Article
Chemistry, Inorganic & Nuclear
Yuto Seo, Wahyu S. Putro, Miftah Faried, Vladimir Ya Lee, Tomoteru Mizusaki, Yukio Takagi, Yoong-Kee Choe, Kazuhiro Matsumoto, Jun-Chul Choi, Norihisa Fukaya
Summary: A series of R3Si-NHC-Pd complexes were successfully tested as pre-catalysts for the Suzuki-Miyaura cross-coupling reaction, showing good-to-excellent yields. The experiment highlighted the crucial role of the preliminary pre-catalyst activation step, which was facilitated by the electron-donating trialkylsilyl groups on the NHC ligands.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Junhao Li, Nan Zheng, Xuelun Duan, Rui Li, Wangze Song
Summary: A Pd-catalyzed C-glycosylation reaction was developed using Achmatowicz rearrangement products as donors and methylcoumarins as acceptors under mild conditions, featuring stereodivergent synthesis of C-glycosides with control over stereodiversity in donors and fluorescent performance in acceptors.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xibing Zhou, Guoying Zhang, Renbin Huang, Hanmin Huang
Summary: The study presents an efficient strategy utilizing H-2 as the sole reductant for a palladium-catalyzed allyl-allyl reductive coupling reaction, allowing for smooth synthesis of organic compounds._DYNAMIC_LATEST_VERSION
Article
Chemistry, Multidisciplinary
Ross F. Koby, Alicia M. Doerr, Nicholas R. Rightmire, Nathan D. Schley, William W. Brennessel, Brian K. Long, Timothy P. Hanusa
Summary: In mechanochemically driven synthesis without solvents, high-energy, non-stoichiometric products can be generated, such as a non-stoichiometric calciate formed by ball milling reagents with calcium. This compound rearranges in arenes to form a coordination polymer, and rearranges much faster in alkanes. The structures have been modeled with DFT calculations, and one of them initiates the anionic polymerization of methyl methacrylate and isoprene under mild conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Siou-Wei Liang, Yingjie Guo, Wan-Ching Lee, Pin-Rui Zeng, Tzu-Hao Lin, Pei-Zhen Xie, Hsuan-Hao Kang, I-Chung Lu, Yu-Chang Chang
Summary: Two newly designed Pd(II) precatalysts were synthesized and used to efficiently convert unreactive aryl chlorides, benzyl chlorides, and benzoyl chlorides. The deprotonation of the precatalysts led to the dissociation of NHC, and the proposed Pd(II) species could be reduced to Pd(0) using ethoxide. The size of salt additive cations and the basicity of the base were found to influence the catalytic properties.
Article
Chemistry, Physical
Yanhong Liu, Aili Feng, Rongxiu Zhu, Chengbu Liu, Dongju Zhang
Summary: Density functional theory (DFT) calculations were performed to investigate the mechanism of copper-catalyzed four-component borocarbonylative coupling of alkenes with alkyl halides using bis(pinacolato)diboron as the boron reagent under CO atmosphere. The theoretical results revealed an unexpected reaction mechanism involving CuI as the sole catalyst, with a two-ligand relay mechanism and no radical participation, proceeding through SN2-type C-C coupling. The experimental observations of regio- and chemoselectivities, as well as the inhibition of the reaction by radical trapping reagents, were rationalized by the theoretical analysis.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Applied
Xavier Marset, Marti Recort-Fornals, Malkaye Kpante, Adam Zielinski, Christopher Golz, Lawrence M. Wolf, Manuel Alcarazo
Summary: A series of strong it-acceptor polyfluorinated and dicationic chelating phosphines were synthesized and evaluated in the Rh-catalysed dimerization of norbornadiene, leading to the selective formation of specific products and site-selective arylation reactions. Theoretical calculations were performed to understand the origin of the observed regioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
George Dhimba, Alfred Muller, Koop Lammertsma
Summary: This study investigates the mechanisms of ligand rearrangement in octahedral chiral-at-metal complexes. The lowest energy cis isomer and its interconversion with other isomers are calculated. The connectivity of all enantiomeric minima and transition structures is summarized, and the influence of N-substitution on the favored pathway is evaluated.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
David S. Casadio, Santeri Aikonen, Anna Lenarda, Martin Nieger, Tao Hu, Stefan Taubert, Dage Sundholm, Mikko Muuronen, Tom Wirtanen, Juho Helaja
Summary: The study demonstrates that oxidative dehydrogenative couplings of benzo[b]fused heteroaryl 2,2'-dimers to chiral 3,3'-coupled cyclooctatetraenes or carbazole-type migrative products can be catalyzed by mildly thermal air or HNO3 oxidized activated carbons. DFT calculations reveal that radical cation and Scholl-type arenium cation mechanisms result in different products, corresponding to experimental product distributions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Ningjing Luo, Zhufeng Hou, Guo-Liang Chai
Summary: This study systematically explores the catalytic activity of tungsten monocarbide (WC) by studying the methane dehydrogenation and C-C coupling processes on WC surfaces using density functional theory (DFT) calculations. The results indicate that the W-terminated WC(0001) surface is the most favorable exposed surface with a lower surface energy. Additionally, the Co(111), Ni(111), and W-terminated WC(0001) surfaces exhibit similar catalytic properties in methane dehydrogenation, and the rate-limiting step on the W-terminated WC(0001) surface is the dissociation of CH*. C-C coupling through CH* intermediates on the W-terminated WC(0001) surface favors the formation of C2H2 kinetically.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
Dan Song, Jing Chen, Rui Wang, Zhenguo Guo, Jianhui Xie, Yingying Liu
Summary: In this study, the water oxidation of Ru WOCs with different substituents on the ligands was investigated. The proposed water oxidation mechanism involves the bimolecular coupling of two seven-coordinate Ru=O species. The use of bulky phenyl groups helps stabilize the high oxidation Ru-oxo intermediates.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Vivek Gupta, Sadhana Singh, Sharad Kumar Sachan, BrijKishor Maurya, Subhamoy Char, Dasari L. V. K. Prasad, Ganapathi Anantharaman
Summary: This study investigates the reaction properties and products of acyclic palladium amidine chloride under different conditions. It is found that cyclic six-membered (triazapentadiene)palladium complexes can be obtained by reacting palladium complexes or formamidinium salts with acetonitrile, but different products are obtained with acetonitrile or acrylonitrile.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Robin Sievers, Malte Sellin, Susanne M. Rupf, Joshua Parche, Moritz Malischewski
Summary: This study successfully synthesized the fluorocarbon-soluble complex [Rh(COD)(C-5(CF3)(5))] through salt metathesis, demonstrating for the first time the coordination ability of the weakly basic [C-5(CF3)(5)](-) ligand. The byproduct [Rh(COD)(C-5(CF3)(4)H)] was also isolated and characterized. DFT studies showed that the interaction energy between the [C-5(CF3)(5)](-) ligand and the 12-electron fragment [Rh(COD)](+) is significantly lower compared to [C-5(CH3)(5)](-), indicating reduced electrostatic interactions and weaker pi-donor properties of the [C-5(CF3)(5)](-) ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Stavroula I. Sampani, Victor Zdorichenko, Jack Devonport, Gioia Rossini, Matthew C. Leech, Kevin Lam, Brian Cox, Alaa Abdul-Sada, Alfredo Vargas, George E. Kostakis
Summary: The introduction of a new hybrid bidentate ligand into 3d transition metal catalysis enables the synthesis of a wide range of propargylamines at room temperature in the absence of additives. Experimental and theoretical calculations reveal the mechanism behind this process, involving exclusive trans coordination at Cu and modulation of charge distribution and flux by different nitrogen atoms in the ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
George Dhimba, Alfred Muller, Koop Lammertsma
Summary: Cis-MoO2(nacnac)(2) (nacnac = β-diketiminate) can act as a viable chiral-at-metal catalyst when its two β-diketiminate ligands are N-substituted to prevent racemization. The introduction of simple methyl groups significantly increases the barriers for racemization in various twists, with the lowest energy barrier reaching ΔG(o)=27.4 kcal/mol when N-substituted t-butyl groups are used. The electronic and steric components of the nacnac ligands in relation to racemization barriers are discussed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
A. Wolpers, F. Baffie, L. Verrieux, L. Perrin, V Monteil, F. D'Agosto
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Physical
Ludmilla Verrieux, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Christophe Boisson, Marie-Noelle Poradowski, Lionel Perrin
Article
Chemistry, Inorganic & Nuclear
Alexis D. Oswald, Aymane El Bouhali, Emmanuel Chefdeville, Pierre-Alain R. Breuil, Helene Olivier-Bourbigou, Julien Thuilliez, Florent Vaultier, Aimery De Mallmann, Mostafa Taoufik, Lionel Perrin, Christophe Boisson
Summary: Yttrium monocationic complexes with various bis-alkyl and bis-allyl ligands were synthesized and characterized. The complexes showed high activity for ethylene polymerization and full conversion of isoprene. The resulting polymers exhibited a bimodal distribution in molar mass, with polyisoprene mainly consisting of cis-1,4 units.
Article
Chemistry, Multidisciplinary
Florian Baffie, Georgios Patias, Ataulla Shegiwal, Fabrice Brunel, Vincent Monteil, Ludmilla Verrieux, Lionel Perrin, David M. Haddleton, Franck D'Agosto
Summary: Two scalable polymerisation methods have been combined to synthesize ethylene and methacrylate block copolymers. Kinetic measurements and analyses suggest that MMA(n) is involved in a degradative chain transfer process, resulting in the formation of (MMA)(n)-b-PE block copolymers. Molecular modeling and studies on the effect of MMA(n) molar mass and composition were also conducted to support the overall reactivity scheme.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Haosheng Liang, Jordan Rio, Lionel Perrin, Pierre-Adrien Payard
Summary: Halide salts facilitate the oxidative addition of organichalides to Pd(0) through a combination of anionic, cationic, and Pd-Pd cooperative effects. Chlorides promote phosphine release, leading to a mixture of mononuclear and dinuclear Pd(0) complexes. Anionic Pd(0) dinuclear complexes exhibit cooperativity between Pd(0) centers, favoring the oxidative addition of iodobenzene.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexis D. Oswald, Ludmilla Verrieux, Pierre-Alain R. . Breuil, Helene Olivier-Bourbigou, Julien Thuilliez, Florent Vaultier, Mostafa Taoufik, Lionel Perrin, Christophe Boisson
Summary: A yttrium complex was synthesized and evaluated for its reactivity and selectivity in isoprene polymerization. Both experimental and computational investigations identified the mechanism and stable heterobimetallic complexes formed.
Article
Chemistry, Organic
Jordan Rio, Lionel Perrin, Pierre-Adrien Payard
Summary: The main parameters influencing the structure-reactivity relationship of organozinc and organozincate reagents are summarized in this perspective article. The influences of substituents, inorganic salts, and solvents are discussed and exemplified with literature examples. Molecular modeling considerations are introduced to enhance the understanding at the molecular scale of the structure-activity relationships of these reagents in solution.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ming-Yu Chen, Sylvain Charvet, Pierre-Adrien Payard, Marie-Eve L. Perrin, Julien C. Vantourout
Summary: A robust electrochemically driven nickel-catalyzed halogen exchange reaction has been reported, allowing the conversion of heavy halogens or polar atoms to lighter and more lipophilic chloride groups to modify properties or block undesired reactivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Renhe Tang, Julien Petit, Yi Yang, Achim Link, Florian Bachle, Marie-Eve L. Perrin, Abderrahmane Amgoune, Anis Tlili
Summary: The nickel-catalyzed trifluoromethylselenolation of aryl and vinyl triflates has been studied in this research, including the development of synthesis methods and understanding the reaction mechanism. The Xantphos/Ni(COD)(2) catalytic system is found to be efficient in synthesizing aryl and vinyl trifluoromethylselenides, and the key steps of the catalytic cycle have been investigated through experimental and computational mechanistic studies. The results support a Ni-0/Ni-II process.
Article
Chemistry, Physical
Jordan Rio, Haosheng Liang, Marie-Eve L. Perrin, Luca A. A. Perego, Laurence Grimaud, Pierre-Adrien Payard
Summary: This perspective presents a summary of selected mechanistic studies of the Pd(0)-to-Pd(II) oxidative addition process involving organic halides and pseudohalides, with a focus on systems relevant to catalytic reactions. The results are classified and described according to the nature of supporting ligands, highlighting general trends and the most relevant examples. The survey includes the formation of active species from precatalysts and the influence of different species present under catalytic conditions on the oxidative addition process, providing guidelines for improving the understanding and efficiency of catalytic reactions.
Article
Chemistry, Organic
Jordan Francois, Jordan Rio, Erwann Jeanneau, Marie-Eve L. Perrin, Maiwenn Jacolot, Pierre-Adrien Payard, Florence Popowycz
Summary: Taking advantage of our preliminary observations, we successfully achieved the direct C-C borrowing hydrogen functionalization on isosorbide using an Ir-based organometallic homogeneous catalyst with excellent diastereocontrol. The reaction involves a catalytic dehydrogenation, in situ aldol condensation/crotonisation, and a catalytic dehydrogenation to yield the desired homologated product. Through a computational mechanistic investigation, we elucidated the stereoelectronic effects and the roles of the Na counter-cation in guiding the hydride addition and coordinating the substrate's oxygen atoms, thus rationalizing the experimental selectivity at the molecular level.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Gaetano Angelici, Nicholus Bhattacharjee, Maxime Pypec, Laurent Jouffret, Claude Didierjean, Franck Jolibois, Lionel Perrin, Olivier Roy, Claude Taillefumier
Summary: The synthesis and conformational study of N-substituted beta-alanines with tert-butyl side chains are described in this article. Experimental solution NMR spectroscopy, X-ray crystallography, and molecular modeling were used to investigate the conformational preferences of these compounds. It was found that despite their higher flexibility, they still adopt preferred secondary structures including helical and ribbon-like conformations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Joshua Heck, Fabian Metz, Soeren Buchenau, Melissa Teubner, Benjamin Grimm-Lebsanft, Thomas P. Spaniol, Alexander Hoffmann, Michael A. Ruebhausen, Sonja Herres-Pawlis
Summary: Copper guanidine quinolinyl complexes with distorted structures are good models for the entatic state, leading to high similarity between Cu(i) and Cu(ii) complexes. In this study, guanidine quinolinyl ligands with different substituents were synthesized to examine their influence on the electron transfer properties of the corresponding copper complexes. Experimental and theoretical methods were applied to study the effects of substituents on the properties of the complexes.
Article
Polymer Science
Nicolas Baulu, Marie-Noelle Poradowski, Ludmilla Verrieux, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Lionel Perrin, Franck D'Agosto, Christophe Boisson
Summary: Two divalent bis-metalated chain transfer agents were designed, synthesized, and applied in the polymerization reaction. Their coordination chain transfer (co)polymerization features and initiation mechanism were studied, and the intermediates formed in the reaction were investigated theoretically using computational chemistry methods.
Article
Chemistry, Physical
Nicholus Bhattacharjee, Lionel Perrin, Franck Jolibois
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2020)
