Article
Chemistry, Inorganic & Nuclear
Eugene V. V. Dokuchits, Tatyana Yu. Kardash, Tatyana V. V. Larina, Yuliya N. N. Bespalko, Tatyana P. P. Minyukova
Summary: Highly dispersed LaCo1-x-yCuxTiyO3/KIT-6 perovskites were synthesized with the addition of inert mesoporous KIT-6, and the KIT-6 matrix was removed to obtain highly dispersed perovskites. The dispersion of perovskites may vary depending on the largest cation and its content at the B position of the ABO(3) structure.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Maximilian Roca Jungfer, Laura Elsholz, Ulrich Abram
Summary: Optimized synthetic approaches to key technetium hydrido compounds, [TcH3(PPh3)(4)] (1) and mer-trans-[TcH(CO)(3)(PPh3)(2)] (5), have been reported, providing pure and stable complexes. The solid-state structures of these compounds have been determined, and experiments coupled with DFT calculations suggest a fluxional structure for some mixed-phosphine complexes.
Article
Chemistry, Multidisciplinary
Saidkhodzha Nematulloev, Ren-Wu Huang, Jun Yin, Aleksander Shkurenko, Chunwei Dong, Atanu Ghosh, Badriah Alamer, Rounak Naphade, Mohamed Nejib Hedhili, Partha Maity, Mohamed Eddaoudi, Omar F. Mohammed, Osman M. Bakr
Summary: This study presents a novel synthesis method for Cu NCs with bright emission in the near-infrared region and crystallization-induced emission enhancement phenomena, providing essential insights into the origins of their optical properties.
Article
Chemistry, Multidisciplinary
Xinzhang Lin, Junying Zhang, Jie Tang, Yang Yang, Chao Liu, Jiahui Huang
Summary: Atomically precise metal complexes, such as the Pt-2(S-Adam)(4)(PPh3)(2) complexes synthesized in this study, play a crucial role in controlled synthesis and catalytic applications. The crystal structure analysis revealed various packing modes of these complexes, and their UV-visible absorption spectra showed distinct absorption peaks. Moreover, these Pt complexes demonstrated high catalytic activity and selectivity in the propane dehydrogenation reaction.
Article
Chemistry, Organic
Pavel K. Elkin, Nathaniel D. Durfee, Viresh H. Rawal
Summary: The study explores the cycloaddition reactions of 1-alkoxy-1-amino-1,3-butadienes, which are prepared from crotonic acid chloride and its derivatives. These doubly activated dienes react with electron-deficient dienophiles to form cycloadducts under mild conditions, providing versatile building blocks for complex molecule synthesis. Hydrolysis of the DA cycloadducts yields 6-substituted and 6,6-disubstituted 2-cylohexenones, while the corresponding HDA cycloadducts afford 6-substituted 5,6-dihydropyran-2-ones.
Article
Chemistry, Multidisciplinary
Scott T. Shreiber, David A. Vicic
Summary: The solvated nickel complexes react with organic electrophiles to synthesize fluoroalkylated organic products. Electrochemical analysis reveals that nickel complexes can act as reservoirs of CF3 groups under certain conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ya-Nan Yang, Lei Qiao, Zhong-Ming Sun
Summary: In this study, the reactivity of homoatomic clusters [E-9](4-) (E = Si-Pb) and intermetalloid clusters [M@E-9](q-) was investigated. Two new compounds were synthesized and characterized using various analytical techniques. Quantum chemical calculations were conducted to analyze the relationships between the geometries and electronic structures of different clusters.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Duy-Khoi Dang, Damla Cehreli, Benjamin S. Rich, Terry E. Haas, Frank R. Fronczek, Rein U. Kirss
Summary: The reaction between CpRu(PPh3)(2)NCS and PMePh2, as well as the formation of isomers CpRu(PPh3)(PMePh2)NCS and CpRu(PPh3)(PMePh2)SCN, were studied. The compounds were characterized by X-ray crystallography, and the kinetics of the reaction were found to be consistent with a dissociative interchange mechanism.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Asmaa Yousofvand, Mojtaba Amini, Mojtaba Hosseinifard, Jan Janczak
Summary: A new polyoxomolybdate compound was synthesized, characterized, and used as a catalyst for the azide-alkyne cycloaddition reaction with high yields. The compound consists of [Co(H2O)6]2+ and N-methyluroptropine cations, a polyanion [C6H12N2CoMo6O24]4-, and lattice water molecules.
Article
Chemistry, Inorganic & Nuclear
Maximilian Roca Jungfer, Ulrich Abram
Summary: A new and highly reactive [Tc(OH2)(CO)(3)(PPh3)(2)](+) cation was successfully synthesized, and its ligand exchange reactions with various neutral ligands were systematically studied. The resultant complexes exhibited different levels of stability and reactivity, offering interesting possibilities for the development of Tc-99m complexes. The ready displacement of the aqua ligand highlights the synthetic value of [Tc(OH2)(CO)(3)(PPh3)(2)](+) as a reactive entry point for further studies in the field of organometallic chemistry of technetium.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Maria Victoria Toledo, Carla Jose, Carlos R. Llerena Suster, Sebastian E. Collins, Raquel Portela, Miguel A. Banares, Laura E. Briand
Summary: In this study, the esterification of rac-ibuprofen and rac-ketoprofen with glycerol using Novozym(R) 435 as the catalyst was investigated, showing different conversion rates and selectivities under various molar ratios. Molecular level analysis confirmed the reaction progress, and the interaction between CALB and ibuprofen was found to impact the structure of the lipase, potentially improving catalytic performance.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Physical
Prerna Upale, Seema Verma, Satishchandra B. Ogale
Summary: A novel nanostructure was developed to improve the performance of the oxygen evolution reaction. The NiCoFe spinel oxide nanocomposite with hierarchical porous nanowire morphology was synthesized and showed enhanced mass-transport, improved conductivity, and excellent electrochemical stability at high current density. The synergistic effects of the structural and compositional advantages contributed to the superior oxygen evolution reaction performance.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Punit Kumar, Dayadeep S. S. Monder
Summary: This study uses first principles calculations to investigate the electronic structure and catalytic activity of Ni on Pd core-shell catalysts. The results show that the adsorption of O and CO is more favorable on Ni/Pd core-shell structures compared to pure Ni surface. The energetics of O-2 dissociation and CO oxidation reactions are also studied, and it is found that both adsorption and dissociation are easier on Ni/Pd surfaces. However, CO oxidation is unfavorable on Ni/Pd compared to Ni.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Travis G. Novak, Paul A. DeSario, Michelle D. Johannes, Todd H. Brintlinger, Ryan H. DeBlock, Jeffrey W. Long, Christopher N. Chervin, Rhonda M. Stroud, Debra R. Rolison
Summary: CeO2 aerogel-supported Ni(OH)(2) nanoparticles demonstrate superior activity and stability in CO oxidation reaction. The intimate contact between Ni(OH)2 NPs and the bonded nanoparticulate CeO2 network prevents the conversion to NiO. CO has lower adsorption energy on Ni(OH)(2) compared to NiO, resulting in reduced poisoning of active surface sites.
CHEMISTRY OF MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Yan-Cheng Hu, Yingying Zhao, Boshun Wan, Qing-An Chen
Summary: Ynamides are unique alkynes with a carbon-carbon triple bond directly attached to the nitrogen atom, showing both nucleophilic and electrophilic properties which make them ideal candidates for catalytic intermolecular annulations.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Daniel Rixson, Gunes Gunay Sezer, Emre Alp, Mary F. Mahon, Andrew D. Burrows
Summary: This article investigates the metal-organic frameworks formed from the reaction between cadmium(ii) salts and the semi-rigid 5-((carboxymethyl)amino)isophthalic acid (H(3)cmai) in water. The combination of different salts leads to different frameworks. Compound 8 shows photocatalytic activity.
Article
Chemistry, Inorganic & Nuclear
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin
Summary: This study explores the reactions of a seven-membered heterocyclic potassium diamidoalumanyl with Cu(i), Ag(i), and Au(i) chloride N-heterocyclic carbene adducts, characterizing the resulting group 11-Al bonded derivatives through NMR spectroscopy and X-ray diffraction. It was found that while reactions leading to reduction of the group 11 cations to base metals were observed, solid-state authentication of an Ag-Al sigma bond was also achieved. Furthermore, the reactivity of the NHC-supported Cu, Ag, and Au alumanyl derivatives with unsaturated small molecules was assessed, with observations of asymmetric Cu-C and Ag-C bonded isomers in certain cases.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Rex S. C. Charman, Mary F. Mahon, John P. Lowe, David J. Liptrot
Summary: Three ring-expanded N-heterocyclic carbene-supported copper(I) triphenylstannyls were synthesized and characterized. Reactions with various substrates yielded copper(I) benzamidinate, benzamide and benzothiamide via phenyl transfer from the triphenylstannyl anion. However, attempts to utilize this reactivity under a catalytic regime were hindered by rapid copper(I)-catalyzed dismutation reactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Lia Sotorrios, Fedor M. Miloserdov, Anne-Frederique Pecharman, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey
Summary: The syntheses, reactivity, and electronic structure analyses of [Ru(PPh3)(2)(ZnMe)(4)H-2] and [Ru(PPh3)(2)(ZnPh)(4)H-2] are reported. [Ru(PPh3)(2)(ZnMe)(4)H-2] exhibits an 8-coordinate Ru center with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in [Ru(PPh3)(2)(ZnMe)(4)H-2] undergo facile, sequential exchange with ZnPh2 to give [Ru(PPh3)(2)(ZnPh)(4)H-2], which shows a 3 : 1 arrangement of ZnPh ligands. Mechanisms for ZnMe/ZnPh exchange and isomerization are proposed using DFT calculations, and the relationships of these {Ru(ZnR)(4)H-2} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Connie J. Isaac, Fedor M. Miloserdov, Anne-Frederique Pecharman, John P. Lowe, Claire L. McMullin, Michael K. Whittlesey
Summary: The reaction pathways between [Ru(PPh3)(C6H4PPh2)(2)H][Li(THF)(2)] and AlMe2Cl or SnMe3Cl have been investigated. It was found that complete reactions occurred at different temperatures to yield spectroscopically characterized trihydride complexes. In the presence of CO, complex 6 underwent a series of transformations to form an acylated phosphine complex. Complex 6 also reacted with an N-heterocydic carbene through addition and substitution reactions.
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Emma Richards
Summary: Ionic compounds containing sodium cations are known for their stability and resistance to redox reactivity. However, when treated with non-reducible organic bases, a low oxidation state {Mg2Na2} species undergoes selective extrusion of sodium metal and oxidation of the Mg-I centers. Quantum chemical studies indicate that intramolecular electron transfer is facilitated by the molecular orbitals of the {Mg2Na2} ensemble.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Laura E. English, Thomas M. Horsley Downie, Catherine L. Lyall, Mary F. Mahon, Claire L. McMullin, Samuel E. Neale, Carla M. Saunders, David J. Liptrot
Summary: The (IPr)CuOtBu catalysed reduction of 11 aryl and alkyl isocyanates with pinacolborane resulted in the formation of boraformamides, pinBN(R)C(O)H, in most cases. Overreduction was observed only for electron poor aryl isocyanates (4-NC-C6H4NCO, 4-F3C-C6H4NCO, 3-O2N-C6H4NCO). Computational analysis revealed that the stability of [(IPr)CuH](2), proposed as the catalyst resting state, influences selectivity and offers a potential solution to prevent overreduction in future work. In the case of iPrNCO, the formation of [(IPr)CuH](2) prevents overreduction kinetically. However, for 4-NC-C6H4NCO, the barrier height for the first step of overreduction is much lower, resulting in unselective reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kyle G. G. Pearce, Michael S. S. Hill, Mary F. F. Mahon
Summary: Reaction of BeCl2 with dilithium diamide yields the dimeric chloroberyllate, leading to the formation of a 2-coordinate beryllium amide. Reduction of the beryllium amide using lithium or sodium in benzene produces relevant organoberyllate products, likely through transient Be(i) radicals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Henry T. W. Shere, Michael S. Hill, Samuel E. Neale, Mary F. Mahon, Claire L. McMullin, Andrew S. S. Wilson
Summary: This article investigates the contrasting reactivities of molecular beta-diketiminato (BDI) calcium hydride and n-hexyl derivatives towards bis(pinacolato)diboron (B(2)pin(2)). The study finds that the dimeric calcium hydride forms an unusual diborane(6) dianion, while the initially dimeric organocalcium reagent converts to a calcium diboranate monomer. Attempts to induce heterolysis of the B-B bond in the calcium diboranate monomer were unsuccessful, resulting in either dismutation or the generation of N-donor adduct derivatives. These different reactivities can be explained by density functional theory (DFT) calculations, which attribute them to the larger radius and lower steric congestion of the third-row group 2 cation.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Erika M. Roberts, Fedor M. Miloserdov, Victor Varela-Izquierdo, Mary F. Mahon, Michael K. Whittlesey
Summary: The addition of excess ZnMe2 to a mixture of [Ru(PPh3)(3)HCl] and IMes resulted in the formation of a bis-cyclometallated complex [Ru(IMes)(PPh3)(2)] 2 and a mono-cyclometallated Ru-Zn heterobimetallic complex [Ru(IMes)'(PPh3)(2)(ZnMe)] 3. Further reactions of these complexes with H-2, PhSiH3, pinacolborane, and CO were investigated. Compounds 1, 4, 5, and 6 were synthesized and structurally characterized.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Rosalyn L. Falconer, Esme Owen, Michael J. Cowley, John P. Lowe, Claire L. McMullin, Mary F. Mahon, Michael K. Whittlesey
Summary: Treatment of [Ru(L)(PPh3)2(CO)H2] (L = PPh3, IMes) with an N-mesityl amidophosphine aluminium dihydride complex (Al(P-N)H2) gives [Ru(PPh3)2(CO)H3{Al(P-N)H}] (2) and [Ru(IMes)(PPh3)(CO)H3{Al(P-N)H}] (4), which are present in solution as mixtures of diastereomers. Crystal structure determinations and density functional theory (DFT) calculations suggest both 2 and 4 can be formulated as [Ru(L)(PPh3)(CO)H3][Al(P-N)H] complexes with bridging hydride ligands.
Article
Chemistry, Inorganic & Nuclear
Henry T. W. Shere, Michael S. Hill, Mary F. Mahon
Summary: This contribution describes the formation of homonuclear sigma bonding between boron mediated by alkaline earth metals. The reaction between alkaline earth bis-(trimethylsilyl)amides and bis(pinacolato)diboron resulted in the formation of group 2 silazide diborane adducts. Further reaction with bis(pinacolato)diboron led to the formation of bis-triboranate derivatives. These complexes provide rare examples of catena-boron species with propagated B-B bonds beyond the common diboranes.
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Benjamin L. Morrison
Summary: [{SiNDipp}MgNa](2) reacts directly with H-2 to form a heterobimetallic hydride. Computational density functional theory (DFT) studies suggest that this reactivity is initiated by orbitally-constrained sigma(Mg-Mg)-> sigma*(H-H) and sigma(H-H) -> n*(Na(3s)) interactions between the frontier MOs of both H-2 and the tetrametallic core of [{SiNDipp}MgNa](2).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin
Summary: The copper(i) alumanyl derivative reacts with up to three equivalents of various terminal alkynes, resulting in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate, and bis(alkynyl)aluminate derivatives. The alkene liberation process in the latter step is a unique case of alkyne transfer semi-hydrogenation.
