Article
Chemistry, Multidisciplinary
Tsz-Fai Leung, Dandan Jiang, Ming-Chun Wu, Dengmengfei Xiao, Wei-Min Ching, Glenn P. A. Yap, Tao Yang, Lili Zhao, Tiow-Gan Ong, Gernot Frenking
Summary: Diatomic C-2 is a highly reactive species that has been stabilized and studied using a specific ligand method, despite being difficult to isolate in the condensed phase in the past. Experimental and quantum chemical analysis showed that both carbon atoms of this complex have carbene character and exhibit specific reactivity.
Article
Chemistry, Multidisciplinary
Jinghang Shen, Thayalan Rajeshkumar, Genfeng Feng, Yue Zhao, Shuao Wang, Laurent Maron, Congqing Zhu
Summary: We report a new method for the synthesis of molecular uranium complexes featuring a cis-[M ->-> U <-<- M] core. The complexes were prepared by reacting [{U{N(CH3)((CH2CH2NPPr2)-Pr-i)(2)}(Cl)(2)[(mu-Cl)M(COD)](2)}] (M=Rh, Ir) with MeMgBr or MeLi. Theoretical calculations confirmed the presence of two U <-<- M double dative bonds in these complexes. This study enriches the chemistry of U <-<- M multiple bonds and provides an opportunity to explore the bonding of actinide elements.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Hao Tang, Yang Xiang, Huahan Zhan, Yinghui Zhou, Junyong Kang
Summary: Using density functional theory (DFT), the adsorption energy, charge density, and density of states of HCl gas adsorbed on graphene and six different transition metal-doped graphenes (TMDGs) were investigated. It was found that TMDGs have higher adsorption energy and chemical adsorption capacity compared to graphene. Among the TMDGs, Fe-doped graphene demonstrated the best adsorption capacity and stability, while Mn- and Co-doped graphenes showed magnetic changes after HCl adsorption. Mn-doped graphene exhibited fast responsiveness and recovery time at a certain temperature, making it the most suitable material for HCl gas detection.
DIAMOND AND RELATED MATERIALS
(2023)
Article
Chemistry, Physical
Abdulrahman Allangawi, Mazhar Amjad Gilani, Khurshid Ayub, Tariq Mahmood
Summary: Doping of late first-row transition metals on B12P12 and Al12P12 nano-cages as single atom catalysts (SACs) was studied using density functional theory (DFT) calculations. All transition metals were chemisorbed on the support, with interaction energies ranging from -0.65 to -3.85 eV. The designed Ni@Al12P12, Ni@B12P12, and Co@B12P12 SACs showed great potential as noble metal-free, sufficiently stable, and highly efficient electrocatalysts for hydrogen evolution reaction.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Physical
Shuoqi Zhang, Rong Gu, Shigeyoshi Sakaki, Guixiang Zeng
Summary: The mechanism of the N-N cross-coupling of nitroarene and aniline catalyzed by 1,2,2,3,4,4-hexamethylphosphetane oxide (1PO) was investigated using DFT and DLPNO-CCSD(T) calculations. The study revealed the formation of active species 1P through deoxygenation of 1PO and the extraction of one oxygen atom from nitroarene to produce nitrosoarene. The formation of azo-cation intermediate and stable hydrazinylphosphonium species were also identified. The study proposed that substitution of a dimethylamino group for the methyl group in 1P could improve its activity.
Review
Chemistry, Applied
Priyanka Chaudhary, Jeyakumar Kandasamy, Allan Patrick G. Macabeo, Ramuel John Inductivo Tamargo, Yong Rok Lee
Summary: This review explores the recent advancements in the C-H functionalization of N-nitrosoanilines, highlighting the versatility of nitroso group as a directing group for ortho C-H activation and introducing various functional groups to generate aromatic derivatives with diverse properties. The reaction mechanisms for different transition metal-catalyzed functionalizations are discussed in detail, showcasing their potential for synthesizing valuable intermediates and unique heterocyclic compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Analytical
Muhammad Kashif Saleem, Niaz Ahmad Niaz, Khaled Fahmi Fawy, Shaimaa A. M. Abdelmohsen, Meznah M. Alanazi, Fayyaz Hussain, Muhammad Naeem Ashiq, Umbreen Rasheed, Yasir Abbas, Muhammad Shuaib Khan
Summary: In this study, Ni-Co-Fe3O4 nanospheres were synthesized via a simple hydrothermal approach and evaluated as electrocatalysts for the oxygen evolution reaction (OER). Characterization confirmed the successful co-doping of Ni and Co into Fe3O4. The Ni-Co-Fe3O4 nanospheres exhibited enhanced electrochemical properties compared to Fe3O4, Co-Fe3O4, and Ni-Fe3O4. At a current density of 10 mA cm-2, the Ni-Co-Fe3O4 electrocatalyst showed a lower overpotential of 243 mV and a tafel value of 54.84 mV dec-1. Additionally, Ni-Co-Fe3O4 demonstrated excellent electrochemical stability in 1 M potassium hydroxide solution for 25 hours. The outstanding OER activity of Ni-Co-Fe3O4 can be attributed to its unique morphology and lower hydroxyl ion adhesion energy. This research provides a promising option for future electrode nanomaterials based on transition metal oxides for water electrolysis applications.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Applied
Yongchao Yang, Leo Lai, Li Wei, Yuan Chen
Summary: Atomically dispersed transition metal and nitrogen co-doped carbon electrocatalysts show great potential in electrochemical conversion and energy storage, but their commercialization is hindered by rapid degradation. Current understanding of their active sites and degradation mechanisms is still limited.
JOURNAL OF ENERGY CHEMISTRY
(2021)
Article
Chemistry, Physical
Amlan J. Kalita, Shahnaz S. Rohman, Chayanika Kashyap, Sabnam S. Ullah, Indrani Baruah, Lakhya J. Mazumder, Prem P. Sahu, Ankur K. Guha
Summary: This study reports the unprecedented quadruple bonding between a silicon atom and a transition metal fragment in the (1)A(1) electronic ground state of C-3v symmetric SiRu(CO)(3), involving one usual Si-Ru sigma bond, two usual Si-Ru pi bonds, and one additional Si -> Ru dative sigma bond. Bonding analyses reveal the nature of the Si(sic)Ru quadruple bonding interaction.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
R. Eric Sikma, Seth M. Cohen
Summary: This study reports the rational design and synthesis of three-dimensional metal-organic frameworks (MOFs) with Pd-0 and Pt-0 nodes using tetratopic phosphine ligands. Five new MOFs have been synthesized by varying the phosphine ligands and metal precursors, and they are the first examples of phosphine-metal bonded MOFs. These MOFs exhibit solid-state luminescence with significantly red-shifted emission maxima compared to Pd(PPh3)(4). Additionally, a Rh-I low-valent coordination solid based on the same linker design is reported, which displays solid-state luminescence not observed in the molecular analogue.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Gaurav Awasthi, Pawan Kumar
Summary: In this study, four 1,3,5-tricarboxylic benzoic acid-based metal organic frameworks (BTC-MOFs) were synthesized using Fe, Ni, Cu, and Zn as metal ions and 1,3,5-tricarboxylic benzoic acid as organic linkers in an aqueous medium. The structural features of BTC-MOFs were confirmed through morphological and spectroscopic analysis. A comparison study was conducted on the water stability and absorption capacity of BTC-MOF at different temperatures, and it was found that Fe-BTC had the highest water stable structure among the four BTC-MOFs.
Article
Chemistry, Physical
Jing-Jing Zhong, Shi-Ping Huang, Jia-Fang Gu, Yi Li, Kai-Ning Ding, Yong-Fan Zhang, Wei Lin, Wen-Kai Chen
Summary: Converting hydrogen into liquid ammonia is an efficient method for its storage, transport, and utilization. The study investigates the catalytic electro-oxidation of liquid ammonia on surfaces of transition metal dimer anchored in g-CN monolayer and finds that Rh and Ir atoms exhibit excellent performance for the hydrogen evolution reaction, suggesting their potential as efficient bifunctional catalysts.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Jayasmita Jana, K. C. Bhamu, Yen-Linh Thi Ngo, Sung Gu Kang, Jin Suk Chung, Seung Hyun Hur
Summary: Bimetallic ZnO-Ni(OH)2 composite materials were prepared as efficient catalysts for the oxygen evolution reaction (OER) in electrocatalytic water splitting. Utilizing a hydrothermal process assisted by PVP and dopamine, the catalyst ZNDP-1 with a 3D interconnected structure showed low over potential and high stability in alkaline medium. DFT studies revealed the mechanistic pathway of the catalyst.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Physical
Cagil Kaderoglu, Amir Nasser Shamkhali, Fatemeh Safdari, Marjan Abedi, Sinasi Elliatioglu
Summary: Plasmonic properties of transition metal atoms on graphene surfaces were studied, showing blue shifts of in-plane plasmon peaks after CO adsorption and different characteristics between metal adatom and CO adsorption.
APPLIED SURFACE SCIENCE
(2021)
Review
Chemistry, Physical
DeGuang Liu, ZheYuan Xu, HaiZhu Yu, Yao Fu
Summary: In recent decades, density functional theory (DFT) calculations have been extensively used to investigate the mechanisms of transition metal-catalyzed C-O activation reactions. These studies provide valuable insights into the structure-reactivity/selectivity correlations through theoretical simulations and energy profile analysis. Alcohols, derived from biomass and affordable, have been extensively studied in organic synthesis. This review provides a brief overview of DFT studies conducted since 2017 on C-OH bond activation of alcohols catalyzed by transition metals, covering four main categories: free radical cleavage, metal insertion, nucleophilic attack, and β-OH elimination. Promising strategies and future research directions in this field are also discussed.
Article
Chemistry, Applied
Immanuel Reim, Giovanni Occhipinti, Karl W. Tornroos, Deryn E. Fogg, Vidar R. Jensen
Summary: The study focused on the challenging selective transformation of 1-alkenes into E-olefins, designing a series of catalysts with high E-selectivity. By synthesizing Ru21a-c catalysts with specific ligand orientations and analyzing the reaction mechanism through DFT, guidelines were established for pursuing E-selective 1-alkene metathesis.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Physical
Irina Minenkova, Arseniy A. Otlyotov, Luigi Cavallo, Yury Minenkov
Summary: This study introduces a protocol for predicting the accurate gas-phase enthalpies of formation of polycyclic aromatic hydrocarbons through a two-step scheme. The calculated values provide deviations with respect to the literature and experimental data, emphasizing the importance of computational chemistry approaches.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Astronomy & Astrophysics
I Nardecchia, Y. Minenkov, M. Lorenzini, L. Aiello, E. Cesarini, D. Lumaca, V Malvezzi, F. Paoletti, A. Rocchi, V Fafone
Summary: The optical design of advanced gravitational wave interferometers places increasingly stringent requirements on the components. Thermal effects and deviation of components from specifications need to be addressed to recover the ideal operation of the detector. Ring heaters are thermally coupled actuators designed to tune the radius of curvature of mirrors, and this paper describes the design features and performances of the ring heaters installed in the Advanced Virgo detector.
CLASSICAL AND QUANTUM GRAVITY
(2023)
Article
Chemistry, Inorganic & Nuclear
Arseniy A. Otlyotov, Yury Minenkov, Luigi Cavallo
Summary: An approach to estimate the uncertainty of calculated Gibbs free energy of transfer has been developed and suggested as a measure of reliability. The Na+ free energies of transfer from water to 18 solvents have been assessed, revealing thermodynamic instability for Na+(S)n clusters in certain solvents. Discrepancies in experimental values for certain compounds were resolved and a statistical analysis showed good correlation and deviation with recommended values.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Maxim A. Maltsev, Svetlana A. Aksenova, Igor V. Morozov, Yury Minenkov, Evgenia L. Osina
Summary: In this study, ab initio simulations were conducted to obtain the interatomic interaction potentials for ArN and ArN+ in both ground and excited states. These potentials were then used to calculate the vibrational-rotational partition functions and thermodynamic properties of these molecules in the gas phase at temperatures ranging from 298.15 to 10,000 K. The errors associated with the approximation of interatomic interaction potentials were also estimated for the thermodynamic functions.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yury Minenkov, Luigi Cavallo, Kirk A. Peterson
Summary: The impact of complete basis set extrapolation schemes, diffuse functions, and tight weighted core functions on predicted enthalpies of formation via the DLPNO-CCSD(T1) approach has been investigated for neutral H,C,O-compounds. The results show that all tested extrapolation schemes have a mean unsigned deviation below 2 kJ mol(-1) relative to the experiment. The influence of tight weighted core functions on atomization energies is small, and core-valence correlation effects converge at triple-zeta level. The effect of diffuse function augmentation converges slowly and cannot be reproduced accurately with double-zeta or triple-zeta calculations.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Arseniy A. Otlyotov, Yury Minenkov
Summary: The experimental gas-phase thermochemistry of alkali metal reactions with acetonitrile/ammonia is reproduced. Three approximations are tested and the modified scaled RRHO scheme (msRRHO) provides the most accurate reaction entropies. The msRRHO approach is also used to calculate the enthalpy contribution and reaction Gibbs free energies, ensuring internal consistency. The final increment Gibbs free energy MUEs for msRRHO, sRRHO(100) and sRRHO schemes are 1.2, 3.6 and 3.1 kcal mol(-1).
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Jonas Himmelstrup, Vidar R. Jensen
Summary: Samarium diiodide (SmI2) is an important reductant used in various applications. However, the prediction of its redox and proton-coupled electron transfer reactions using conventional density functional approximations is highly inaccurate. The discrepancy is mainly due to the delocalization error, which leads to destabilization of Sm(III) compared to Sm(II). Including spin-orbit coupling and virtual orbitals in the calculations can help reduce the error. Parametrized double-hybrid methods show promise in further developing the chemistry of SmI2.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Xinrui Ou, Giovanni Occhipinti, Eliza-Jayne Y. Boisvert, Vidar R. Jensen, Deryn E. Fogg
Summary: Ruthenium catalysts bearing cyclic (alkyl)(amino)carbene (CAAC) ligands are highly efficient in olefin metathesis due to their resistance to decomposition. However, turnover numbers in the metathesis of terminal olefins are sensitive to catalyst concentration due to the susceptibility of the methylidene species to decomposition. Understanding the partitioning of CAAC complexes between the precatalyst and the active species is critical for catalyst design.
Article
Chemistry, Physical
Yury Minenkov
Summary: This study presents an alternative continuum model implementation for calculating solvation free energy. The electrostatic contribution is calculated using the noniterative conductor-like screening model, whereas the non-electrostatic interactions are computed through the Caillet-Claverie atom-atom potential method. The method shows good performance in reproducing solvation free energies in both absolute and relative cases, making it suitable for nonaqueous solvents.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Arseniy A. Otlyotov, Daniil Itkis, Lada V. Yashina, Luigi Cavallo, Yury Minenkov
Summary: Sodium cation solvation Gibbs free energies were calculated in various solvents using a refined computational protocol. The method involved conformational search, density functional theory, and cluster coupled cluster calculations, leading to accurate predictions with high correlation to experimental data.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Giovanni Occhipinti, Daniel L. Nascimento, Marco Foscato, Deryn E. Fogg, Vidar R. Jensen
Summary: This study investigates the factors promoting or inhibiting β-H elimination in the metathesis of alcohols and styrene using silicon-cyclic (alkyl)(amino)carbene (CAAC) catalysts and N-heterocyclic carbene (NHC) catalysts. The results show that CAAC catalysts have a stronger trans effect, which inhibits β-H elimination. However, the strong trans effect of CAAC catalysts also accelerates other decomposition pathways of the catalyst.