Article
Chemistry, Physical
Dmitri G. Fedorov
Summary: A method for electron density calculations in the fragment molecular orbital method with periodic boundary conditions has been developed, studying the effects of binding in molecular systems on electron density, including polarization and charge transfer. The formation of hydrogen bonds is particularly elucidated in terms of density changes.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Joseph M. M. Parr, Andreas Phanopoulos, Aaranjah Vickneswaran, Mark R. R. Crimmin
Summary: Activation of C-C sigma-bonds within strained three- and four-membered hydrocarbons at electrophilic Mg and Zn centres was achieved. A two-step process involving hydrometalation of a methylidene cycloalkane followed by intramolecular C-C bond activation was employed. The reactivity is sensitive to ring size, with smaller rings favoring C-C bond activation. The mechanism involves beta-alkyl migration, which is more facile for Mg compared to Zn due to stabilizing interactions between the metal center and the hydrocarbon ring-system.
Article
Biochemistry & Molecular Biology
Seyede Mahtab Hosseini, Azim Soltanabadi, Majid Abdouss, Saeedeh Mazinani
Summary: In this study, density functional theory was used to investigate the adsorption of Folic acid on a carrier made from graphene oxide/chitosan composite. The results showed that in the GO-CS structure, two chitosan molecules were connected to the GO molecule on opposite sides with maximum distance between them. The interaction through hydrogen bonds between molecules was determined, providing insights into the stability of the formed pairs.
JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS
(2022)
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
Dulanjali S. Thennakoon, Marat R. Talipov, Chae S. Yi
Summary: A highly selective C-C bond cleavage method was developed for enones using a ruthenium-catalyzed deaminative coupling reaction with simple amines. When enones were coupled with anilines, a regioselective C-alpha-C-beta bond cleavage of enones was achieved, leading to the formation of N-alkylanilines and 2,4-disubstituted quinolines. The reaction mechanism was elucidated through experimental studies and DFT calculations.
Article
Multidisciplinary Sciences
Pan-Pan Chen, Peter Wipf, K. N. Houk
Summary: Quantum mechanical DFT calculations in this study reveal the concerted reaction mechanism of Rh(I)-catalyzed cycloisomerizations of bicyclo[1.1.0]butanes, which is driven by strain-release and selectively influenced by ligands to control the formation of reaction products.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Xin Huang, Tatiana Besset, Philippe Jubault, Samuel Couve-Bonnaire
Summary: In this study, the phosphorus-Michael addition (PMA) was reported for the first time on alpha-trifluoromethylacrylates and alpha-fluoromethylacrylates. The reaction showed high tolerance towards the substrates and yielded original products with good to excellent yields and diastereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Mengna Bai, Erguang Huo, Yanyan Sun, Shukun Wang, Yunfeng Zhao, Qingfa Zhang, Chenxi Wang, Rongge Zou, Moriko Qian, Hanwu Lei
Summary: In this study, the supercritical water co-gasification mechanism of lignin and LDPE was investigated using ReaxFF molecular dynamic simulations. The co-gasification process, the impacts of lignin content and temperature on the co-gasification were analyzed. The interaction mechanism between H2O and lignin, H2O and phenols in the co-gasification process was also studied. The results showed that CO and H2 were the primary products, with H2 having a higher proportion. The cracking of lignin and LDPE was the first step, forming C5-C10 products and waxes. Increasing the feedstock proportion facilitated the formation of CO and H2. The hydrogen bond formed between lignin and H2O improved the pyrolysis of lignin. This study provides a viable and green route to convert biomass and waste plastics to syngas.
FUEL PROCESSING TECHNOLOGY
(2023)
Article
Multidisciplinary Sciences
Zhengyi Wan, Yurui Gao, Xiangyu Chen, Xiao Cheng Zeng, Joseph S. Francisco, Chongqin Zhu
Summary: This study reveals the anomalous transport behavior of water through carbon nanotubes (CNTs) based on molecular dynamics simulations. The flow rate of water through CNTs with specific diameters exhibits a marked increase followed by a decrease or slight change as the CNT length increases. This behavior is attributed to the mechanical stability of the transient hydrogen-bonding chain connecting water molecules inside and outside the CNTs.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Jun Zhu, Rui Zhang, Guangbin Dong
Summary: A rare reversible C-C single-bond metathesis reaction catalyzed by ruthenium was reported, enabling the synthesis of biaryl compounds under redox-neutral and pH-neutral conditions. The reaction mode involves unexpected 18-electron closed-shell intermediates and is expected to inspire the development of more general C-C single-bond metathesis and orthogonal cross-coupling reactions.
Article
Energy & Fuels
Chaitanya Gend, Ajay Chaudhari
Summary: In this study, the hydrogen uptake properties of Be doped carbon nanoring structures were investigated using density functional theory. The results showed that the doping of Be enhanced the stability of the carbon nanoring structures and increased their hydrogen adsorption capacity. The position of the doping site affected the number of hydrogen molecules adsorbed and the hydrogen uptake capacity.
JOURNAL OF ENERGY STORAGE
(2022)
Article
Chemistry, Physical
Riccardo Capelli, Francesco Muniz-Miranda, Giovanni M. Pavan
Summary: Despite significant efforts, simulating water still poses challenges and questions. By utilizing a data-driven approach, this study reveals that classical models can capture the formation of transient ice-like environments in liquid water, consistent with recent ab initio calculations.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Antony P. Y. Chan, Martin Jakoobi, Chenxu Wang, Robert T. O'Neill, Gulsevim S. S. Aydin, Nathan Halcovitch, Roman Boulatov, Alexey G. Sergeev
Summary: This study reports highly selective ortho-C-H activation in alkylarenes by simple iridium complexes. The capacity of the alkyl substituent to override the typical preference of metal-mediated C-H activation for the least hindered aromatic C-H bonds results from transient insertion of iridium into the benzylic C-H bond. The described chemistry represents a conceptually new alternative to existing approaches for aromatic C-H bond activation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Antony P. Y. Chan, Martin Jakoobi, Chenxu Wang, Robert T. O'Neill, Gulsevim S. S. Aydin, Nathan Halcovitch, Roman Boulatov, Alexey G. Sergeev
Summary: Highly selective ortho-C-H activation in alkylarenes can be achieved by simple iridium complexes, which override the typical preference for activation of the least hindered aromatic C-H bonds. This new approach enables fast iridium insertion into the ortho-C-H bond and regeneration of the benzylic C-H bond, offering a conceptually new alternative to existing methods for aromatic C-H bond activation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Atsushi Seki, Yoshiaki Takahashi
Summary: Through the use of TBBQ as a promoter, alkenylation of N-picolinoylcycloalkylamines with alkenyl iodides can be achieved with up to 82% yield. However, for macrocyclic substrates, the stereoselectivity of the reaction product is influenced by the size of the substrate ring.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Samuel R. Zarcone, Gong M. Chu, Andreas Ehnbom, Ashley Cardenal, Tobias Fiedler, Nattamai Bhuvanesh, Michael B. Hall, John A. Gladysz
Summary: The passage discusses the formation of iron phosphorus complexes through reactions of conjugated diene ligands and diphosphines, with specific crystal structures showing unique molecular configurations.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Taveechai Wititsuwannakul, Michael B. Hall, John A. Gladysz
Summary: The dichloromethane ligand in [(η^5-C5H5)Re(NO)(PPh3)(ClCH2Cl)](+)X- can undergo displacement by various ligands with different reaction pathways, resulting in retention of configuration at rhenium. The substitution reactions can be categorized into concerted frontside displacements with stronger nucleophiles and neighboring group participation with weaker nucleophiles, as studied by density functional theory.
Article
Chemistry, Inorganic & Nuclear
Xuemei Yang, Christopher R. DeLaney, Kyle T. Burns, Lindy C. Elrod, Wenting Mo, Haley Naumann, Nattamai Bhuvanesh, Michael B. Hall, Marcetta Y. Darensbourg
Summary: A self-assembled tetrameric nickel cage with carboxylate linkages was obtained through various synthetic routes. The tetramer can dissociate into monomeric units in solution, and removal of four iodides by silver ion precipitation results in an analogous species with an additional vacant coordination site. Electrochemical experiments demonstrated that trifluoroacetic acid as a proton source led to hydrogen production from both electroprecatalysts, with electrocatalysis primarily developing from uncharacterized deposits on the electrode.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Brenna K. Collins, Melissa Clough Mastry, Andreas Ehnbom, Nattamai Bhuvanesh, Michael B. Hall, John A. Gladysz
Summary: A series of complexes were synthesized and characterized, showing similar NMR and IR properties. However, cyclic voltammetry revealed only irreversible oxidations for these compounds. UV-visible spectra of the complexes displayed intense and red-shifted bands compared to mono-platinum or Pt(C equivalent to C)(2)Pt species.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Dante A. Castillo Molina, Taveechai Wititsuwannakul, Frank Hampel, Michael B. Hall, John A. Gladysz
Summary: Reactions of Li+[(η5-C5H5)Re(NO)(PPh3)](-) with 2- and 4-chloroquinoline or 1-chloroisoquinoline yield sigma quinolinyl and isoquinolinyl complexes. Further reactions or addition of other compounds can lead to the formation of various quinolinium salts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Zachary M. Martinez, Tucker M. Folsom, Yicheng Tong, Ashley K. Archambeau, Donald J. Darensbourg, Michael B. Hall, Cynthia B. Powell, Gregory L. Powell
Summary: The mechanism of CO substitution reaction involving diosmium carbonyl sawhorse complex was studied experimentally and theoretically, revealing a dissociative interchange mechanism. Kinetic measurements and stability studies were in agreement with each other, explaining the unexpected combination of kinetics and stability characteristics observed in the reaction.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Xin Yang, Robert M. Chin, Michael B. Hall
Summary: Density functional theory (DFT) was used to investigate the geometric and electronic structure of Ru compounds. Natural bond orbitals (NBO) and quantum theory of atoms in molecules (QTAIM) were employed for analysis. The results showed that protonation can alter the properties and electron count of the Ru-Ru bond.
Article
Engineering, Chemical
Evgeny E. Tereshatov, Jonathan D. Burns, Amy L. Vonder Haar, Steven J. Schultz, Lauren A. McIntosh, Gabriel C. Tabacaru, Laura A. McCann, Geoffrey Avila, Andrew Hannaman, Kylie N. Lofton, Mallory A. McCarthy, Bowen Zhang, Michael B. Hall, Sherry J. Yennello
Summary: A detailed study has been conducted on the extraction of Bi and At from nitric acid media into conventional solvents, with a mathematical modeling used to fit experimental data and determine extraction and stability constants. A computational study was also performed to evaluate At interaction with the solvents.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Chemistry, Physical
Thilina Gunasekara, Yicheng Tong, Amy L. Speelman, Jeremy D. Erickson, Aaron M. Appel, Michael B. Hall, Eric S. Wiedner
Summary: In this study, a detailed mechanistic study of electrocatalytic benzyl alcohol oxidation using a molecular nickel complex with pendant amines was conducted. The results showed that the coordination geometry of the catalyst has a significant impact on its activity, and the pendant amine only acts as a proton relay in the oxidation of a nickel hydride intermediate without affecting the overall reaction rate.
Article
Chemistry, Multidisciplinary
Taveechai Wititsuwannakul, Michael B. Hall, John A. Gladysz
Summary: This study investigates the mechanism of coupling between methylidene complexes and ethylene complexes using density functional theory. The formation of non-covalent dimers and the SRe/SRe pathway are found to be key steps in the reaction. The experimental results coincide with the theoretical calculations, highlighting the significance of this study in catalytic CH4 and CO/H2 chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jia Guan, Zeyi Guo, Xuelian Li, Hao Tang
Summary: Looking back at the complexity caused by the noninnocent ligands in determining the oxidation state of the transition metal and correlating it with reactivity, the reactions of alkene/alkyne addition to rhenium/ruthenium tris(thiolate) complexes provide valuable insights into the chemistry of the dppbt ligand, including its noninnocent nature, ligand-centered mechanism, and the origin of differential reactivity.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hao Tang, Xuelian Li, Zeyi Guo, Deqing Kong, Junfei Wang, Yazhu Lu, Yingke Wang, Cheng Xu, Luyi Zhu, Jia Guan
Summary: Inspired by the addition reaction of alkene to Ru and Re tris(thiolate) complexes, a comparative study was conducted on the electronic structures, mechanisms, and reactivities of ethylene addition to Os and Tc tris(thiolate) complexes using DFT and high-level ab initio quantum calculations. The results showed that the oxidized Os and Tc complexes have sufficient radical characters on the ligands to react with ethylene, while the neutral Tc tris(thiolate) complex with little radical character showed no reactivity towards ethylene. The differential reactivities can be attributed to the synergy of thiyl radical character, electronegativity, row, and charge. Extending from Ru and Re tris(thiolate) complexes to their Os and Tc counterparts can provide valuable insights for further research on alkene addition to metal-stabilized thiyl radicals.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Dragan B. Ninkovic, Salvador Moncho, Predrag Petrovic, Michael B. Hall, Snezana D. Zaric, Edward N. Brothers
Summary: This study explores a series of complexes derived from a titanium complex capable of activating C-H bonds under mild conditions. In addition to the initial activation of methane, the tautomerization reaction to a terminal methylidene is also investigated. The results predict that vanadium complexes are promising for methane C-H bond activation with low rate-determining barriers.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Manuel Quiroz, Molly M. Lockart, Shan Xue, Dakota Jones, Yisong Guo, Brad S. Pierce, Kim R. Dunbar, Michael B. Hall, Marcetta Y. Darensbourg
Summary: The reaction between nitrosylated-iron metallodithiolate ligand, paramagnetic (NO)Fe(N2S2), and [M(CH3CN)(n)][BF4](2) salts (M = Ni-II, Pd-II, and Pt-II; n = 4 or 6) results in the formation of di-radical tri-metallic complexes with a stairstep type arrangement. These isostructural compounds exhibit similar stretching values, isomer shifts, and electrochemical properties but different magnetic properties. Examination of the magnetic susceptibility, EPR, and DFT studies indicate the presence of antiferromagnetic coupling between {Fe(NO)}(7) units despite the relatively large intramolecular distances. The exchange coupling constants (J) of these compounds follow the trend of Ni-II < Pd-II << Pt-II, reflecting the increased covalency of the M-S bonds. DFT calculations further reveal the correlation between the magnitude of the exchange interaction and the energy difference between the HOMO and HOMO-1 orbitals of the triplet states, indicating the contribution of the central metal in this interaction. These findings highlight the role of sulfur-dense metallodithiolate ligands in facilitating strong magnetic communication through enhanced covalency and polarizability.
Article
Chemistry, Inorganic & Nuclear
Alexander L. Estrada, Taveechai Wititsuwannakul, Klemenz Kromm, Frank Hampel, Michael B. Hall, John A. Gladysz
Summary: This study investigates the reactions of Diphenyldiazomethane and [(eta(5)-C5H5)Re(NO)(PPh3)](+) BF4(-), as well as their reactions with copper powder and NaOCH3, resulting in different compounds. The properties of these compounds are studied through crystal structures and DFT calculations.
DALTON TRANSACTIONS
(2022)