Article
Chemistry, Multidisciplinary
Xin Zhang, Liu Leo Liu
Summary: In this study, a novel free N-aluminylene, carbazolylaluminylene 2b, was synthesized and characterized. The coordination behavior of 2b towards transition metal centers was investigated, revealing diverse coordination modes and the ability to modulate electronic properties without changing coordinated atoms. Furthermore, an unprecedented aluminylene-alumanyl transformation was observed, leading to the formation of a rare terminal Cu-alumanyl complex 8. The electronic structures of these complexes and the mechanism of transformation were studied through density functional theory calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Paul Rathke, Jonathan Rittle
Summary: This report describes the synthesis of a chromium alkyne complex supported by a bidentate phosphinimide ligand. This compound features an unprecedented extent of alkyne activation, exposure of which to an azobenzene derivative leads to a rare 4-electron oxidative addition of an N=N double bond across a single chromium center.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Multidisciplinary
Miguel A. Gonzalvez, Chuyi Su, Craig M. Williams, Paul Bernhardt
Summary: Organocopper(i) complexes are commonly used in chemical synthesis, while organocopper(ii) complexes are rare. A new method to generate organocopper(ii) species using electrochemistry was discovered, which showed high reactivity towards functionalized alkenes under catalytic control. The organocopper(ii) complexes act as a source of masked radicals, reacting with alkenes to form gamma-halonitriles via atom transfer radical addition (ATRA) with good yields. This electrochemical method allows for continuous regeneration of the organocopper(ii) complexes, with low copper loadings and the potential for catalyst recovery.
Article
Chemistry, Multidisciplinary
Suhong Kim, Pan-Pan Chen, K. N. Houk, Robert R. Knowles
Summary: This study presents a case of catalytic carbon-carbon sigma-bond homolysis achieved through coordination-induced bond-weakening effect, with a ruthenium redox couple used for bond weakening. Experimental and computational analysis revealed the stereospecificity of the isomerization reaction and quantified the bond-weakening effect through transition state analysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Chen Fei, Tao Sheng, Li Ning, Dai Bin
Summary: In this study, a type of CNN-type binuclear Cu(I) complexes was used for the direct carboxylation of terminal alkynes under room temperature and atmospheric CO2 conditions. The method showed high yields and a broad range of substrates. It was also successfully applied to hetero arenes carboxylation, with Cs2CO3 promoting hydrogen removal and Cu(I) complexes playing a key role in the activation of terminal alkynes.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Harrison J. Barnett, Anthony F. Hill
Summary: The linear mu-carbido complex reacts with a benzyne equivalent to form a new organometallic compound where the benzyne moiety adds across one of the metal-carbon double bonds.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Mahendra K. Sharma, Christoph Wolper, Stephan Schulz
Summary: Gallaphosphene reacts with polar X-H bonds at ambient temperature, showing selective 1,2 addition at the polar Ga-P double bond. The resulting complexes were characterized using IR and NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander S. S. Budnikov, Igor B. B. Krylov, Ivan E. E. Ushakov, Irina R. R. Subbotina, Fedor K. K. Monin, Gennady I. I. Nikishin, Nikolay N. N. Efimov, Dmitry E. E. Gorbunov, Nina P. P. Gritsan, Evgeny V. V. Tretyakov, Bing Yu, Alexander O. O. Terent'ev
Summary: In this study, the spatial structure of the oxime radical was determined for the first time by stabilizing the diacetyliminoxyl radical in the form of its complex with copper hexafluoroacetylacetonate and conducting X-ray diffraction analysis. It was discovered that the oxime radical can be used as a key building block in the design of molecular magnetic materials, exhibiting both weak ferromagnetic and antiferromagnetic interactions. This finding has significant implications for the field of molecular magnet design.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yue Pang, Markus Leutzsch, Nils Noethling, Felix Katzenburg, Josep Cornella
Summary: The study reports a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, involving a Bi(I)/Bi(III) redox cycle with C(sp(2))-F oxidative addition, F/H ligand metathesis, and C(sp(2))-H reductive elimination steps. Spectroscopic evidence supports the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to regenerate the propagating Phebox-Bi(I). This protocol highlights a unique catalytic example of a main-group center performing three elementary organometallic steps in a low-valent redox manifold.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Ming Wang, Fei-Ying You, Min Gao, Zhi-Ying Chen, Lan-Ye Chu, Lian-Rui Hu, Jun Zhu, Jia-Bi Ma
Summary: This study reports the activation and coupling of N2 and O2 under thermochemical conditions at room temperature. The researchers found that Y2BO+ can react with one N2 and two O2 molecules, and detailed mechanistic studies were conducted using mass spectrometry and quantum chemical calculations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Organic
Shuling Yu, Chao Hong, Zhanxiang Liu, Yuhong Zhang
Summary: In this study, the efficient synthesis of pyranones was achieved through a three-component cascade reaction under ruthenium catalysis using readily available acrylic acids, ethyl glyoxylate, and p-toluenesulfonamide. For the first time, the nucleophilic addition of the vinylic C-H bond of acrylic acids across aldehyde was achieved, followed by intramolecular cyclization and subsequent second insertion to aldehyde to form substituted butenolides. The sulfonamides were eliminated at higher temperature to yield the pyranones.
Article
Chemistry, Inorganic & Nuclear
Yang Li, Chunming Cui
Summary: A new strategy for incorporating a second type of Si atom into silicon cubanes has been developed. The strategy involves the use of a tricyclic hexasilane dianion [Ar6Si6]2- as a starting material. By treating the dianion with Ar ' SiCl3 and subsequently with KC8, new types of octasilacubanes Ar6Ar ' 2Si8 [Ar ' = 2,4,6-iPr2C6H2 (3a), 2-Ph2PC6H4 (3b)] were synthesized in high yields. Remarkably, the reaction of cubane 3b with two phosphine groups with 2 equiv of CuCl in CH2Cl2 resulted in the selective oxidative addition of the newly formed Si-Si bond, leading to the formation of a bis(silyl)copper complex. Single-crystal X-ray analysis revealed the presence of a unique square-planar, four-coordinate Cu cation paired with the [CuCl2]- counteranion.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Lewis R. Thomas-Hargreaves, Sudip Pan, Sergei I. Ivlev, Gernot Frenking, Magnus R. Buchner
Summary: Through a combined experimental and theoretical approach, it was shown that unusually high Be-C bond strength in carbene adducts to beryllium compounds can be rationalized by a Be(II) -> N-heterocyclic carbene (NHC) pi back-donation mechanism. This understanding was achieved through energy decomposition analysis and quantum theory of atoms-in-molecules analysis, shedding light on the bonding situation in these complexes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Pablo Rios, Rocio Martin-de la Calle, Pietro Vidossich, Francisco Jose Fernandez-de-Cordova, Agusti Lledos, Salvador Conejero
Summary: A reversible carbon-boron bond formation has been observed in the reaction between a coordinatively unsaturated Pt(ii) complex and tricoordinated boranes, leading to the formation of several intermediate complexes. Computational methods suggest that the kinetic formation of carbon-boron coupling products is under kinetic control, while the platinum boryl species resulting from competitive C-H bond coupling are thermodynamically more stable. These findings provide valuable insights into productive carbon-boron coupling reactions at transition metal centers.
Article
Chemistry, Multidisciplinary
Sylvain G. Dutremez, Xavier Dumail, Sonia Mallet-Ladeira, Arie van der Lee, Dominique Granier, Nathalie Masquelez, Jean-Sebastien Filhol
Summary: Molecular crystals have been prepared from pentafluorophenylphosphonic acid, incorporating ammonium cations, water molecules, or hydronium ions that act as adhesive agents. They interact via hydrogen bonds and contacts with polar components, resulting in a 2D layered arrangement. The use of perfluoroaryl groups is central in increasing cohesion of nonpolar regions.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Physical
Maxime Boudjelel, Omar Sadek, Sonia Mallet-Ladeira, Yago Garcia-Rodeja, E. Daiann Sosa Carrizo, Karinne Miqueu, Ghenwa Bouhadir, Didier Bourissou
Summary: In this work, Pd complexes derived from ambiphilic ligands were found to preferentially activate acyl chlorides over other functional groups, enabling efficient catalysis in Stille and Negishi couplings. This provides a simple and effective method to selectively form C(=O)-C bonds and access functionalized ketones. Key Pd complexes have been authenticated and reaction profiles analyzed using density functional theory (DFT) calculations to gain insight into their role and influence in the process.
Article
Biochemistry & Molecular Biology
Quentin Vanbellingen, Paul Servin, Anais Coinaud, Sonia Mallet-Ladeira, Regis Laurent, Anne-Marie Caminade
Summary: Pyridine, pyridine imine, and bipyridine imine ligands functionalized with phenol have been synthesized and characterized for their catalytic applications. The grafting of these ligands onto the surface of phosphorhydrazone dendrimers has shown improved complexation ability towards palladium(II), leading to enhanced catalytic efficiency in Heck couplings and Sonogashira couplings. In some cases, a positive dendritic effect has been observed, with catalytic efficiency increasing proportionally with dendrimer generation.
Article
Biochemistry & Molecular Biology
Leonie Berthonnaud, Charlene Esmieu, Sonia Mallet-Ladeira, Christelle Hureau
Summary: The study utilized Cu(II) complex L to detect sulfite and thiosulfate ions in food. The formation of the complexes was monitored using various methods and the solid-state structures were determined. The stability and binding affinity of the complexes were also evaluated.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jessica Rodriguez, Marte Sofie Martinsen Holmsen, Yago Garcia-Rodeja, E. Daiann Sosa Carrizo, Pierre Lavedan, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou
Summary: Pi-allyl complexes play a crucial role in organometallic chemistry, particularly the pi-allyl Pd(II) complexes, and have been a subject of significant interest. Recent studies have shown the reactivity of (P,C)-cyclometalated Au(III) pi-allyl complexes towards beta-diketo enolates, leading to the formation of allylation products through a complex mechanistic pathway. The regioselectivity of nucleophilic attack and C-C coupling in these reactions have been thoroughly investigated, shedding light on the reaction progress and evolution of various gold complexes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Omar Sadek, Arnaud Le Gac, Nereida Hidalgo, Sonia Mallet-Ladeira, Karinne Miqueu, Ghenwa Bouhadir, Didier Bourissou
Summary: A new method has been developed for the synthesis of phosphine-boranes, featuring simplicity, efficiency, and broad substrate scope. The key intermediates were identified as P-stabilized borenium cations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jessica Rodriguez, David Vesseur, Alexis Tabey, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou
Summary: A (MeDalphos)AuCI complex has been discovered to efficiently catalyze the cross-coupling reaction of indoles and allyl acetates/alcohols. The reaction tolerates various functional groups and selectively produces branched C3-allylated products. It utilizes the hemilabile character of the P<^>N ligand.
Article
Chemistry, Multidisciplinary
Yael Juarez-Martinez, Pablo Labra-Vazquez, Alejandro Enriquez-Cabrera, Andres F. Leon-Rojas, Diego Martinez-Bourget, Pascal G. Lacroix, Marine Tasse, Sonia Mallet-Ladeira, Norberto Farfan, Rosa Santillan, Gabriel Ramos-Ortiz, Jean-Pierre Malval, Isabelle Malfant
Summary: This study presents four ruthenium nitrosyl (RuNO) complexes, which have well-characterized crystal structures and spectroscopic features. These complexes show high molecular cross-sections in two-photon absorption and are capable of releasing NO center dot under irradiation, making them promising for drug delivery based on two-photon absorption.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Fatima Zohra Chiboub Fellah, Carine Duhayon, Sonia Mallet-Ladeira, Laure Vendier, Jean-Pierre Costes
Summary: This study confirms the challenge of preparing main ligands that can coordinate 3d and 4f ions and introduce asymmetric centers near Ln ions. Despite difficulties in complexation with LnIII ions, an original reaction pathway was utilized to generate tetranuclear complexes with ferromagnetic Cu-Ln interactions.
Article
Chemistry, Physical
Taline Kerackian, Didier Bouyssi, Guillaume Pilet, Maurice Medebielle, Nuno Monteiro, Julien C. Vantourout, Abderrahmane Amgoune
Summary: This article describes the development and in-depth study of a cross-electrophile coupling of alkyl N-acyl imides with alkyl halides using nickel catalysis and electrochemistry. The method utilizes the stability and easy access of N-acyl imides to selectively synthesize dissymmetric dialkyl ketones. Mechanistic studies reveal the generation of alkyl radicals through single-electron oxidation of alkyl bromides by electrogenerated (bpy)Ni(I) species. The reaction of alkyl N-acyl imides with (bpy)Ni(0) and (bpy)Ni(I) species leads to Ni(II) acyl intermediates. A comprehensive mechanistic picture of this selective cross-electrophile coupling is achieved through these investigations.
Article
Crystallography
Isabelle Sasaki, Sonia Mallet-Ladeira
Summary: The crystal structures of two platinum complexes have been determined by X-ray diffraction. Both complexes crystallize in the monoclinic space group C2/c and have similar unit cell dimensions.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2023)
Article
Chemistry, Multidisciplinary
Tingjun Hu, Mohammad Jaber, Gael Tran, Didier Bouyssi, Nuno Monteiro, Abderrahmane Amgoune
Summary: We have developed a nickel hydride-catalyzed methodology that can selectively convert internal alkynes to E- or Z-alkenes under mild conditions. The process involves a dual nickel/photoredox catalytic system and triethylamine, which acts as both a sacrificial reductant and a source of hydrogen atoms. Mechanistic studies reveal that the control of the stereoselectivity is determined by a final protonolysis step that can be tuned by adjusting the pKa of an alcohol additive.
CHEMISTRY-A EUROPEAN JOURNAL
(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, Multidisciplinary
Gyorgy Szaloki, Julien Babinot, Vlad Martin-Diaconescu, Sonia Mallet-Ladeira, Yago Garcia-Rodeja, Karinne Miqueu, Didier Bourissou
Summary: Chelating P<^>P and hemilabile P<^>N ligands were found to oxidize Au(i) complexes by o-benzoquinones. The resulting Au(iii) catecholate complexes were characterized and the reversibility of the transformation was confirmed. DFT calculations provided insights into the structure and stability of the Au(i) o-quinone and Au(iii) catecholate forms.
Article
Crystallography
Layachi Merabet, Marine Tasse, Sonia Mallet-Ladeira, Lakhemici Kaboub, Isabelle Malfant
Summary: In the title compound, the two pyridine side arms are not coplanar, and the crystal packing is characterized by hydrogen bonds, intermolecular interactions, and pi-pi interactions.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2021)