Article
Chemistry, Physical
Takuya Shimbayashi, Hajime Ito, Mineyuki Shimizu, Hayato Sano, Shigeyoshi Sakaki, Ken-ichi Fujita
Summary: A series of HMB-Ru complexes with metal-ligand cooperative catalysis were synthesized, and their catalytic activities for dehydrogenative oxidation of alcohols were investigated. The order of catalytic activity was found to be different from the simple electron-donating ability, which was attributed to the substituents at specific positions of the ligand.
Article
Chemistry, Multidisciplinary
M. Angeles Fuentes, Riccardo Gava, Noam Saper, Erik Romero, Ana Caballero, John F. Hartwig, Pedro J. Perez
Summary: This study reports a dehydrogenative coupling reaction to form N-alkyl amides by reacting amides with C1-C4 hydrocarbons, using tBuOOtBu as oxidant and a copper complex as catalyst. The reactions showed good yields in benzene or supercritical carbon dioxide as solvents. Compared to previous studies on larger alkanes, the reactivity in this amination process correlated with bond dissociation energies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Peter Szwedo, Travis Jumper, Karie Sanford, Taylor Arnold, Sarah Coffman, Davonte Hokes, Pradip Munshi, Brian Walker, Anindya Ghosh
Summary: This study demonstrates a C-N cross-coupling approach involving oxidative amidations of aromatic aldehydes using an amide-based nickel(II) pincer catalyst. Optimal reaction conditions were identified and moderate to good turnover numbers were achieved for various amide products. Kinetic studies and isotope labeling provided insights into the reaction mechanism, proposing a Ni(I)-Ni(III) pathway.
Article
Chemistry, Inorganic & Nuclear
Jialuo Cai, Cheng Peng, Yong Wang
Summary: This study employed DFT calculations to investigate the mechanism of Ru(II) chelate catalyzed selective functionalization of N-pivaloylindole. The results showed a favorable pathway for C7-H activation and provided mechanistic insights into the observed regioselectivity through distortion-interaction analysis and IRI analysis.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Bivas Chandra Roy, Kasturi Ganguli, Sk. Abdus Samim, Sabuj Kundu
Summary: Alcohol has garnered special attention in the past two decades due to its abundance, low cost, and low toxicity, making it a versatile building block for synthesizing value-added products. Metal-ligand cooperation is a powerful tool for utilizing alcohol in the synthesis of complex molecules. This review focuses on stable metal-ligand cooperative 5d, 4d, and 3d metal-based complexes for effective alcohol dehydrogenative coupling reactions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Wufeng Chen, Jianfeng Li, Chunming Cui
Summary: Activation of Si-H bonds with rare-earth complexes can generate highly reactive rare-earth hydrides or silyl complexes, which are key intermediates for hydrosilylation and cross-coupling reactions. Our laboratory's recent advances in rare-earth-catalyzed hydrosilylation of unsaturated substrates and dehydrogenative coupling of hydrosilanes with amines demonstrate the unique reactivity and selectivity of rare-earth catalysts, enabling unprecedented reactions.
Article
Chemistry, Organic
Nandita Biswas, Dipankar Srimani
Summary: The Ru-catalyzed reaction provides an economical and simple operational strategy for synthesizing biologically active 1,8-dioxodecahydroacridine derivatives with a wide substrate scope and good tolerance toward various functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Roman G. Belli, Jin Yang, Erick Nunez Bahena, Robert McDonald, Lisa Rosenberg
Summary: This study provides a thorough experimental examination of the mechanisms involved in the catalytic hydrophosphination reaction using a series of half-sandwich Ru indenyl complexes. The results highlight the importance of ancillary ligands in the design of active and robust catalysts for this reaction, and reveal the complexity that can arise from simple mechanistic premises.
Article
Chemistry, Physical
Xiangchao Xu, Yao Ai, Rongzhou Wang, Liping Liu, Jiazhi Yang, Feng Li
Summary: A ruthenium complex with a functional ligand was synthesized and found to be an efficient catalyst for the synthesis of quinolines. The NH units in the ligand were crucial for the catalytic activity. This research demonstrates the potential of metal-ligand bifunctional catalysts for acceptorless dehydrogenative reactions.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Michael Rauch, Jie Luo, Liat Avram, Yehoshoa Ben-David, David Milstein
Summary: This study reports a novel synthesis of thioesters and reveals the mechanism of their reverse hydrogenation. Experimental and computational approaches were used to elucidate the likely pathway of the reactions and discuss the impact of hydrogen gas pressure on selectivity. The study also identified the competitive nature of reactions between thiols and alcohols, as well as the stability differences of related catalysts.
Article
Chemistry, Organic
Hongrui Qi, Yiyan Yan, Yunfeng Liao, Furong Jiang, Hualan Gao, Guo-Jun Deng
Summary: In this novel I-2-catalyst oxidative dehydrogenative tandem cyclization reaction, 2-methylquinolines, arylamines, and 1,4-dioxane were used as substrates to construct 2-([2,2'-biquinolin]-3-yloxy)ethan-1-ol derivatives under metal-free conditions. This transformation involved the cleavage of 7 C-H bonds, 2 N-H bonds, and 1 C-O bond, leading to the formation of 2 C-C bonds, 1 C-N bond, and 1 O-H bond, with the opening of the 1,4-dioxane ring and the formation of a 2-(vinyloxy)ethan-1-ol group in the process.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Yang Liu, Mikael La Roch, Alessia Mori, Alexandre Pradal, Giovanni Poli, Julie Oble
Summary: The article introduces a Pd(II)-catalyzed [3+2] annulation strategy, which replaces α,β-unsaturated-γ-oxy carbonyls with β,γ-unsaturated carbonyl derivatives as bis-electrophiles. The study provides experimental optimization and demonstrates the synthetic versatility in forming diverse heterocyclic structures. This dehydrogenative strategy represents a more economical version than the previous redox-neutral couplings.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Soheil Zamani Anbardan, Javad Mokhtari, Ahmad Yari, Abolfazl Hassani Bozcheloei
Summary: The oxidative dehydrogenative homo-coupling of amines to imines and cross-coupling of amines with alcohols to amides can be efficiently achieved at room temperature in THF using Cu-MOF as a heterogeneous catalyst with high to moderate yields. Different primary benzyl amines and alcohols can be utilized for the synthesis of various amides and imines. The Cu-MOF catalyst can also be recycled and reused four times without losing catalytic activity.
Article
Chemistry, Applied
Xin-Hua Peng, Rui Bai, Shanshan Liu, Zhuo Li, Lin-Yu Jiao
Summary: A novel and efficient protocol for the rare-earth metal salt-catalyzed substitution of phosphoryl azides with amines was disclosed. The methodology generated a series of phosphoryl amides, but secondary analogues or anilines were reluctant to undergo desired transformations.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Roberto Sala, Gredy Kiala, Luis F. Veiros, Gianluigi Broggini, Giovanni Poli, Julie Oble
Summary: A method for the directed alkenylation of 2-carboxaldimine-heterocyclopentadienes using Ru3(CO)12 catalyst has been developed. This reaction enables coupling of various electron-poor alkenes with furan, pyrrole, indole, and thiophene 2-carboxaldimines, and does not require additional sacrificial oxidants. Mechanistic insights have been obtained through density functional theory calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qaim Ali, Zhewei Li, Lin Zhang, Chenguang Luo, Min Pu, Ming Lei
Summary: In this paper, the cross-coupling reaction of methanol with benzyl alcohol to form methyl benzoate catalyzed by Mn-PNN pincer complex was investigated using density functional theory (DFT). The reaction process consists of the dehydrogenation of benzyl alcohol to benzaldehyde, the coupling of benzaldehyde with methanol to hemiacetal, and the subsequent dehydrogenation of hemiacetal to methyl benzoate. The results showed that the dehydrogenation processes are influenced by inner and outer sphere competitive mechanisms. The rate-determining step is the dehydrogenation of benzyl alcohol to benzaldehyde, with an energy barrier of 22.1 kcal/mol. Additionally, the regeneration of the catalyst is crucial, and the dehydrogenation assisted by formic acid is more advantageous. This work provides theoretical insights for the design of affordable transition-metal catalysts for dehydrogenation reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Bin Wang, Chunying Rong, Ming Lei, Shubin Liu, Frank De Proft
Summary: Designing efficient and selective catalysts for carbon dioxide reduction is an active area of research in homogeneous catalysis. In this study, the catalytic activity of a newly reported Mn(I)-PNP-pincer catalyst with an embedded aromatic ring is investigated. The study systematically examines the catalyst's capability to yield different products and explores the importance of ligand aromaticity and steric effects on metal-ligand cooperativity. The reactivity of the catalyst is probed using conceptual density functional theory and an information-theoretic approach, leading to a novel partitioning of the reaction coordinate into three relevant regions. The results demonstrate that different properties govern the reactivity in these different regions, such as steric effects, electrophilicity/nucleophilicity, or aromaticity. The methodology and analytical tools employed in this study have the potential to be generalized and extended to other catalytic systems, offering insights towards designing improved catalysts.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kailyn M. Schueller, Henry F. Mull, Justin T. Turney, Henry F. Schaefer III
Summary: This paper investigates the four constitutional isomers of Si2H2+, namely the butterfly, vinylidene-like, monobridged, and trans structures. The lowest energy is found in the butterfly isomer, followed by vinylidene-like and monobridged structures, while the trans structure has the highest energy. The study also compares these isomers with their neutral counterparts, analyzes the partial charges, and predicts vibrational frequencies, infrared intensities, and dipole moments to facilitate the spectroscopic identification of Si2H2+.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Polymer Science
Fang Yu, Tian Ma, Wenbin Liang, Ming Lei
Summary: N-acyloxyamine is an excellent radical initiator for controlled degradation of polypropylene (PP), with CR-76 being one of the most important ones. Experiments showed that 2 wt% CR-76 caused significant degradation and reduction in molecular weight of PP. Density functional theory calculations revealed that the N-O bond cleavage of enol-CR-76 results in the generation of nitrogen and (CH2COO)-C radicals, which play important roles in the degradation process. Small molecule radicals produced, such as CH3COO, (CH3)(2)CH, and (CH3)(2)CHCH2, showed higher activity in the hydrogen abstraction of PP compared to other radicals generated. Additionally, NO, NOO, and ROO radicals were found to be important in the radical coupling and beta-scission of PP, providing new insights into the controlled degradation process and offering theoretical guidelines for the design of new N-acyloxyamine radical initiators for polymer degradation.
JOURNAL OF APPLIED POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Andy Jiang, Justin M. Turney, Henry F. Schaefer III
Summary: We propose a reduced scaling method for evaluating the perturbative triples energy in coupled-cluster theory using tensor hypercontraction. Our method reduces the scaling of the energy calculation and exhibits good accuracy compared to CCSD(T). We also demonstrate the convergence of our method and its sublinear to linear error growth with system size.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Yangqiu Liu, Hexiang Qi, Ming Lei
Summary: The improved elastic image pair (EIP) method is a reliable approach to approximate transition states between two local minima. By modifying the moving procedure and convergence strategy of the image pair, combined with rational function optimization, exact transition states can be achieved. Testing on a set of 45 different reactions demonstrates the reliability and efficiency of this method in finding transition states.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Addison K. Bralick, Erica C. Mitchell, Anna C. Doner, Annabelle R. Webb, Matthew G. Christianson, Justin M. Turney, Brandon Rotavera, Henry F. Schaefer
Summary: Vacuum UV absorption spectroscopy is widely used for identification, structure analysis, and quantitative measurement of species. This study compared the performance of EOM-CCSD and 10 TD-DFT functionals in producing reliable vacuum UV absorption spectra. The results showed that M06-2X was consistently the top performing TD-DFT method, with BMK, CAM-B3LYP, and omega B97X-D also producing reliable spectra for these small combustion species.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Editorial Material
Chemistry, Physical
T. Daniel Crawford, Anna I. Krylov, Henry F. Schaefer, Troy Van Voorhis
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Phuong M. Tran, Yuzhong Wang, Mitchell E. Lahm, Pingrong Wei, Christopher J. Molnar, Henry F. Schaefer, Gregory H. Robinson
Summary: This article reports a series of Lewis base-coordinated germanium(II) dithiolene complexes and investigates their chemical properties, particularly the reactions between germylene and dithiolene, through experimental and theoretical methods.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Yulan Dai, Zhewei Li, Min Pu, Ming Lei
Summary: The reaction mechanism of synthesizing 1,1-diborylalkanes from alkenes and borane was investigated using density functional theory (DFT). The role of reducing reagents in the equilibrium of self-contradictory reactivity was elaborated. The use of H-2 as a reducing agent was found to be more advantageous and the & sigma;-bond metathesis was identified as the rate-determining step.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Mitchell E. Lahm, Marcus A. Bartlett, Tao Liang, Liang Pu, Wesley D. Allen, Henry F. Schaefer
Summary: The reaction mechanism of i-propyl + O-2 was studied using quantum chemical methods, establishing it as a benchmark for secondary alkyl radical combustion. Focal point analyses were performed, extrapolating to the ab initio limit. The optimization of all reaction species and transition states was carried out, removing flaws in literature reference geometries. Important species and transition states were identified, and exhaustive conformational searches were conducted.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Stephen M. Goodlett, Justin M. Turney, Henry F. Schaefer
Summary: Multifidelity modeling is a technique that combines information from multiple datasets into one model, which is advantageous when one dataset has few accurate results and the other has many less accurate results. In modeling potential energy surfaces, a large number of inexpensive energy computations can be used for the low-fidelity dataset, while the high-fidelity dataset provides fewer but more accurate electronic energies. In this study, neural network-based approaches for multifidelity modeling are compared, and it is found that the four methods mentioned outperform a traditional neural network with the same amount of training data. The Delta-learning approach is shown to be the most practical and provides the most accurate model.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Haohao Wang, Caiwei Yue, Jirui Du, Min Pu, Ming Lei
Summary: A density functional theory study was conducted to investigate the mechanism of nitrobenzene hydrogenation by a Ni-1/CeO2-x single-atom catalyst. The most favorable pathway for the hydrogenation of nitrobenzene to aniline by Ni-1/CeO2-x (111) was determined. The rate-determining step of the overall reaction was identified as the fourth hydrogen transfer step with an energy barrier of 1.24 eV.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Review
Chemistry, Multidisciplinary
Ma Xuelu, Li Meng, Lei Ming
Summary: In this study, the role of trinuclear transition metal complexes in catalytic reactions is investigated. The complexes are classified based on metal centers and the characteristics of their ligands are summarized. The geometric structure and electronic characteristics of the complexes are discussed. The catalytic applications involving specific chemical bonds activation are focused on, and the potential future applications in this emerging field are outlooked.
ACTA CHIMICA SINICA
(2023)
Article
Chemistry, Physical
Yunfan Yue, Tian Ma, Hexiang Qi, Yaqi Zhao, Xiaofan Shi, Yanhui Tang, Min Pu, Ming Lei
Summary: In this study, a series of bowl-shaped quadridentate ligands and their manganese catalysts were designed for the hydrogenation of unsaturated bonds using density functional theory. The calculated results suggest that the bowl-shaped structure of the ligands and their connection to the Si-N-Si-C-Si-C six-membered ring core significantly affect the catalytic activity and selectivity. This work provides theoretical insights for designing new transition metal catalysts.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
