molecules under mild conditions. This method can effectively produce cyclopentane or cyclopentene derivatives with different functional groups.
Article
Chemistry, Inorganic & Nuclear
Anukta Jain, Jade Fostvedt, Benjamin M. Kriegel, David W. Small, Lauren N. Grant, Robert G. Bergman, John Arnold
Summary: In this study, the reactivity between a beta-diketiminate-supported niobium(III) imido complex and alkyl azides was demonstrated, resulting in the formation of niobatetrazene complexes. The reaction mechanism was also determined using computational methods.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Michael A. Boreen, Christopher Z. Ye, Andrew Kerridge, Karl N. McCabe, Brighton A. Skeel, Laurent Maron, John Arnold
Summary: This study investigates the mechanism of isomerization of uranium complexes. Experimental and computational studies reveal two different intramolecular C-H activation mechanisms involved.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tianchang Liu, Ryan P. Murphy, Patrick J. Carroll, Michael R. Gau, Neil C. Tomson
Summary: This report describes the first examples of unassisted C(sp)-C(sp(2)) and C(sp)-C(sp(3)) bond oxidative addition reactions that yield thermodynamically favorable products. The reactions were achieved using a diiron complex supported by a flexible macrocyclic ligand. The study demonstrates the significant potential of C-C sigma-bond functionalization reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Erik T. Ouellette, Julian S. Magdalenski, Robert G. Bergman, John Arnold
Summary: We report the synthesis and characterization of a novel rhenium-group 9 heterobimetallic diazenido species and its related diazenido and hydride complexes. Furthermore, we demonstrate the possibility of N-C bond formation in heterobimetallic complexes and investigate their properties using spectroscopy and computational studies.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Christopher Z. Ye, Iker Del Rosal, Michael A. Boreen, Erik T. Ouellette, Dominic R. Russo, Laurent Maron, John Arnold, Clement Camp
Summary: Reaction of potassium pentamethylcyclopentadienyl iridate tris-hydride with UCl4 and ThCl4 led to the generation of multimetallic complexes with different hydride bonding modes. Computational studies suggest that the bonding between U/Th and Ir is significant and involving f-orbitals. The variation in hydride bonding is attributed to differences in dispersion effects.
Article
Chemistry, Inorganic & Nuclear
Qiuran Wang, Michael R. R. Gau, Brian C. C. Manor, Patrick J. J. Carroll, Neil C. C. Tomson
Summary: A series of Ag-I complexes supported by a flexible macrocyclic ligand are reported, with different Ag-Ag interactions depending on the ancillary ligand and counterion. Solution-phase studies found rapid interconversion through a mechanism that retained the multi-nuclearity. Analysis of the solid-state structures revealed nearly identical Ag-Ag interactions, while a weak inter-ligand interaction between isocyanide units contributed to the folded-ligand geometry.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ariana Z. Spentzos, Sam R. May, Alex M. Confer, Michael R. Gau, Patrick J. Carroll, David P. Goldberg, Neil C. Tomson
Summary: This article focuses on the synthesis, characterization, and reactivity of a series of C (3v )-symmetric diiron complexes. The complexes were studied using various techniques, including crystallography, spectroscopy, and computation. The redox behavior of the complexes revealed that oxidation is localized to one metal center (Fe-C), and S-atom transfer chemistry led to the formation of Fe4S and Fe4S2 products. Treatment of the neutral complex with Ph3SH resulted in the formation of Fe4S x clusters.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Marko H. Nowack, Jules Moutet, Bo W. Laursen, Thomas L. Gianetti
Summary: Trianguleniums are versatile and tunable organic photoredox catalysts that can be used for both photooxidations and photoreductions.
Article
Chemistry, Inorganic & Nuclear
Sam H. Brooks, Corey A. Richards, Patrick J. Carroll, Michael R. Gau, Neil C. Tomson
Summary: This study investigates the chemistry of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers for constructing multicopper complexes that can activate small molecules in materials and enzymatic systems. By improving ligand design and synthetic strategies, a series of dicopper complexes with improved solubility have been developed. Various bridging ligands were introduced into the macrocycle-supported complexes, allowing for the capture of different anions.
Article
Materials Science, Multidisciplinary
Jules Moutet, Marko H. Nowack, David D. Mills, Diego L. Lozier, Bo W. Laursen, Thomas L. Gianetti
Summary: This study presents the use of a bipolar molecule as a redox active material in a fully organic symmetrical flow battery, showing excellent performance and stability, which has the potential to promote the development of NAORFB technology.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Alexander B. Weberg, Ryan P. Murphy, Neil C. Tomson
Summary: The power of oriented electrostatic fields (ESFs) to influence chemical bonding and reactivity has attracted growing interest. Strong ESFs have been found to contribute significantly to enzyme activity, where alignment of a substrate's changing dipole moment with a strong, local electrostatic field is responsible for enhancing the enzymatic rate. Researchers have also explored the impacts of internal electrostatic fields through the addition of ionic salts and charged functional groups, as well as externally through bulk fields between electrode plates. Incorporating charged moieties into homogeneous inorganic complexes to generate internal ESFs has great potential for novel catalyst design.
Review
Chemistry, Multidisciplinary
Gabriela I. Vargas-Zuniga, Michael A. Boreen, Daniel N. Mangel, John Arnold, Jonathan L. Sessler
Summary: The diverse coordination modes and electronic features of actinide complexes of porphyrins and related oligopyrrolic systems have been the subject of interest since the 1960s. Most work has focused on thorium and uranium, but the ligand environments provided by porphyrinoids have led to the stabilization of unique complexes with early actinides. This review summarizes key examples of prophyrinoid actinide complexes, with emphasis on synthesis, structure, electronic features, and reactivity patterns of representative systems.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Materials Science, Multidisciplinary
Jules Moutet, David Mills, Md Mubarak Hossain, Thomas L. Gianetti
Summary: The study demonstrates that nitration treatment enhances the electrochemical performance of DMQA(+) as an electrolyte for SORFBs. Results show that C-NO2(+) exhibits excellent stability and high coulombic efficiencies, making it a promising option for high cycle numbers and energy density in large-scale energy storage applications.
MATERIALS ADVANCES
(2022)