Article
Spectroscopy
Qin Yang, Marco Fuse, Julien Bloino, Vincenzo Barone
Summary: Chiroptical spectra are effective techniques for studying the electronic states of chiral systems, but their interpretation requires accurate computational models that consider stereo-electronic and vibrational effects. This contribution focuses on the latest developments in computational methods rooted in density functional theory for describing stereo-electronic effects in organometallic systems. Additionally, chiral iridium complexes are highlighted as a suitable case study for investigating bright phosphorescence and tuning properties for applications such as OLEDs and biomarkers.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This paper discusses the tuning of structure and properties of main-group species (E) by controlling pi-conjugation and/or pi-donation using classical N-heterocyclic vinyl (NI-IV) ligands. By selecting appropriate carbene units, the electronic structure of derived species can be precisely controlled, resulting in stable solid materials.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Inorganic & Nuclear
Rahat Gupta, Priya Sahni, Salil K. Jana, Anshul Negi, Amlan K. Pal
Summary: In this study, two novel deep-blue Ir-NHC emitters were synthesized with strategically designed pro-carbenic imidazolium ligands incorporating a heavy bromine atom. These emitters exhibited enhanced emission properties in both solution and film forms, with a 15 times higher photoluminescence quantum yield compared to benchmark complexes.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jayaraman Selvakumar, Scott M. Simpson, Eva Zurek, Kuppuswamy Arumugam
Summary: This study successfully synthesized a series of iron bis(dithiolene) complexes with high yield and characterized them by NMR spectroscopy and X-ray diffraction. The research also showed that these iron complexes can release NHC upon electrochemical reduction, which can be used as a catalyst for synthesis.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Maria Kashina, Konstantin Luzyanin, Eugene A. Katlenok, Alexander S. Novikov, Mikhail A. Kinzhalov
Summary: In this study, platinum and palladium complexes were synthesized through metal-mediated coupling reactions, and thiocyanate complexes were prepared through ligand exchange reactions. The characterization and evaluation of these compounds were performed, and the electronic structure and bonding nature were studied through X-ray diffraction and theoretical considerations. Additionally, it was demonstrated that two of the thiocyanate derivatives formed supramolecular dimers with symmetrical pairs. Furthermore, some of the compounds were evaluated as photocatalysts.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Angela Vivancos, Adrian Jimenez-Garcia, Delia Bautista, Pablo Gonzalez-Herrero
Summary: A series of bis-cyclometalated Pt(IV) complexes incorporating mesoionic aryl-NHC ligand trz with either 1-phenylpyrazole or 2-arylpyridine ligands are reported, showing phosphorescent emissions in the blue to yellow color range with high quantum yields. The addition of trz ligand leads to lower nonradiative decay rates and higher quantum efficiencies compared to homologous species with two equal 2-arylpyridine ligands. Computational calculations substantiate the effect of the carbene ligand on the energy levels and emissive properties of the complexes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Janis Musso, Jordan De Jesus Silva, Mathis J. Benedikter, Jonas Groos, Wolfgang Frey, Christophe Coperet, Michael R. Buchmeiser
Summary: Recent studies have shown that cationic d(0) group 6 olefin metathesis catalysts exhibit higher activity compared to their neutral counterparts, and their catalytic performance is greatly enhanced by immobilization on silica.
Review
Chemistry, Inorganic & Nuclear
Moushakhi Ghosh, Shabana Khan
Summary: This article highlights the recent developments in silylene-coinage metal chemistry, focusing on synthetic approaches, unusual properties, and catalytic efficiency of these complexes. Further research is needed to explore the potential of silylene-coinage metal complexes in various chemical reactions.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Sai Zhao, Zhibing Yang, Guizhi Jiang, Sheng Huang, Mianli Bian, Yunlong Lu, Wukun Liu
Summary: NHCs have been introduced as a new platform for the development of anticancer metal complexes, with platinum NHC complexes showing comparable activities to cisplatin and exhibiting different mechanisms of action, including the induction of biochemical hallmarks of immunogenic cell death (ICD) as a type II ICD inducer. These features make them promising candidates in the field of anticancer research.
COORDINATION CHEMISTRY REVIEWS
(2021)
Review
Chemistry, Multidisciplinary
Fady Nahra, Catherine S. J. Cazin
Summary: This review critically presents catalysts based on palladium and ruthenium bearing N-heterocyclic carbene ligands, which have enabled a more sustainable approach to catalysis and catalyst uses. Aspects of sustainability associated with these in terms of catalytic uses or synthetic access are reviewed.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Magnus R. Buchner, Deniz F. Bekis
Summary: The reactivity of MeIPr and IDipp in dichloromethane was investigated. MeIPr reacts slowly and selectively with the solvent, forming imidazolium salt, while IDipp reacts unselectively to various imidazolium salts. Due to their slow decomposition rates in CH2Cl2, reactions with free carbenes and Lewis acids can be performed.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Magnus R. Buchner, Deniz F. Bekis
Summary: This study investigates the reactivity of two free carbenes in dichloromethane. It is found that MeIPr reacts slowly and selectively with the solvent, forming an imidazolium salt. In contrast, IDipp reacts unselectively to various imidazolium salts. The slow decomposition rates of the carbenes in CH2Cl2 allow reactions with Lewis acids to be performed.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Daven Foster, S. M. Borhanuddin, Reto Dorta
Summary: Chiral ligands play a crucial role in asymmetric transition-metal catalysis, with N-heterocyclic carbenes (NHCs) exhibiting high levels of enantioselectivity. The field is expected to continue advancing in the future.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Mirjam J. Krahfuss, Udo Radius
Summary: This study highlights the recent developments of N-heterocyclic silylenes (NHSis) as ambiphilic activators and ligands in organometallic chemistry, comparing their properties with N-heterocyclic carbenes (NHC) and phosphine ligands. NHSis show different ligation properties due to their unique frontier orbital region compared to NHCs, with donor properties closer to phosphines. They exhibit a stronger tendency to act as bridging ligands between metal centers and achieve more facile insertion reactions into metal-ligand bonds than NHCs, providing novel reactivities in basic organometallic chemistry and catalysis.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Multidisciplinary
Peter Bellotti, Maximilian Koy, Matthew N. Hopkinson, Frank Glorius
Summary: N-Heterocyclic carbenes have attracted significant interest due to their versatility, modularity and strong coordinating properties, leading to a rapid increase in utilization across various fields in the past decade. Future directions and recent developments in the field are also highlighted in this review.
NATURE REVIEWS CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Raquel Puerta-Oteo, Ana Ojeda-Amador, M. Victoria Jimenez, Jesus J. Perez-Torrente
Summary: This article highlights recent developments on the application of transition metal-based zwitterionic complexes in catalysis, including selected zwitterionic catalysts in polymerization reactions and advances in hydrogenation/dehydrogenation reactions related to energy applications.
DALTON TRANSACTIONS
(2022)
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
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, Inorganic & Nuclear
Susana Garcia-Abellan, Vincenzo Passarelli, Manuel Iglesias
Summary: 2a and 2b [Ir(CI)(COD)(NHC)] (1,5-cyclooctadiene as COD) were synthesized by transmetallation from NHC-Ag complexes. Analogously, [Rh(CI)(COD)(NHC)] (4) was prepared. [Ir({kappa-C,N-(NHC-acetamide-1H)}(COD)] (3c) was synthesized by transmetallation from deprotonated NHC-Ag complex. [IrCp*({kappa-C,N-(NHC-acetamide-1H)}] (5) (Cp*=pentamethylcyclopentadienyl) was obtained analogously. [Ir(CI)(CO)(2)(NHC)] (6) and [Ir({kappa-C,N-(NHC-acetamide-1H)}(CO)(2)] (7) were prepared by carbonylation of 2b and 3c, respectively. The catalytic activity of these complexes in formic acid dehydrogenation was evaluated under solventless conditions, in the presence of water as a cosolvent, and in a 5 : 2 HCOOH/Et3N mixture, with the best TOF values obtained in the latter case. Stoichiometric experiments suggest COD hydrogenation as the preactivation step.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Pablo Hermosilla, Daniel Funes-Hernando, Ricardo Castarlenas, Andrea Di Giuseppe, Ramon Azpiroz, Eugenio Vispe, Jesus J. Perez-Torrente
Summary: The catalytic system of [Rh(mu-Cl)(IPr)(eta 2-coe)]2/pyridine efficiently facilitates the polyhydrothiolation reaction between dithiols and dialkynes, resulting in the formation of sulfur-rich poly(vinylidene sulfide)s with high molecular weights and high vinylidene sulfide content. The combination of different types of dithiols and dialkynes allows the preparation of poly(vinylidene sulfide)s with varying properties.
EUROPEAN POLYMER 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)
Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Miguel Gonzalez-Lainez, M. Victoria Jimenez, Vincenzo Passarelli, Jesus J. Perez-Torrente
Summary: Neutral and cationic cyclooctadiene rhodium(i) complexes with a lutidine-derived polydentate ligand have been synthesized and found to efficiently catalyze the hydrosilylation of 1-hexyne with high selectivity. These catalysts exhibit a different β-(Z) selectivity compared to previously reported rhodium(i) catalysts based on 2-picolyl-functionalized NHC ligands. Kinetic studies suggest an energy barrier of 19.8±2.0 kcal mol(-1) for the hydrosilylation reaction.
DALTON TRANSACTIONS
(2023)
Article
Urology & Nephrology
Susana Garcia-Abellan, Vincenzo Passarelli, Manuel Iglesias
Summary: Two Ir complexes, 2a and 2b, with the ligand [Ir(CI)(COD)(NHC)] (COD=1,5-cyclooctadiene), were synthesized through transmetallation from NHC-Ag complexes. Analogously, another Rh complex, 4, was prepared using the same method. By transmetallation from the deprotonated NHC-Ag complex, another Ir complex, 3c, with the ligand [Ir({kappa-C,N-(NHC-acetamide-1H)}(COD)], was synthesized. Similarly, [Ir(CI)(CO)(2)(NHC)] (6) and [Ir({kappa-C,N-(NHC-acetamide-1H)}(CO)(2)] (7) were obtained through carbonylation of 2b and 3c respectively. The catalytic activity of these complexes in formic acid dehydrogenation was evaluated, with the highest turnover frequency (TOF) observed in the presence of a 5:2 HCOOH/Et3N mixture. Stoichiometric experiments suggested COD hydrogenation as the preactivation step.
Article
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: A comparative study of the catalytic activity of two iridium(III) complexes has been performed, and it was found that complex 3 showed the highest activity in the solventless formic acid dehydrogenation reaction at 373 K. The best performance was achieved at 353 K, with a reaction rate of approximately 1210 h(-1) and no observable CO.
DALTON TRANSACTIONS
(2023)
Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: This article investigates the catalytic performance of iridium complexes in the dehydrogenation of formic acid and examines the effect of auxiliary ligands on the catalytic performance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Susana Garcia-Abellan, Daniel Barrena-Espes, Julen Munarriz, Vincenzo Passarelli, Manuel Iglesias
Summary: The novel P-N ligand based on a benzotriazole scaffold was prepared and used to synthesize chelate complexes. These complexes acted as catalysts in the fluorination reactions of aromatic and aliphatic acyl chlorides. The reaction rate and substrate scope were improved by using organic carbonates as solvents. Comparative studies and theoretical calculations were conducted to understand the reaction mechanism.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marco Palmese, Jesus J. Perez-Torrente, Vincenzo Passarelli
Summary: This study investigates the reaction mechanism and structures of the iridium(III) derivatives produced from the reactions of [IrCl(cod)(SiNP)] and [Ir{kappa C-3,P,P '-(SiNP-H)}(cod)] with various oxidants. The reactions include allyl chloride and tert-butyl isocyanide, as well as [FeCp2]X, I-2, and CF3SO3CH3. The crystal structures of selected compounds confirm the products of these reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marco Palmese, Jesus J. Perez-Torrente, Vincenzo Passarelli
Summary: In this study, the iridium(I)-aminophosphane complex [Ir{kappa C-3,P,P'-(SiNP-H)}(cod)] was prepared by reaction of [IrCl(cod)(SiNP)] with KCH3COO. It was found that this reaction proceeds through an unexpected outer sphere mechanism. Various iridium(III) derivatives were obtained by reacting [IrCl(cod)(SiNP)] or [Ir{kappa C-3,P,P'-(SiNP-H)}(cod)] with different oxidants. The crystal structures of selected compounds were determined.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marco Palmese, Jesus J. Perez-Torrente, Vincenzo Passarelli
Summary: In this study, a novel iridium(III) hydride compound was obtained and its reaction mechanism was investigated using NMR spectroscopy and DFT calculations. The reactivity of the compound was also studied. Furthermore, the crystal structures of several compounds were determined by X-ray diffraction measurements.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
