Article
Chemistry, Multidisciplinary
Sebastian Koniarz, Kinga Szydelko, Michal J. Bialek, Karolina Hurej, Piotr J. Chmielewski
Summary: A family of transition metal complexes based on meso-aryl-2-aza-21-carbaporphyrin (N-confused porphyrin, NCP) derivatives were synthesized and characterized. The chirality of these complexes was demonstrated by enantiomeric separation and analysis. Preliminary catalytic study showed the activity of iridium(III) ortho-metallated complexes in the N-heterocyclization of primary amines with diols.
Article
Chemistry, Multidisciplinary
Jun Takaya
Summary: Recent research has demonstrated the promising utility of transition metal complexes with M-E bonds stabilized by multidentate ligands, where E represents a main group metal or metalloid element. Main group metal and metalloid ligands provide unique electronic and steric environments to transition metals, leading to remarkable catalytic activity and product selectivity. This perspective highlights the potential of these compounds as a new class of supporting ligands for transition metal catalysts in synthetic chemistry.
Review
Chemistry, Multidisciplinary
Chiara Bisio, Fabio Carniato, Matteo Guidotti
Summary: This review provides an overview of the use and role of coordination complexes as precursors for the generation of hybrid catalysts in oxidation reactions for fine chemical synthesis. The understanding of active site formation in hybrid catalysts is emphasized, and different families of coordination precursors are considered. Each example includes a brief analysis of synthesis, characterization, and catalytic performance. Special attention is given to the chemical environment of the active metal center's first coordination sphere. By integrating advantages of both homogeneous and heterogeneous systems, catalysts obtained through heterogenization, grafting, or anchoring of homogeneous catalysts exhibit enhanced catalytic performance. Deposition of coordination complexes onto preformed supports offers a versatile strategy for designing novel catalysts with tailored and controlled properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Marta Estrader, Katerina Soulantica, Bruno Chaudret
Summary: This article discusses the synthesis of magnetic metal nanoparticles using organometallic precursors, as well as their properties and potential applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Wenbo Dong, Yi Yang, Yonggang Xiang, Shengyao Wang, Pei Wang, Jianxiang Hu, Li Rao, Hao Chen
Summary: The newly designed dual nickel/photocatalysis 2D covalent organic framework (COF) has successfully overcome the difficulties of recycling photosensitizers or nickel complexes, efficiently converting aryl bromides to aryl alkyl ethers with good substrate compatibility and functional group tolerance.
Article
Chemistry, Inorganic & Nuclear
Jin Young Koo, Jongwon Oh, Gyeongeun Hyun, Hee Cheul Choi, Intek Song, Seok Min Yoon
Summary: A new oxo-bridged chromium-molybdenum heterometallic complex, O-CrMoHC, was synthesized by a solvothermal reaction. The complex exhibits anisotropic conductivity in single crystals, with higher electrical conductivity along the [01-1] direction compared to the [100] direction. This is the first report of anisotropic conductivity observed in a monomeric heterometallic complex single crystal.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yanan Yu, Zhao Wang, Ziping Li, Xinxin Hang, Yanfeng Bi
Summary: Three cobalt-thiacalix[4]arene coordination clusters were synthesized using a solvothermal self-assembly method, featuring adenine-functionalized secondary building units. The structures exhibit different coordination modes and symmetries, formed by linking multiple basic units through ligand bridging.
Review
Chemistry, Multidisciplinary
Paolo Destito, Cristian Vidal, Fernando Lopez, Jose L. Mascarenas
Summary: Developing non-natural biocompatible transformations in biologically relevant media has attracted significant interest in the past decade, with the use of transition metal complexes offering unique possibilities. This translation of metal catalyst potential to biological environments poses challenges, but describing the most relevant advances and key challenges helps identify issues from an organometallic perspective.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Giarita Ferraro, Nicola Demitri, Luigi Vitale, Giuseppe Sciortino, Daniele Sanna, Valeria Ugone, Eugenio Garribba, Antonello Merlino
Summary: The study investigated the interaction between the V-picolinato complex and RNase A, revealing specific residue binding of V to RNase A and its impact on enzymatic activity without altering the overall structure and stability of the protein.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Cristian Vicent, Victor Martinez-Agramunt, Viraj Gandhi, Carlos Larriba-Andaluz, Dmitry G. Gusev, Eduardo Peris
Summary: The study investigated the encapsulation of tetracationic palladium metallosquare with four pyrene-bis-imidazolylidene ligands using ESI TWIM-MS and determined Collision Cross Sections (CCS). The host exhibited expansion when fullerenes or polycyclic aromatic hydrocarbons were encapsulated, with expansions ranging from 13 to 49 angstrom(2). DFT calculations were used to obtain energy-minimized structures of the complexes in the gas phase.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Roel F. J. Epping, David Vesseur, Minghui Zhou, Bas de Bruin
Summary: Discovered in the 1970s as organometallic curiosities, carbene radicals have become essential in modern homogeneous catalysis. These radicals exhibit nucleophilic reactivity different from electrophilic Fischer carbenes. The successful catalytic application of carbene radicals has led to the synthesis of diverse carbon and heterocyclic compounds. This Perspective provides an overview of the coordination chemistry, reactivity, and catalytic application of carbene radicals using transition metal complexes and catalysts since 2011.
Review
Chemistry, Inorganic & Nuclear
Joy H. Farnaby, Tajrian Chowdhury, Samuel J. Horsewill, Bradley Wilson, Florian Jaroschik
Summary: This review summarizes the progress in organo-f-element chemistry in 2019, focusing on the discovery of new types of complexes, diverse reactivities of lanthanide metals, and reports on novel catalytic reactions. Advancements in hydrocarbyl complexes of the actinides are also highlighted.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Ernesto Soto, Katherine L. Helmink, Colleen P. Chin, Michael Ferguson, Steven J. Peters, Lisa F. Szczepura
Summary: Three organometallic rhenium-based clusters containing phenylacetylide ligands were synthesized and characterized. Reactivity studies showed that the formation of vinylidene species did not occur as predicted, but instead the elimination of the acetylide moiety was observed. The isolated reaction products were characterized, and the relative reactivities of the electrophilic agents were compared. Computational studies provided useful information about the nature of the [Re6Se8]2+-acetylide bond and aided in understanding the reactivity of this cluster complex.
Article
Chemistry, Inorganic & Nuclear
Ernesto Soto, Katherine L. Helmink, Colleen P. Chin, Michael Ferguson, Steven J. Peters, Lisa F. Szczepura
Summary: Three rhenium-based clusters with phenylacetylide ligands were synthesized and characterized. Reactivity studies showed that the formation of the predicted vinylidene species did not occur, and instead, elimination of the acetylide moiety was observed. Characterization of the reaction products and computational studies provided insights into the reactivity of this cluster complex.
Article
Chemistry, Multidisciplinary
Shashi Kumar, Deeptesh K. Patra, Arnab Rit
Summary: The heterobimetallic IrIII-M and PdII-IrIII complexes were synthesized by using a suitable ligand platform. These complexes showed superior catalytic activities compared to both their homobimetallic and monometallic counterparts. The IrIII-PdII complex exhibited better cooperativity and higher activity than the IrIII-IrIII and PdII-PdII complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biotechnology & Applied Microbiology
Isaac O. Omari, Hannah M. Charnock, Alexa L. Fugina, Euan L. Thomson, J. Scott McIndoe
Summary: This study found a divergence in outcomes of all-malt and adjunct brewing driven by magnesium-catalyzed color formation, with rice playing a key role in this difference.
JOURNAL OF THE AMERICAN SOCIETY OF BREWING CHEMISTS
(2021)
Article
Chemistry, Multidisciplinary
Isaac Omari, Lars P. E. Yunker, Johanne Penafiel, Darlene Gitaari, Atzin San Roman, J. Scott McIndoe
Summary: Organotrifluoroborates are used as coupling partners in the Suzuki-Miyaura reaction, but require hydrolysis before the coupling reaction. Electrospray ionization mass spectrometry (ESI-MS) allows real-time monitoring of their hydrolysis, complemented by pH analysis. The induction periods and reaction rates during hydrolysis were found to be sensitive to the R group of the borates, the shape of the reaction vessel, and stir rate.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Anuj Joshi, Scott Collins, Mikko Linnolahti, Harmen S. Zijlstra, Elena Liles, J. Scott McIndoe
Summary: Hydrolysis of trimethylaluminum in polar solvents was monitored by ESI-MS, showing different anion distributions in hydrolytic methylaluminoxane (h-MAO). NMR spectroscopy revealed variations in activator contents of MAO synthesized under different conditions, with significantly different properties from non-hydrolytic MAO containing incorporated boron. The formation of oligomeric anions in MAO prepared by direct hydrolysis was observed, evolving into a mixture dominated by an anion with m/z 1375.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Scott Collins, Galib Hasan, Anuj Joshi, J. Scott McIndoe, Mikko Linnolahti
Summary: Density functional theory calculations on neutral sheet models for methylaluminoxane suggest that 5-coordinate and 4-coordinate aluminum structures may be precursors to ion pairs observed during the hydrolysis of trimethylaluminum. The studies show that low molecular weight 5-coordinate sheets mainly ionize through [Me2Al](+), while higher molecular weight 4-coordinate sheets are more likely to ionize through [Me](-) from Me3Al-OMTS. Additionally, comparisons of anion stabilities per mole of aluminoxane repeat unit indicate that certain anions are especially stable compared to higher homologues, despite their unstable neutral precursors.
Article
Biochemical Research Methods
Anuj Joshi, Charles Killeen, Tanner Thiessen, Harmen S. Zijlstra, J. Scott McIndoe
Summary: Mass spectrometry is a powerful tool in chemistry, but its sensitivity can be a challenge when studying highly reactive organometallic compounds. Creative solutions have been developed to handle reactive samples, including selecting appropriate ionization methods and preventing decomposition caused by oxygen or moisture.
JOURNAL OF MASS SPECTROMETRY
(2022)
Article
Chemistry, Applied
Antonio Rosales Martinez, Lourdes Enriquez, Martin Jaraiz, Tanner Thiessen, Jaspreet Sidhu, J. Scott McIndoe, Ignacio Rodriguez-Garcia
Summary: Reduction of Cp2TiCl2 with manganese dust in dry THF results in a green solution that turns deep blue when traces of water are added. Mass spectrometric analysis and DFT calculations were used to gain a better understanding of the species present after water interacts with reduced Cp2TiCl2. The deep blue solution serves as a convenient visual indicator for qualitative determination of water in THF.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Charles Killeen, Jie Liu, Harmen S. S. Zijlstra, Florian Maass, James Piers, Reid Adams, Allen Oliver, J. Scott McIndoe
Summary: Ring-closing metathesis (RCM) is a versatile method for forming cyclic structural elements. Real-time analysis using electrospray ionization mass spectrometry (ESI-MS) was applied to study the RCM reaction, revealing the presence of by-products and the decomposition of the catalyst. Isomerization reactions play a significant role in affecting the yield of the desired product, especially in slow RCM reactions.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Peter J. H. Williams, Charles Killeen, Ian C. Chagunda, Brett Henderson, Sofia Donnecke, Wil Munro, Jaspreet Sidhu, Denaisha Kraft, David A. Harrington, J. Scott McIndoe
Summary: Continuous addition kinetic elucidation (CAKE) is a method to address the challenges in catalytic reactions by continuously injecting a catalyst and monitoring reaction progress, reducing workload and improving reproducibility.
Review
Chemistry, Multidisciplinary
Gilian T. Thomas, Sofia Donnecke, Ian C. Chagunda, J. Scott McIndoe
Summary: Pressurized sample infusion is a simple and effective method for continuously introducing a solution to a mass spectrometry source, allowing real-time data acquisition. It is applicable for various reactions that require real-time information.
Article
Education, Scientific Disciplines
Jaspreet Sidhu, J. Scott McIndoe
Summary: Understanding molecular scale is crucial for chemistry students. Using 3D printing to scale up molecules allows students to better comprehend the difference between molecular scale and handheld scale.
CHEMISTRY TEACHER INTERNATIONAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Gilian T. Thomas, Kiera Ronda, J. Scott McIndoe
Summary: The cross-coupling of N-tosylhydrazones and aryl halides to form carbon-carbon bonds, producing 1,1-disubstituted alkenes, has been widely used in chemistry, but its mechanism remains experimentally unexplored. The combination of benchtop NMR and real-time mass spectrometry allows for monitoring of catalytic intermediates and the rate of product formation.
DALTON TRANSACTIONS
(2021)
Article
Polymer Science
Ian C. Chagunda, Gregory T. Russell, J. Scott McIndoe
Summary: As the average molecular weight of polymers increases, mass spectrometric approaches to polymer analysis become increasingly ineffective due to factors such as signal distribution over a wider range of species, polyisotopic contributions becoming more significant, signal width increasing, and limitations caused by solubility properties and solvent adducts. These factors, along with the drop in polymer concentration during sample preparations for MALDI analysis, ultimately result in a signal-to-noise problem that restricts the ability of mass spectrometry to determine molecular weight distribution for high mass polymers.
Article
Chemistry, Organic
Bruna Papa Spadafora, Francisco Wanderson Moreira Ribeiro, Jullyane Emi Matsushima, Elaine Miho Ariga, Isaac Omari, Priscila Machado Arruda Soares, Diogo de Oliveira-Silva, Elisangela Vinhato, J. Scott McIndoe, Thiago Carita Correra, Alessandro Rodrigues
Summary: This study reports the regio- and diastereoselective synthesis of oxazolidinones via a Pd-catalyzed vicinal C-N/C-Cl bond-forming reaction from internal alkenes of allylic carbamates. The products are obtained in high yields and excellent diastereoselectivities. Detailed mechanistic studies were carried out to describe the reaction process, including the role of Cu(ii) in a C-Cl bond-forming mechanism step.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Physical
Michelle Y. C. Ting, Lars P. E. Yunker, Ian C. Chagunda, Katherine Hatlelid, Meghan Vieweg, J. Scott McIndoe
Summary: Understanding catalytic reactions is challenging due to the diverse forms catalysts take throughout the reaction. Modern mass spectrometric methods show promise in continuously probing all stages of the reaction in real time.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Anuj Joshi, Harmen S. Zijlstra, Elena Liles, Carina Concepcion, Mikko Linnolahti, J. Scott McIndoe
Summary: Using electrospray ionization mass spectrometry, the real-time synthesis of methylalumoxane (MAO) was successfully tracked, revealing rapid oligomerization within a minute followed by slow aggregation. The principal activated product from benchtop synthesis matches that observed in industrial samples.
