Article
Chemistry, Inorganic & Nuclear
Javier Ruiz, Maria A. Mateo
Summary: An isocyanide-functionalized imidazole was synthesized from 4-(1H-imidazol-1-yl)aniline using the Ugi method, and subsequently converted into the corresponding imidazolium salt. Coordination of the isocyanide residue allowed the synthesis of several transition metal complexes containing a peripheral imidazolium cation, which serve as suitable starting materials for the formation of mixed ligand isocyanide-NHC heterometallic complexes.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Guillermo Marcos-Ayuso, Marconi N. Penas-Defrutos, Ana M. Gallego, Max Garcia-Melchor, Jesus M. Martinez-Ilarduya, Pablo Espinet
Summary: This article discusses the method and importance of synthesizing aryl-alkynyl compounds. The traditional Sonogashira catalysis method is inefficient for fluorinated aryls, but an alternative method using alkynylstannanes and hemilabile PN ligands has been reported. The revision of literature reveals the existence of unreported byproducts and other factors that explain the conflict and provide clues for designing efficient alternatives for synthesizing the desired compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Malte Fischer, Matthew M. D. Roy, Sascha Hueller, Marc Schmidtmann, Ruediger Beckhaus
Summary: The N-heterocyclic olefin (NHO) ImMe(4)=CH2 was used to synthesize a titanium complex with an NHO ligand. The reaction between NHO intermediate and a pentafulvene titanium complex resulted in the formation of a titanium complex with an anionic NHO ligand. The complex was characterized using NMR spectroscopy, single crystal X-ray diffraction, and quantum chemical calculations.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Applied
Heng-Tong Qu, Zeng-Hui Wu, Guo-Chen Zhong, Yan-Chun Zhang, Cheng-Tao Feng, Kun Xu
Summary: An aerobic Mn(III)-catalyzed one-pot three-component synthesis of 5-cyano-pyrazolo[1,5-a]pyrimidines has been developed, which relies on the synergistic combination of Strecker reaction and oxidatively-induced 6 pi-azacyclization. This protocol offers a step-economic, regioselective, and functionally tolerant strategy to obtain 5-cyano-pyrazolo[1,5-a]pyrimidines, distinct from previous reports using toxic cyanating agents or multistep synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Benson M. Kariuki, James A. Platts, Paul D. Newman
Summary: An asymmetric bipy/NHC ligand L was utilized to create Au/Au, Au/Ag, and Au/Cu bimetallic complexes by first coordinating NHC to Au(i) and then introducing the second group 11 metal ion to the bipy donor of the hybrid ligand.
Article
Chemistry, Multidisciplinary
Eloy P. Gomez-Oliveira, Daniel Reinares-Fisac, Lina M. Aguirre-Diaz, Fatima Esteban-Betegon, Mercedes Pintado-Sierra, Enrique Gutierrez-Puebla, Marta Iglesias, M. Angeles Monge, Felipe Gandara
Summary: This study synthesized and characterized three new bismuth metal-organic frameworks (MOFs), and demonstrated their catalytic activity in the one-pot multicomponent Strecker reaction. Among the MOFs, BiPF-7 exhibited high stability and catalytic activity, and the interaction between catalytic substrates and metal centers was analyzed through crystallography.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Fachao Yan, Zijun Huang, Chen-Xia Du, Jian-Fei Bai, Yuehui Li
Summary: The FeI2-catalyzed reductive Strecker type reaction of formamides was reported, which successfully produced amino acetonitriles instead of aldehydes with higher yields than Ir or Rh catalysts. This method demonstrated the ability to one-pot construct complex molecules and conveniently produce homologated carboxylic acids from aldehydes.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Niklas F. Both, Anke Spannenberg, Haijun Jiao, Kathrin Junge, Matthias Beller
Summary: The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. Various aromatic and aliphatic esters were successfully hydrogenated at mild temperatures and low catalyst loadings using complexes 3 with KHBEt3 as additive, highlighting the efficiency of the novel catalytic system. Additionally, the versatility of the developed catalytic system was demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes, and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Gaoxin Zhou, Yang Chen, Wenhao Chen, Hao Wu, Yun Yu, Chunlong Sun, Benhui Hu, Yun Liu
Summary: A nanozyme-catalyzed cascade reaction is used to release carbon monoxide (CO) for high-efficacy photothermal therapy (PTT)-combined CO therapy of cancer. Gold-based porphyrinic coordination polymer nanosheet (Au-0-Por) is used as a carrier for CO release. It shows high tumor-targeting efficiency, nanomaterial retention, and good biocompatibility.
Article
Chemistry, Inorganic & Nuclear
Susana Herrera, Kennett Rivero, Alexis Guzman, Jonathan Cedeno, Jaroslava Miksovska, Raphael G. Raptis
Summary: This study synthesized a new family of mononuclear indium complexes, trianionic hexanuclear indium complexes, and multicolour emitting polymeric complexes. The complexes were characterized using crystallography and NMR techniques. The study found that these complexes exhibit fluxional behavior and identified the causes of this behavior.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Thibaut Martinez, Avassaya Vanitcha, Claire Troufflard, Nicolas Vanthuyne, Jeremy Forte, Geoffrey Gontard, Gilles Lemiere, Virginie Mouries-Mansuy, Louis Fensterbank
Summary: In this study, a new family of carbene ligands based on an indolizine-ylidene (Indolizy) moiety is reported, with corresponding gold(I) complexes exhibiting strong sigma-donating and pi-accepting properties. Cationization of the gold(I) complexes generates catalytic species for diverse reactions, and bifunctional carbene ligands with specific structural features enable highly enantioselective heterocyclizations. DFT calculations provide rationalization and highlight the critical roles of the phosphine oxide group and the tosylate anion in asymmetric cyclizations of gamma-allenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Justus Diekamp, Thomas Seidensticker
Summary: The recycling of homogeneous catalysts in a homogeneous matrix is a challenging task for many reactions aiming for industrial applications. Although various synthetic approaches for recyclable homogeneous catalysts exist, a concise overview of catalyst modifications is lacking in the literature. This review aims to fill this gap by summarizing the existing synthesis pathways for polar, non-polar, fluorous, and molecular-weight-enlarged catalysts and examining their modular and late-stage approaches. Additionally, the potential for a generally applicable tag library to facilitate catalyst modifications for specific recycling strategies is explored.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tingrui Li, Yilitabaier Julaiti, Xiaopeng Wu, Jie Han, Jin Xie
Summary: The gold-catalyzed ring-opening rearrangement of cyclopropenes provides an efficient method for synthesizing polysubstituted naphthols or aryl-substituted furans. The reaction selectivity between naphthols and furans can be switched by using different gold-carbenes or gold-carbocations as catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Renat Kadyrov
Summary: An efficient and simple catalytic system has been developed for the hydrogenation of carboxylic esters using commercially available Ru-salts and imidazolium salts. This combination enables the reduction of esters to alcohols at moderate temperature and pressure, offering a practical method for alcohol synthesis.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Hui Shen, Zhen Xu, Maryam Sabooni Asre Hazer, Qingyuan Wu, Jian Peng, Ruixuan Qin, Sami Malola, Boon K. Teo, Hannu Hakkinen, Nanfeng Zheng
Summary: Deciphering the atomic arrangement of hybrid surface ligands on metal nanoparticles is a key step towards understanding their complex geometrical and electronic structures, which can have potential bio-applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Cesar Ruiz-Zambrana, Rajeev K. Dubey, Macarena Poyatos, Aurelio Mateo-Alonso, Eduardo Peris
Summary: A series of rhodium and iridium complexes with a N-heterocyclic carbene (NHC) ligand decorated with a perylene-diimide-pyrene moiety were studied. These complexes can undergo reduction events associated with the attached perylene-diimide-pyrene moiety, leading to an increase in the ligand's electron-donating character. The rhodium complex showed redox-switchable behavior in the [3+2] cycloaddition reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Susana Ibanez, Eduardo Peris
Summary: Two different metallotweezers were used as hosts for a series of planar aromatic guests. The binding strength and models of the two metallotweezers differed due to their structural differences.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Cesar Ruiz-Zambrana, Macarena Poyatos, Eduardo Peris
Summary: A gold complex with a naphthalene-di-imide-functionalized N-heterocyclic carbene (NHC) ligand was prepared and its reversible redox properties and catalytic activity in the hydroamination of terminal alkynes were studied.
Article
Chemistry, Multidisciplinary
Alejandro Lopez-Moreno, Susana Ibanez, Sara Moreno-Da Silva, Luisa Ruiz-Gonzalez, Natalia Martin Sabanes, Eduardo Peris, Emilio M. Perez
Summary: Mechanically interlocked derivatives of carbon nanotubes (MINTs) are interesting and stable nanotube products. This study explores the encapsulation of single-walled carbon nanotubes within a palladium-based metallosquare, revealing the sensitivity of MINT formation to structural variations of the metallo-assemblies. The study also demonstrates the potential application expansion of MINTs through supramolecular coordination complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Eric A. Assaf, Sergio Gonell, Chun-Hsing Chen, Alexander J. M. Miller
Summary: A ruthenium catalyst with a bidentate bis(carbene) ligand was prepared and studied for CO2 electroreduction. The catalyst showed high activity and efficiency at low overpotentials, with the bis(carbene) ligand playing a crucial role in CO2 activation.
Article
Chemistry, Multidisciplinary
Sebastian Martinez-Vivas, Macarena Poyatos, Eduardo Peris
Summary: H-1 NMR studies showed that a cationic complex with a pyridine-di-imidazolylidene pincer ligand exhibited high binding affinity with coronene in CH2Cl2. This binding was established through π-stacking interactions between coronene and the planar Rh-I complex. The interaction influenced the electron-donating strength of the pincer CNC ligand and increased the reaction rate of nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, as well as enhancing its catalytic activity in the cycloisomerization of 4-pentynoic acid. These findings highlight the significance of supramolecular interactions in modifying the reactivity and catalytic activity of square-planar metal complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Susana Ibanez, Katarzyna Swiderek, Eduardo Peris
Summary: Mechanically interlocked molecules (MIMs) have attracted attention for their unique properties in various applications. This study presents a tetragold(I) rectangle-like metallobox that can easily encapsulate a pyrene molecule with four octynyl substituents. Unlike typical MIMs, this molecule can release the guest by the addition of coronene, which compresses the flexible limbs of the guest to facilitate its sliding in and out of the metallobox.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Lucas H. R. Passos, Victor Martinez-Agramunt, Dmitry G. Gusev, Eduardo Peris, Eduardo N. dos Santos
Summary: The reduction of esters and aldehydes to alcohols is an important reaction in the chemical industry. The behavior of three commercially available Ru-catalysts for the hydrogenation of these feedstocks is reported. Selective hydrogenation of the ester or aldehyde functionality while keeping the C=C double bond intact is possible, and mild reaction conditions and a sustainable solvent are suitable for these catalytic hydrogenations.
Article
Chemistry, Inorganic & Nuclear
Cristian Gutierrez-Pena, Macarena Poyatos, Eduardo Peris
Summary: A series of dimetallic and monometallic Cp*Ir(III) complexes with naphthalene-diimide-decorated N-heterocyclic carbene/pyridine ligands were synthesized and characterized. The complexes showed C,C-chelating coordination of the NHC-pyridine ligand, with cyclometallation occurring on the pyridine ring. Spectroelectrochemical studies revealed that the complexes underwent two successive reduction events associated with the NDI moiety of the ligand. The complexes displayed good activity and selectivity in the dehydrative etherification by cross-coupling of primary alcohols, and a reaction mechanism involving a redox-neutral acid-catalyzed pathway was proposed based on mechanistic studies.
Article
Chemistry, Multidisciplinary
Sebastian Martinez-Vivas, Dmitry G. Gusev, Macarena Poyatos, Eduardo Peris
Summary: We report a rhodium(I) complex with modulable electronic nature through supramolecular and redox stimuli. The complex shows strong pi-pi-stacking interaction with coronene, affecting its electron-richness. Addition of tetrabutylammonium fluoride sequentially reduces the ligand's NDI moiety, enhancing its electron-donor strength. The complex's catalytic activity in the cycloisomerization of alkynoic acids can be modulated by the addition of fluoride, resulting in four levels of activity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Cristian L. Gutierrez-Pena, Macarena Poyatos, Eduardo Peris
Summary: Two bis-(propyl-imidazolium)-napthalenediimide (NDI) salts were prepared and used as N-heterocyclic carbene (NHC) precursors to prepare dimetallic complexes of rhodium and iridium. Infrared spectroelectrochemical studies suggest that the metals are responsive to changes in the electronic state of the NDI moiety. Catalytic testing in the cycloisomerization of alkynoic acids showed that the rhodium and iridium complexes possess effective redox-switching properties.
CHEMICAL COMMUNICATIONS
(2022)
