Article
Chemistry, Inorganic & Nuclear
Betty Y. T. Lee, Andrew D. Phillips, Muhammad Hanif, Kelvin K. H. Tong, Tilo Sohnel, Christian G. Hartinger
Summary: This study discovered that incorporating an N-flanking anthracenyl moiety into [Rh(Cp*)(NHC)Cl-2] complexes can lead to the formation of an intramolecular C-C bond between the Cp* and anthracenyl moieties, resulting in unique cationic complexes with additional auxiliary interactions between the metal and the anthracenyl ring system. Computational modeling supported a reaction mechanism involving metallocycloaddition of Rh(eta(4)-tetramethylfulvene) intermediates and the abstraction of a chlorido ligand to produce these unique complexes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Chad M. Bernier, Christine M. DuChane, Justin S. Martinez, Joseph O. Falkinham, Joseph S. Merola
Summary: A range of Rh-III and Ir(III) piano-stool complexes were synthesized and characterized, showing high antimicrobial activities against various microbes, particularly Mycobacterium smegmatis. Rh complexes were generally more potent than their Ir analogues, and activity increased with the hydrophobicity of the ligands.
Article
Chemistry, Inorganic & Nuclear
Sara Fernandez-Moyano, Marconi N. Penas-Defrutos, Camino Bartolome, Pablo Espinet
Summary: Analysis of bonding contributions in transition metal complexes [(MCp)-Cp-III*(L)XY] (M = Rh, Ir; Cp* = C5Me5; L = CO, CN-, CNR) revealed a variety of new interactions, including direct lateral donations and hybrid donations, accounting for approximately 20% of the electron donation to the pi*(CO) orbitals.
INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Nilanjana Mukherjee, Bhaskar Mondal, Tarak Nath Saha, Ramananda Maity
Summary: Chiral ligands are crucial in asymmetric catalysis, and electron-rich chiral N-heterocyclic carbenes (NHCs) have emerged as effective ligands for enantioselective organic transformations. Tailored ligand design has led to the development of novel transition-metal complexes, and the modular synthesis of NHCs allows for easy customization. This review article summarizes the recent advances in enantioselective catalysis using well-defined transition-metal complexes with chiral NHC donor ligands.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Alice Johnson, Cameron G. Royle, Claire N. Brodie, Antonio J. Martinez-Martinez, Simon B. Duckett, Andrew S. Weller
Summary: Rhodium-alkene complexes with different alkenes have been studied for their reactivity towards H-2, with only COD showing significant reaction to form a COE complex. The differences in reactivity are attributed to intramolecular alkene-assisted reductive elimination in the COD complex. Further experiments on ethene complex suggest that reductive elimination from a reversibly formed alkyl hydride intermediate is likely rate-limiting and with a high barrier.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Chandrababu Naidu Kona, Rikuto Oku, Yuji Nishii, Masahiro Miura
Summary: The study describes iridium-catalyzed acylmethylation and rhodium-catalyzed amidation of naphthalene derivatives using sulfoxonium ylides and dioxazolones as carbene and nitrene transfer agents. The use of an SMe group as a directing group is crucial for achieving peri-selective functionalization, which can be easily removed or transformed after the catalysis into other synthetically useful functionalities.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Koichiro Masada, Shuhei Kusumoto, Kyoko Nozaki
Summary: In this study, a novel method for synthesizing metallabenzenes by replacing the phosphorus atom in an aromatic phosphinine ring with transition metal fragments was reported. Iridabenzene and rhodabenzene were successfully synthesized by triggering the replacement of the phosphorus atom with iridium and rhodium fragments, respectively. The aromaticity of the newly synthesized metallabenzenes was evaluated experimentally and theoretically.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yik Ki Au, Jie Zhang, Yangjian Quan, Zuowei Xie
Summary: This study presents a new method for the selective amination of o-carboranes with NH3 gas via Ir catalysis, providing a convenient and efficient access to a series of 3-NH2-o-carborane derivatives. The use of NH3 gas as the amination reagent with H2 as the sole byproduct makes the protocol economical, practical, and environmentally friendly.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Kelvin K. H. Tong, Mie Riisom, Euphemia Leung, Muhammad Hanif, Tilo Sohnel, Stephen M. F. Jamieson, Christian G. Hartinger
Summary: In this study, organometallic complexes with a piano-stool structure and di- or tridentate ligand systems were reported, showing improved biological activity and impact on cytotoxic activity.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: Enantioselective C-H functionalization is a powerful tool for synthesizing chiral molecules. The combination of high-valent group 9 metals with achiral Cp-x ligands and chiral carboxylic acids has shown promise in enabling selective cleavage and functionalization of enantiotopic C-H bonds. This Perspective provides a detailed summary of the background, catalyst design, applied reactions, and future directions in this field.
Article
Chemistry, Multidisciplinary
Pragati Biswal, Tanmayee Nanda, Shyam Kumar Banjare, Smruti Ranjan Mohanty, Ranjit Mishra, Ponneri C. Ravikumar
Summary: This article reports a novel reaction method for the highly stereoselective C(sp(2))-H propenylation using N-allyl benzimidazole as a catalyst. Detailed mechanistic studies were conducted to understand the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Chan Li, Yanchen Yang, Feifei Fang, Chaoyi Liu, Chunpu Li, Dechuan Wang, Hong Liu
Summary: In this study, a Rh(III)-catalyzed C-H activation strategy of N-nitrosoanilines and iodonium ylides was developed to construct novel tetralydrocarbzol-4-one scaffolds, providing valuable templates for sequential C-H functionalization at the C-5 position. Gram-scale synthesis and further transformations of tetralhydrocarbzol-4-one derivatives demonstrated the utility of this protocol in the concise and diverse construction of biologically active molecules.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Kriti Pathak, Shivankan Mishra, Chandan Nandi, Suvam Saha, Sundargopal Ghosh
Summary: Several dihydridoborate group 7 metal complexes with different chelation modes have been synthesized and their structures and bonding nature have been described. Photolysis of [M-2(CO)(10)] with these borate species resulted in the formation of dihydridoborate complexes. The electronic structures of these complexes have been investigated using density functional theory calculations.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Jan-Hendrik Schobel, Philipp Elbers, Khai-Nghi Truong, Kari Rissanen, Carsten Bolm
Summary: Two different protocols were presented for the preparation of three-dimensional aza-analogues of 1,2-benzothiazine 1,1-dioxides from sulfonimidamides. The first method involves a rhodium-catalyzed annulation reaction to produce 4-unsubstituted benzothiazine derivatives, while the second method utilizes an iridium catalyst under solvent-free mechanochemical conditions to obtain products with 3,4-disubstituted thiazine rings.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Jack Emerson-King, Adrian B. Chaplin
Summary: The synthesis and solid-state characterization of a heterobimetallic rhodium(III)/silver(I) complex [Rh(2,2'-biphenyl)(CxP(2))Cl]superset of Ag+ is reported, in which CxP(2) is a trans-spanning calix[4]arene-based diphosphine ligand and the silver cation is dative bond to the chloride ligand within the cavity of the macrocycle.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jefferson Guzman, Asier Urriolabeitia, Victor Polo, Marta Fernandez-Buenestado, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: The study achieved solventless selective dehydrogenation of formic acid, with the activation of the C-H bond identified as the rate-determining step. The research provides insights into the catalytic cycle and mechanism involved in the process.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Pablo Hermosilla, Pilar Garcia-Orduna, Pablo J. Sanz Miguel, Victor Polo, Miguel A. Casado
Summary: The reaction of an amido pincer complex with carbon dioxide resulted in a neutral complex, which then underwent a coupling reaction with primary amines to form cationic complexes. The study revealed a novel reactivity trend in alkyne activation, showing a metal-ligand cooperative mechanism involving electrophilic attack and proton rearrangement.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Maria Carmona, Roberto Perez, Joaquina Ferrer, Ricardo Rodriguez, Vincenzo Passarelli, Fernando J. Lahoz, Pilar Garcia-Orduna, Daniel Carmona
Summary: This article investigates the reactions between [(Cp*MCl)(2)(mu-Cl)(2)] and Ph2PCH2CH2NC(NH(p-Tolyl))(2) under different conditions, leading to the synthesis of a series of metal complexes. The structures and reaction mechanisms of these complexes were characterized and studied.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Pilar Garcia-Orduna, Jefferson Guzman, Israel Fernandez, Francisco J. Fernandez-Alvarez
Summary: The study demonstrates the formation of [IrH(Cl)(κ2-NSitBu2)(L)] species through the reaction of [IrH(Cl)(κ2-NSitBu2)(coe)] with PCy3 or PHtBu2. The structures and properties of these complexes are characterized by NMR spectroscopy and X-ray diffraction studies.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Gemma M. Rodriguez-Muniz, Miguel Gomez-Mendoza, Paula Miro, Pilar Garcia-Orduna, German Sastre, Miguel A. Miranda, M. Luisa Marin
Summary: This study provides fundamental insight into the role of topology and excited state multiplicity in governing the balance between photosensitized thymine-thymine formation and repair.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Daniel Barrena-Espes, Sergio Boneta, Victor Polo, Julen Munarriz
Summary: Catalytic systems based on sub-nanoclusters deposited over different supports show promise in various chemical transformations, such as electrocatalytic processes like the ORR. These systems are highly fluxional, capable of changing shape and interconverting between different structures in the presence or absence of adsorbates. Accurately characterizing their catalytic activity requires considering ensemble effects and not just isolated structures. By applying density functional theory (DFT) and global optimization techniques, we investigated the characteristics of Pt-6 sub-nanoclusters on a carbon-based support (graphene), which is of electrocatalytic relevance. We also analyzed magnetism, charge transfer, and the dependence of dispersion effects on ensemble properties. The results showed that the computed ensembles with and without dispersion corrections are qualitatively similar, indicating a primarily covalent binding to the surface. However, there were significant variations in the relative stability of certain clusters, which would impact their population in the ensemble composition.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
M. Pilar del Rio, B. Eva Villarroya, Jose A. Lopez, Ana M. M. Geer, Fernando J. J. Lahoz, Miguel A. A. Ciriano, Cristina Tejel
Summary: This study describes the synthesis of neutral and dicationic tetrametallic iridium chains connected by an iridium-iridium bond. The complexes exhibit fractional averaged oxidation states and electronic delocalization along the metallic chain. The absorption spectra of the complexes show characteristic bands that can be fine-tuned by varying the terminal capping ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Ana Luque-Gomez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias
Summary: A new method for preparing Co(I)-NHC complexes has been developed, which involves the direct reaction of imidazolium salts with Co(0) complex. The obtained complexes have shown efficient catalytic activity in the reductive amination of furfural and levulinic acid, using silanes as reducing agents. The side reaction of hydrosilylation process, dehydrocoupling of the silane, has also been observed.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sophie Beard, Alejandro Grasa, Fernando Viguri, Ricardo Rodriguez, Jose A. Lopez, Fernando J. Lahoz, Pilar Garcia-Orduna, Pilar Lamata, Daniel Carmona
Summary: This article presents transition metal frustrated Lewis pair compounds and their activation of bonds in small molecules, discussing their mechanisms and catalytic properties.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Alvaro G. Tejero, Maria Carmona, Ricardo Rodriguez, Fernando Viguri, Fernando J. Lahoz, Pilar Garcia-Orduna, Daniel Carmona
Summary: An improved synthesis method was used to prepare a rhodium compound with an achiral tetradentate ligand. The derived solvate complexes were resolved into their enantiomers and used as catalysts in various reactions, achieving high enantioselectivity by optimizing the catalyst structure.
Article
Chemistry, Inorganic & Nuclear
Pablo Hermosilla, Asier Urriolabeitia, Manuel Iglesias, Victor Polo, Miguel A. Casado
Summary: In this study, the complex [(CNC)Rh-Mes(PMe2Ph)]PF6 (1) was found to be an effective catalyst for solventless formic acid (FA) dehydrogenation, producing only H2 and CO2 as decomposition products. The addition of a base as a co-catalyst, particularly HCOONa, significantly enhanced the catalyst efficiency. Water was also found to greatly increase the catalytic activity. Kinetic experiments and DFT calculations provided insights into the reaction mechanism, revealing the crucial steps and the nature of intermediate species involved.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Mohammad El-Khateeb, Alaa Al-Momani, Pilar Garcia-Orduna, Fernando J. Lahoz
Summary: In this study, iron thiosulfonato complex and its selenosulfonato analogue were prepared and characterized. The new compounds' structures were determined by elemental analyses, IR, NMR, UV-Vis spectroscopy, and X-ray crystallography.
JOURNAL OF CHEMICAL SCIENCES
(2022)
