Article
Chemistry, Multidisciplinary
Janis Musso, Jordan De Jesus Silva, Mathis J. Benedikter, Jonas Groos, Wolfgang Frey, Christophe Coperet, Michael R. Buchmeiser
Summary: Recent studies have shown that cationic d(0) group 6 olefin metathesis catalysts exhibit higher activity compared to their neutral counterparts, and their catalytic performance is greatly enhanced by immobilization on silica.
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
Chemistry, Inorganic & Nuclear
Jordan De Jesus Silva, Margherita Pucino, Feng Zhai, Deni Mance, Zachariah J. Berkson, Darryl F. Nater, Amir H. Hoveyda, Christophe Coperet, Richard R. Schrock
Summary: In this study, the catalytic performances of molybdenum oxo alkylidene species with different anionic O ligands were evaluated in metathesis reactions of internal and terminal olefins. It was found that the presence of the ORF9 ligand significantly increased catalytic activity, particularly in the molecular form. In contrast, molecular complexes with large aryloxy anionic ligands showed little activity, while their silica-supported counterparts exhibited improved activity.
INORGANIC CHEMISTRY
(2021)
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, Multidisciplinary
Jun Zhu, Rui Zhang, Guangbin Dong
Summary: A rare reversible C-C single-bond metathesis reaction catalyzed by ruthenium was reported, enabling the synthesis of biaryl compounds under redox-neutral and pH-neutral conditions. The reaction mode involves unexpected 18-electron closed-shell intermediates and is expected to inspire the development of more general C-C single-bond metathesis and orthogonal cross-coupling reactions.
Article
Chemistry, Inorganic & Nuclear
Dmitry S. Belov, Carlos M. Acosta, Miquel Garcia-Molina, Kelly L. Rue, Xavier Solans-Monfort, Konstantin V. Bukhryakov
Summary: This study reports the reactivity of V oxo NHC chloride and alkoxide alkylidenes and their preference for the formation of 1,3-metallacyclobutane (MCB) in cycloaddition/cycloreversion steps with olefins.
Article
Chemistry, Physical
Anne V. Le, Biplab Rajbanshi, Raul F. Lobo, Peng Bai
Summary: In this study, DFT calculations were used to investigate the mechanisms of propene metathesis catalyzed by WOx/SiO2. The results showed that there are still many mechanisms of heterogeneous catalyzed metathesis reactions that are not well understood. The pseudo-Wittig mechanism was found to be the most favorable method for generating initial alkylidene active sites. The allylic and vinylic C-H activations are more difficult and require the reduction of surface sites to W(+4).
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Yi Peng, Martin Oestreich
Summary: A B(C6F5)3-catalyzed reductive denitrogenation of aromatic nitriles is reported, achieving the metal-free transformation of a cyano into a methyl group in a single synthetic operation. Tris(phenylsilyl)amine is liberated as the nitrogen-containing byproduct.
Article
Chemistry, Inorganic & Nuclear
Michael R. Buchmeiser, Dominik Imbrich, Dongren Wang, Stefan Naumann
Summary: The authors synthesized a series of tungsten (VI) imido alkylidene N-heterocyclic olefin (NHO) complexes and found that the catalysts showed improved activity in ring-closing metathesis by adjusting the number and type of NHO ligands. The results indicate that further optimization of the catalysts' performance can be achieved by ligand tuning.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Darryl F. Nater, Maxime Boudjelel, Lukas Laetsch, Richard R. Schrock, Christophe Coperet
Summary: Tungsten oxo adamantylidenes are a new class of easily accessible alkylidenes, which can be used to evaluate a wider range of molecular and supported olefin metathesis catalysts. The high thermal stability of the perfluoro-tert-butoxide complex, even in its dimer form, allows for grafting through sublimation. Evaluation of these supported species using standardized protocols demonstrates their high activity toward internal and terminal olefins.
HELVETICA CHIMICA ACTA
(2022)
Article
Chemistry, Inorganic & Nuclear
Maxime Boudjelel, Feng Zhai, Richard R. Schrock, Amir H. Hoveyda, Charlene Tsay
Summary: The molybdenum and tungsten oxo 2-adamantylidene complexes were prepared by adding 2-methylene- or 2-ethylideneadamantane to neophylidene or neopentylidene complexes. The tungsten complex 2(w) is a thermally stable dimer with unsymmetrically bridging oxo ligands, while the molybdenum complex 2(Mo) is a stable monomer. These complexes are reactive olefin metathesis initiators with dimers 5(Mo) and 5(w) being relatively poor initiators.
Article
Chemistry, Inorganic & Nuclear
Y. Bouhoute, D. Grekov, N. Merle, K. C. Szeto, C. Larabi, I. Del Rosal, L. Maron, L. Delevoye, R. M. Gauvin, M. Taoufik
Summary: O-17-labelled tungsten siloxide complexes were studied to propose guidelines linking O-17 NMR parameters and the coordination sphere of tungsten oxo species. The grafting of the complexes onto SiO2-700 resulted in the formation of a material with different surface species, as confirmed by elemental analysis and various NMR techniques. DFT calculations supported the observed reactivity and indicated the presence of multiple isomeric species for the grafted W centers.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Darryl F. Nater, Christoph J. Kaul, Lukas Laetsch, Hayato Tsurugi, Kazushi Mashima, Christophe Coperet
Summary: Tailored molybdenum (VI)-oxo complexes can catalyze olefin metathesis reaction under specific conditions, and the structural, spectroscopic and electronic characteristics of the catalyst precursor have an influence on the initiation and catalytic efficiency of the final product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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, 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
Steven Giese, Katrin Klimov, Antal Mikehazi, Zsolt Kelemen, Daniel S. Frost, Simon Steinhauer, Peter Mueller, Laszlo Nyulaszi, Christian Mueller
Summary: The yet unknown 2-amino-substituted lambda(3),sigma(2)-phosphinines are phosphorus-containing aniline derivatives. Our experimental and theoretical investigations reveal that 2-aminophosphinines are missing links in the series of known 2-donor-functionalized phosphinines. These compounds show high pi-density at the phosphorus atom due to strong interaction with the pi-donating NR2 group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Gayathri B. Gange, Amanda L. Humphries, Dmitry E. Royzman, Mark D. Smith, Dmitry Peryshkov
Summary: The metal-free bond activation by carboranyl diphosphine 1-(PBu2)-Bu-t-2-(PPr2)-Pr-i-C2B10H10 involves the formal oxidation of phosphine groups and concomitant reduction of the boron cage in reactions with main group hydrides and alcohols. This new approach is driven by the cooperation between electron-donating exohedral substituents and electron-accepting cluster, and is reminiscent of oxidative addition to transition metal centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Bennett J. Eleazer, H. D. A. Chathumal Jayaweera, Gayathri B. Gange, Mark D. Smith, Corey R. Martin, Kyoung Chul Park, Alexey A. Popov, Dmitry Peryshkov
Summary: The synthesis of well-defined heterometallic complexes is a challenging frontier in inorganic chemistry. A new approach involving sequential insertion of electrophilic metal fragments into electron-rich Ru-B bonds has been reported, leading to the selective preparation of bimetallic and trimetallic complexes. Structural and theoretical analysis of chemical bonding features within Ru-B-B-Cu and Ru-B-B-Pd fragments were presented.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Andre K. Eckhardt, Martin-Louis Y. Riu, Peter Muller, Christopher C. Cummins
Summary: In this study, further reactivity studies of the N(3)PA molecule were conducted, including strain-promoted 1,3-dipolar cycloaddition with cyclooctyne and Staudinger-type reactivity. The click reaction was found to be faster than the dissociation of N(3)PA. The Staudinger-type reactivity allowed transfer of the NPA fragment to a base-stabilized silylene.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Andre K. Eckhardt, Martin-Louis Y. Riu, Mengshan Ye, Peter Muller, Giovanni Bistoni, Christopher C. Cummins
Summary: A novel phosphorus mononitride precursor is reported, which can release PN molecules in solution and serve as a PN transfer reagent for synthesis.
Article
Chemistry, Inorganic & Nuclear
Gayathri B. Gange, Amanda L. Humphries, Mark D. Smith, Dmitry V. Peryshkov
Summary: In this study, we report the reactivity of carboranyl diphosphine with terminal alkynes, resulting in the formation of boron-containing phosphacycles. The reaction combines the activation of electron-deficient alkynes by phosphine groups and the redox behavior of carborane clusters, leading to the formation of a fused product of alkenylphosphonium cycle and reduced carborane cluster.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Quinton J. Bruch, Akira Tanushi, Peter Muller, Alexander T. Radosevich
Summary: This study demonstrates that hydride transfer catalysis can be enabled by a transition metal-bound low symmetry tricoordinate phosphorus ligand. The reactivity of the phosphorus ligand enables catalytic hydrodechlorination, making it a significant finding in the field of catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tomoaki Sakurada, Yeongsu Cho, Watcharaphol Paritmongkol, Woo Seok Lee, Ruomeng Wan, Annlin Su, Wenbi Shcherbakov-Wu, Peter Mueller, Heather J. Kulik, William A. Tisdale
Summary: This work reports a chemically robust yellow emissive one-dimensional (1D) semiconductor, silver 2,6-difluorophenylselenolate-AgSePhF2(2,6), which belongs to the class of hybrid low-dimensional semiconductors. Introduction of fluorine atoms at the (2,6) position of the phenyl ring induces a structural transition from 2D sheets to 1D chains. AgSePhF2(2,6) exhibits strongly dispersive conduction and valence bands along the 1D crystal axis. Visible photoluminescence with prompt and delayed components is observed at room temperature.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Taryn D. Palluccio, Meaghan E. Germain, Marco Marazzi, Manuel Temprado, Jared S. Silvia, Peter Mueller, Christopher C. Cummins, Jack V. Davis, Leonardo F. Serafim, Burjor Captain, Carl D. Hoff, Elena V. Rybak-Akimova
Summary: This study describes the synthesis and structures of nitrile complexes of V (N[(t) Bu] Ar) (3), 2 (Ar = 3,5-Me2C6H3). The thermochemical and kinetic data for their formation were determined using various techniques. The extent of back-bonding from metal to coordinated nitrile reveals a different role of electron donation compared to the related complex Mo (N[(t) Bu] Ar) (3), 1. Kinetic studies show similar rate constants for nitrile binding to 2, but the activation parameters depend on the nature of R in RCN. Density functional theory (DFT) calculations support the formation of a π-stacking interaction between a pendant arene of the metal anilide and the arene substituent on the incoming nitrile in favorable cases.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Mohammad Jahirul Islam, Kyoung Chul Park, Olivia M. M. Manley, Mark D. D. Smith, Thomas M. M. Makris, Dmitry V. V. Peryshkov
Summary: We describe the synthesis and characterization of a nickel(II) complex with a dicarboranyl CNC dianionic pincer ligand, which can activate acetonitrile through C-C bond cleavage. By deprotonating the relatively acidic C-H bond of coordinated acetonitrile with potassium t-butoxide, a C-bound cyanomethylene ligand is formed at the metal center. Unlike most previously characterized Ni(II) cyanoalkyls, this complex can rapidly transform under aerobic conditions at room temperature to form CNC-ligated nickel(II) cyanide, indicating facile cleavage of the C-CN bond. The cyanoalkyl and cyanide complexes were isolated in excellent yields and characterized by NMR spectroscopy and single-crystal X-ray diffraction.
Article
Chemistry, Multidisciplinary
Gregory D. Thiabaud, Miriam Schwalm, Sajal Sen, Ali Barandov, Jacob Simon, Peter Harvey, Virginia Spanoudaki, Peter Muller, Jonathan L. Sessler, Alan Jasanoff
Summary: This study successfully synthesized a molecular probe that allows assessment of intracellular calcium levels through fluorescence, photoacoustic, and magnetic resonance imaging techniques, which can be detected in brain tissue.
Article
Chemistry, Multidisciplinary
Bryce C. Nussbaum, Amanda L. Humphries, Gayathri B. Gange, Dmitry V. Peryshkov
Summary: Icosahedral closo-dodecaboranes have the ability to accept two electrons, transforming into a dianionic nido-cluster. This transformation can be used for electron storage, bond activation, or altering coordination to metal cations. In this feature article, we present cases demonstrating the redox activity of carborane leading to unique products. We emphasize the impact of exohedral substituents on reactivity and product stability through conjugation with the cluster.
CHEMICAL COMMUNICATIONS
(2023)
Article
Materials Science, Multidisciplinary
William J. Mullin, Peter Mueller, Anthony J. Schaefer, Elisa Guzman, Steven E. Wheeler, Samuel W. Thomas
Summary: This study investigates the stacking interactions between aromatic rings and heterocycles, revealing that fluorinated side-chains and electron-rich units have interactions in the solid state, while electron-deficient units are incompatible. These interactions play a significant role in compound stability.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Organic
Brandon K. Redden, Robert W. Clark, Ziyuan Gong, Md Mamdudur Rahman, Dmitry Peryshkov, Sheryl L. Wiskur
Summary: The mechanism of the asymmetric silylation of alcohols with isothiourea catalysts was studied using reaction progress kinetic analysis, revealing the significance of silyl chloride in the reaction. The findings contribute to understanding the catalytic mechanism of the reaction and offer insights for further research.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
H. D. A. Chathumal Jayaweera, Md Mamdudur Rahman, Perry J. Pellechia, Mark D. Smith, Dmitry Peryshkov
Summary: This work presents the synthesis and structural characterization of the free ortho-carboranyl [C2B10H11](-) and the doubly deprotonated 1,1'-bis(o-carborane) anion [C2B10H10](2)(2-), which are important intermediates in carborane chemistry. The study represents the first examples of a stable, discrete C(H)-deprotonated carborane anion and a discrete molecular dicarbanion, respectively. These findings contribute to the understanding of carbon vertex chemistry in carborane clusters.
