Article
Chemistry, Multidisciplinary
Soukaina Bennaamane, Maria F. Espada, Andrea Mulas, Theo Personeni, Nathalie Saffon-Merceron, Marie Fustier-Boutignon, Christophe Bucher, Nicolas Mezailles
Summary: The catalytic formation of borylamines from atmospheric N2 was achieved for the first time using a series of homogeneous (triphosphine)Mo complexes. Stepwise functionalization of the (triphosphine)Mo-nitrido complex with chloroborane led to the synthesis of the imido complex. Electrochemical characterization revealed that the (PPP)Mo-borylimido complexes are more easily reduced than the (PPP)Mo-nitrido complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
John J. Kiernicki, Matthias Zeller, Nathaniel K. Szymczak
Summary: A series of zerovalent iron complexes containing allylic substituents attached to a 2,6-bis(imidazol-2-ylidene)pyridine pincer ligand were synthesized to study the requirements and limitations of late-stage hydroboration. Complicating factors arising from complexes containing labile M-L bonds were identified and discussed.
Article
Chemistry, Multidisciplinary
Hannah K. Wagner, Hubert Wadepohl, Joachim Ballmann
Summary: A new [PCCP]-coordinated molybdenum platform was used for the cleavage of molecular dinitrogen, leading to the formation of N-functionalized imido complexes. The study also revealed that, contrary to common belief, the strong N equivalent to N bond could be cleaved in the presence of a weaker, spatially constrained C equivalent to C bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Justin C. Wedal, Jeffrey M. Barlow, Joseph W. Ziller, Jenny Y. Yang, William J. Evans
Summary: Electrochemical measurements were conducted on tris(cyclopentadienyl)thorium and uranium compounds in different oxidation states with various ligands. The reduction potentials of uranium and thorium complexes were found to correlate with the electron donating abilities of the cyclopentadienyl ligand. Isolated Th(ii) complexes showed surprising similarity in their redox behavior with Th(iii)/Th(ii) and Th(iv)/Th(iii) couples in Cp ''-ligated complexes, indicating the possibility of preparing Th(ii) complexes from Th(iv) precursors.
Article
Chemistry, Physical
Diep T. H. Nguyen, Marilyne Belanger-Bouliga, Lorianne R. Shultz, Arunava Maity, Titel Jurca, Ali Nazemi
Summary: Gold nanomaterials have been traditionally stabilized and functionalized by sulfur-containing ligands, but there is recent interest in using N-Heterocyclic carbenes (NHCs) as alternative stabilizers. This study introduces polymeric mesoionic NHC-Au(I) complexes as precursors to stable AuNPs, which demonstrate exceptional stability against harsh conditions and high concentrations of glutathione in aqueous media. Furthermore, the use of macromolecular substrates leads to the formation of larger AuNPs with enhanced stabilities, showing promise for applications in nanomedicine.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Organic
Rui-jun Peng, Yuan Chen, Xue-jing Zhang, Ming Yan
Summary: A Rh(iii)-catalyzed ortho C-H migratory insertion of N-nitrosoanilines with naphthoquinone carbenes has been developed, yielding the desired products in good yields under mild reaction conditions. Diverse elaborations of the products were also explored, making this method valuable for the synthesis of biarylamines and their derivatives.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Yongtao Tan, Yuling Zhu, Haibo Li
Summary: The Mo2N nanoparticles embedded in N, O co-doped carbon sheets composite (Mo2NNPs/NOCS) is a promising electrode material for supercapacitors. These nanoparticles are fabricated by in-situ growth on the surface of self-sacrifice C3N4. The optimized material shows a maximum specific capacitance of 294 F g-1 at 0.5 A g-1. Moreover, when assembled with a commercial activated carbon YP50 as a positive electrode, the supercapacitor device achieves a high energy density of 13.6 Wh kg-1 in an acid electrolyte.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Chemistry, Multidisciplinary
Yanyang He, Yanzhao Yin, Chenwei Liu, Xiao-Feng Wu, Zhiping Yin
Summary: An efficient and sustainable intramolecular electrochemical cyclization method was reported for the synthesis of various halogenated oxazolines, using lithium halogen salts as redox media and halogen sources in an undivided cell. A wide range of oxazolines, including five- and six-membered heterocycles, and iodo-, bromo-, and chloro-methyl oxazolines were constructed in moderate to good yields at room temperature. Notably, this electrochemical oxidative cyclization obviates the use of external oxidants.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Dan-Dan Zhai, Shuo-Qing Zhang, Si-Jun Xie, Rong-Kai Wu, Feng Liu, Zhen-Feng Xi, Xin Hong, Zhang-Jie Shi
Summary: This study presents a novel method for N-2 splitting using (n-Bu)(4)NBr as a catalyst to facilitate the process on a Mo(III) platform. Experimental and theoretical investigations suggest that X- anions play a crucial role in inducing the catalysis at the early stage, leading to the generation of a catalytically active species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Bin Wang, Hongyuan Ren, Hou-Ji Cao, Changsheng Lu, Hong Yan
Summary: Efficient transformation of nitroaromatics into N-heterocycles has been achieved using a photoexcited nitro-induced strategy. The metal- and photocatalyst-free reaction proceeds through intramolecular redox C-N coupling and has been demonstrated to have broad substrate scope, high yields, and wide applications.
Article
Chemistry, Multidisciplinary
Diep Thi Hong Nguyen, Lorianne R. Shultz, Titel Jurca, Ali Nazemi
Summary: N-heterocyclic carbenes (NHCs) have gained attention for stabilizing metallic nanoparticles, particularly gold nanoparticles, but the stability of silver nanoparticles (AgNPs) with NHCs has been overlooked. This study reports the synthesis of monomeric and polymeric NHC-Ag(I) complexes as precursors to NHC-tethered AgNPs. The stability of these NHC-functionalized AgNPs was investigated and their application in catalysis was demonstrated.
Article
Chemistry, Multidisciplinary
Sara Sabater, David Schmidt, Heidi (nee Schneider) Schmidt, Maximilian W. Kuntze-Fechner, Thomas Zell, Connie J. Isaac, Nasir A. Rajabi, Harry Grieve, William J. M. Blackaby, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Udo Radius, Michael K. Whittlesey
Summary: Addition of various phosphines to two-coordinate nickel species leads to a series of terminal phosphido nickel complexes with unique geometries. Smaller NHCs and phosphines facilitate the formation of bis-phosphido complexes, while DFT calculations show that P-P activation can be achieved through unconventional phosphine adducts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Siripurapu Mounika, Valle Krishnaveni, Marilyn Esclance Dmello, Suresh Babu Kalidindi
Summary: In recent years, amine boranes, particularly ammonia borane, have been under the spotlight as potential candidates for on-board hydrogen storage. Chemists have been working on developing effective catalysts for hydrogen release from ammonia borane, leading to the discovery of new and interesting chemistry of ammonia borane. This has expanded the potential applications of ammonia borane beyond hydrogen storage, such as in nanoparticle synthesis, transfer hydrogenation, and organic synthesis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jiapeng Gao, Zipeng Xing, Meijie Liu, Yichao Wang, Na Zhang, Zhenzi Li, Peng Chen, Wei Zhou
Summary: Na-doped g-C3N4/NiO 2D/2D laminated p-n heterojunction nanosheets were fabricated, which showed high photocatalytic activity and hydrogen production rate due to the high specific surface area, surface reactivity, and enhanced charge separation and transport.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Analytical
Nathaniel L. Dominique, Shelby L. Strausser, Jacob E. Olson, William C. Boggess, David M. Jenkins, Jon P. Camden
Summary: This study investigates the stability and potential biological applications of N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on gold surfaces, while utilizing laser desorption ionization mass spectrometry (LDI-MS) to explore the surface chemistry of NHC. By studying NHC-functionalized gold nanoparticles using LDI-MS, insights into the packing of NHC monolayers on gold surfaces and the stability of NHC ligands post-ligation were gained. The ability of LDI-MS to probe postsynthetic modifications of anchored NHCs, such as the reduction of nitro-NHC-AuNPs to amine-NHC-AuNPs, highlights its importance for current and future applications of NHC surfaces.
ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jinyi Song, Qian Liao, Xin Hong, Li Jin, Nicolas Mezailles
Summary: The study presents a new method for the direct synthesis of nitriles from N-2 through a nitrile-alkyne cross-metathesis process, offering a novel strategy for N-2 fixation chemistry. Experimental and theoretical calculations revealed the crucial role of the oxidation state of the molybdenum center in this process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Leo Angele, Sebastien Dreyfuss, Benoit Dubertret, Nicolas Mezailles
Summary: The role of indium carboxylate precursors in synthesizing monodisperse InP quantum dots was explored. The presence of carboxylic acid affected the reaction kinetics and optical properties of the InP QDs, leading to less controlled formation of nanocrystals. Luminescent quantum dots with a gradated ZnSeS shell were successfully obtained from the synthesized InP core.
INORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Irina Osadchuk, Nele Konrad, Khai-Nghi Truong, Kari Rissanen, Eric Clot, Riina Aav, Dzmitry Kananovich, Victor Borovkov
Summary: The complexation of BTI with bis(ZnOEP) forms a 1:2 host-guest complex, where BTI molecules coordinate to the zinc ions of the porphyrin subunits of the host. Experimental and computational results agree, and the CD spectrum is shown to be sensitive to the spatial arrangement of the porphyrin subunits.
Article
Chemistry, Multidisciplinary
Soukaina Bennaamane, Maria F. Espada, Andrea Mulas, Theo Personeni, Nathalie Saffon-Merceron, Marie Fustier-Boutignon, Christophe Bucher, Nicolas Mezailles
Summary: The catalytic formation of borylamines from atmospheric N2 was achieved for the first time using a series of homogeneous (triphosphine)Mo complexes. Stepwise functionalization of the (triphosphine)Mo-nitrido complex with chloroborane led to the synthesis of the imido complex. Electrochemical characterization revealed that the (PPP)Mo-borylimido complexes are more easily reduced than the (PPP)Mo-nitrido complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Luca Demonti, Nathalie Saffon-Merceron, Nicolas Mezailles, Noel Nebra
Summary: The role of silver as an additive or co-catalyst in cross-coupling reactions is often underestimated, despite its importance in oxidative trifluoromethylation of arenes. New evidence demonstrates the significance of Ag-I/Ag-III redox catalysis for achieving this transformation, showcasing the utility of organosilver(III) compounds in cross-coupling reactions. This work challenges previous misconceptions about the catalytic capabilities of silver in cross-coupling reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Irina Osadchuk, Riina Aav, Victor Borovkov, Eric Clot
Summary: In this study, the influence of various controlling factors on electronic circular dichroism (ECD) spectra was investigated by modeling sixteen different zinc porphyrins using DFT and TD-DFT approaches. The factors mainly affected the excitation energy of electronic transitions and their intensity.
Article
Chemistry, Inorganic & Nuclear
Ramaraj Ayyappan, Koushik Saha, Mary Grellier, Eric Clot, Laure Vendier, Sundargopal Ghosh, Sylviane Sabo-Etienne, Sebastien Bontemps
Summary: A series of anionic ruthenium pentahydride complexes with different structural features were synthesized and characterized using various techniques. X-ray diffraction provided snapshots of some isomeric structures, while NMR analysis showed these complexes exhibited highly dynamic behavior. The rapid H-D exchange between Ru-H and D-2 was attributed to Li-Ru interactions in the absence of crown-ether.
Review
Chemistry, Inorganic & Nuclear
Julien Petit, Lionel Magna, Nicolas Mezailles
Summary: This review focuses on the selective transformation of ethylene and alkenes, particularly the involvement of metallacyclopentane in the reaction mechanism, and covers studies on the synthesis of cyclobutane and butadiene derivatives. Studies deciphering the precise mechanism of the transformations through the synthesis of postulated intermediates, labelling experiments, and DFT calculations are also presented.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Soukaina Bennaamane, Barbara Rialland, Lhoussain Khrouz, Marie Fustier-Boutignon, Christophe Bucher, Eric Clot, Nicolas Mezailles
Summary: This article introduces a new method that uses boron-centered radicals to activate N-2 and convert it into NH3 under mild conditions. The mechanism and effectiveness of this method are demonstrated through experiments and calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Luca Demonti, Daniel Joven-Sancho, Noel Nebra
Summary: Ag-III compounds are strong oxidizers of difficult handling and their involvement in cross-coupling reactions has been frequently discarded. However, recent studies have shown the existence of organosilver(III) compounds and the possibility of cross-coupling reactions enabled by Ag-I/Ag-III redox cycles. This review summarizes the most relevant contributions in this field, focusing on aromatic fluorination/perfluoroalkylation and the identification of Ag-III key intermediates. Comparison between the activity of (AgRF)-R-III compounds and its (CuRF)-R-III and (AuRF)-R-III congeners in aryl-F and aryl-CF3 couplings is also discussed, providing a deeper understanding of the scope of these transformations and their associated pathways.
Article
Chemistry, Multidisciplinary
Anais Coffinet, David Specklin, Quentin Le De, Soukaina Bennaamane, Luna Munoz, Laure Vendier, Eric Clot, Nicolas Mezailles, Antoine Simonneau
Summary: Two different dinitrogen-derived molybdenum nitrido complexes with different geometries, ligand spheres, and oxidation states were found to bond with the strong Lewis acid B(C6F5)(3) through their N ligand. The stable adducts were then used for heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C6F5)(2) in a frustrated Lewis pair-type manner. The results showed successful Si-H bond activation and substitution of B(C6F5)(3) by HB(C6F5)(2), depending on the nature of the nitrido complex. No B-H bond splitting was observed. The computed thermodynamics by DFT were consistent with the experimental outcomes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Luca Demonti, Hana Tabikh, Nathalie Saffon-Merceron, Noel Nebra
Summary: The synthesis of Naumann's Ag-I/Ag-III mixed valence salt [Ag-I](+)[Ag-III(CF3)(4)](-) (Ag-1) is revisited and a safe and scalable method for its synthesis is reported. The use of Ag-1 to build novel Ag-I/Ag-III salts and the excellent catalytic activity of cationic Au-I catalysts prepared from (PPh3)AuCl and Ag-1 are demonstrated.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel Joven-Sancho, Luca Demonti, Antonio Martin, Nathalie Saffon-Merceron, Noel Nebra, Miguel Baya, Babil Menjon
Summary: Neutral Ag(iii) complexes with monodentate ligands have been confirmed in this study. The acidity of the metal center in square-planar (CF3)(3)Ag(L) compounds with Group 15 donor ligands enables additional ligand coordination without constraints.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Julien Petit, Anthony Cavaille, Nathalie Saffon-Merceron, Marie Fustier-Boutignon, Nicolas Mezailles
Summary: The reduction of a high spin paramagnetic complex by two electrons under N-2 resulted in the formation of two isomeric low spin diamagnetic complexes, which were successfully isolated and characterized. DFT calculations provided insights into the mechanism of double alpha,alpha CH bond insertion into a single sp(3) CH2 moiety. Fast exchange positions of hydrides in the cis dihydride complex were observed using NMR spectrocscopy.
DALTON TRANSACTIONS
(2021)
