Article
Chemistry, Multidisciplinary
Nikolaus Gorgas, Andrew J. P. White, Mark R. Crimmin
Summary: The reactions of transition metal complexes involve the participation of molecular orbitals centered on the transition metal. However, this study found that including an aluminum-based ligand in a low-spin iron complex can lead to unexpected reactivity, specifically the intermolecular C-H bond activation of pyridines. Mechanistic analysis suggests that C-H activation proceeds through a reductive deprotonation, with the Fe and Al acting as a frustrated Lewis pair. These findings have important implications for the design of reagents and catalysts based on first-row transition metals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zeynab Imani, Venkateswara Rao Mundlapati, Valerie Brenner, Eric Gloaguen, Katia Le Barbu-Debus, Anne Zehnacker-Rentien, Sylvie Robin, David J. Aitken, Michel Mons
Summary: The delta conformation, a local secondary structure in proteins, is stabilized by specific side-chain/backbone N-H interactions in derivatives of a cyclic amino acid with a sulphur atom in the gamma-position. This allows the delta conformation to compete with classical C5 and C7 hydrogen bonded conformers, expanding the range of small-molecule models beyond rigid proline-type compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jia Dong, Jerome R. Robinson, Ze-Hua Gao, Lai-Sheng Wang
Summary: This study reports the synthesis of a new undecagold cluster with a bidentate phosphine ligand. The cluster can undergo hydroauration reaction with alkynes containing electronwithdrawing groups, forming key gold-alkenyl semihydrogenation intermediates, which can be selectively converted to Z-alkenes under acidic conditions. By isolating and characterizing the intermediates, atomic-level insights into the active sites and mechanisms of semihydrogenation reactions catalyzed by gold-based nanomaterials are provided.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nisha Kamboj, Ghanshyam Mali, Prem Lama, Rohan D. Erande, Ramesh K. Metre
Summary: This paper reports the synthesis of a copper complex based on the phenalenyl unit and its application in the oxidation reactions of important organic compounds. The complex shows dual activity and can react under mild conditions.
Article
Chemistry, Inorganic & Nuclear
Nisha K. Agrawal, S. Gayathridevi, Soumya R. Dash, Kumar Vanka, Balaji R. Jagirdar
Summary: Treatment of trans-[Ir(H)(N)(2)((iPr)4)(POCOP)(DMAP)][BAr4f] with H-2 under ambient conditions resulted in the formation of trans-[Ir(H)(?(2)-H-2)((iPr)4)(POCOP)(DMAP)][BAr4f]. Computational studies suggest that the exchange of hydrogen atoms between H-2 and the hydride ligands involves metal-ligand cooperativity.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Md Estak Ahmed, Mahdi Raghibi Boroujeni, Pokhraj Ghosh, Christine Greene, Subrata Kundu, Jeffery A. Bertke, Timothy H. Warren
Summary: This study reports a novel copper catalyst for the oxidation of ammonia to dinitrogen under homogeneous conditions. The catalyst shows high efficiency and stability for ammonia oxidation under moderate overpotential. Mechanistic investigations reveal the involvement of oxidation and deprotonation processes in the catalytic transformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Esko Salojarvi, Anssi Peuronen, Jani Moilanen, Hannu Huhtinen, Johan Linden, Akseli Mansikkamaki, Mika Lastusaari, Ari Lehtonen
Summary: This study reports the syntheses of two iron complexes and their magnetic properties. The first complex has a diamagnetic ground state due to strong antiferromagnetic coupling between a low-spin Fe(iii) ion and a radical ligand. The second complex undergoes a thermally induced process when crystalline, with some molecules changing to a diamagnetic low-spin state.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Stephan M. Rummelt, Paul O. Peterson, Hongyu Zhong, Paul J. Chirik
Summary: The study demonstrates the two-electron oxidative addition of aryl and alkyl halides to a reduced iron dinitrogen complex with a strong-field tridentate pincer ligand. Results show that the relative rate of oxidative addition of aryl halides varies with the halide type, and the pathways for obtaining products differ for different substrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Diego Sorbelli, Leonardo Belpassi, Paola Belanzoni
Summary: A gold-aluminyl complex has been reported to have an unconventional gold nucleophilic center, with the reaction mechanism found to be cooperative. The Au-Al bond is primarily of an electron-sharing nature, with the metal fragments displaying a diradical-like reactivity with CO2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jiarui Chang, Man Ding, Jia-Xue Mao, Jie Zhang, Xuenian Chen
Summary: A palladium(ii) hydride complex supported by a benzene-based PNCNP pincer ligand has been synthesized via two different routes and exhibits strong deprotonating ability and versatile catalytic activity. It can readily deprotonate acetamide to form the corresponding acetamido complex and catalyze the dehydrogenation of methanol to formaldehyde under mild conditions, as well as the direct hydration of nitriles to primary amides. The direct hydration of nitriles catalyzed by this complex is the most efficient palladium catalytic system for this type of reaction, achieving 100% selectivity and good to excellent yields.
DALTON TRANSACTIONS
(2022)
Article
Multidisciplinary Sciences
Teng-Xiang Huang, Bin Dong, Seth L. Filbrun, Aisha Ahmad Okmi, Xiaodong Cheng, Meek Yang, Nourhan Mansour, Sidong Lei, Ning Fang
Summary: By gaining insight into the catalytic dynamics at individual structural defects of two-dimensional materials, we quantitatively revealed heterogeneous photocatalytic dynamics and surface diffusion behaviors, finding that vacancies exhibit the highest catalytic activity and more active defects have lower reactant adsorption strength and slower product dissociation/diffusion rates.
Article
Chemistry, Multidisciplinary
Yangbin Shen, Luqi Wang, Ziwen Xu, Fandi Ning, Yulu Zhan, Chuang Bai, Xiaochun Zhou
Summary: This study successfully developed a novel reaction pathway for low-temperature methanol reforming through synergistic catalysis, improving hydrogen production efficiency and showing potential for commercial applications.
Article
Chemistry, Multidisciplinary
Claire G. Page, Simon J. Cooper, Jacob S. DeHovitz, Daniel G. Oblinsky, Kyle F. Biegasiewicz, Alyssa H. Antropow, Kurt W. Armbrust, J. Michael Ellis, Lawrence G. Hamann, Evan J. Horn, Kevin M. Oberg, Gregory D. Scholes, Todd K. Hyster
Summary: This study presents a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. A unique mechanism involving a charge-transfer complex formed between an alkene, alpha-chloroamide, and flavin hydroquinone ensures radical formation only occurs when both substrates are present within the protein active site. This work demonstrates the potential for new biocatalytic transformations enabled by photoenzymatic catalysis through previously unknown electron transfer mechanisms.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Yu-Shan Zhang, Zhen Huan, Jin-Dong Yang, Jin-Pei Cheng
Summary: The unique heterocyclic skeletons of N-heterocyclic phosphines (NHPs) make them have excellent hydridic reactivity. Recently, their applications in radical reductions, particularly in a catalytic fashion, have become a promising cutting-edge area. This new reaction pattern, different but complementary to the traditional hydride pathway, can greatly expand the reaction scope.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Alexander Y. Samuilov, Yakov D. Samuilov
THEORETICAL CHEMISTRY ACCOUNTS
(2019)
Article
Chemistry, Organic
A. Ya. Samuilov, M. V. Korshunov, Ya. D. Samuilov
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Physical
A. Ya Samuilov, D. R. Alekbaev, Ya D. Samuilov
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
(2019)
Article
Polymer Science
A. Ya. Samuilov, M. V. Korshunov, Ya. D. Samuilov
POLYMER SCIENCE SERIES B
(2020)
Article
Thermodynamics
Alexander Y. Samuilov, Yakov D. Samuilov
Summary: The interaction of urea and carbamic acid methyl ester with different degrees of association of methanol to form products was investigated using density functional methods. Results showed that enthalpies and entropies of transformations increase with an increase in the degree of association of alcohol, and the free energy changes of the reactions are mainly controlled by the entropy term.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2021)
Article
Chemistry, Physical
Alexander Y. Y. Samuilov, Yakov D. D. Samuilov
Summary: The complex process of methanolysis of urea with the formation of O-methylcarbamate was investigated in this study. It was found that the reaction consists of multiple stages, with the decomposition of urea to isocyanic acid and ammonia catalyzed by alcohol molecules being the first stage. In the second stage, it was observed that the methanol dimer exhibits higher activity compared to the monomer, and the main route for the formation of O-methylcarbamate is the reaction between isocyanic acid and methanol catalyzed by the carbamate itself.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Physical
A. Ya Samuilov, Ya D. Samuilov
Summary: Theoretical studies show that the reactions of urea and methanol to form O-methyl carbamate and dimethyl carbonate proceed through a concerted mechanism. Reactions involving methanol monomers are not favorable pathways for product formation. The rate-determining step for the formation of dimethyl carbonate is the interaction between O-methyl carbamate and methanol associates.
Article
Chemistry, Physical
A. Ya Samuilov, Ya D. Samuilov
Summary: Quantum-chemical methods were used to study the mechanism and thermodynamic parameters of the reactions between dimethyl carbonate and methylamine. It was found that these transformations proceed through cyclic transition states, and the formation of a complex in the catalytic reactions results in significant orbital interactions.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
