Article
Chemistry, Multidisciplinary
Jonas Weiser, Jingjing Cui, Rian D. Dewhurst, Holger Braunschweig, Bernd Engels, Felipe Fantuzzi
Summary: This study computationally investigates the properties of group 13-15 homodimers stabilized by a rigid expanded pincer ligand based on the 1,8-naphthyridine core. The results demonstrate the versatility of the ligand in generating various structural motifs and element-element interaction modes, suggesting potential applications in synthetic chemistry.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jeffrey M. Lipshultz, Gen Li, Alexander T. Radosevich
Summary: In the past decade, there has been rapid development in organopnictogen redox catalysis, with a focus on the atomic structure and bonding of pnictogens providing a fundamental backdrop. Key challenges and forward-looking directions in this field have been identified, showcasing the potential for new catalytic discoveries driven by the intrinsic redox reactivity of pnictogens.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This paper discusses the tuning of structure and properties of main-group species (E) by controlling pi-conjugation and/or pi-donation using classical N-heterocyclic vinyl (NI-IV) ligands. By selecting appropriate carbene units, the electronic structure of derived species can be precisely controlled, resulting in stable solid materials.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Inorganic & Nuclear
E. Maslowsky Jr
Summary: In contrast to the extensive research on transition metal carbonyl complexes, the study of carbonyl complexes of main-group elements has only recently begun. Several carbonyl complexes of main-group elements have been reported, possessing various structures and bonding types as neutral, anionic, or cationic species, or as CO complexes on different surfaces. These complexes offer new possibilities in synthetic and catalytic chemistry, and contribute to our understanding of chemical bonding. Vibrational studies, especially the recording of infrared spectra, have played a crucial role in verifying the preparation and determining the structures of these often-unstable complexes. Theoretical calculations have also been used to assign vibrational spectra and predict the structures and stabilities of hypothetical complexes.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Jan-Michael Mewes, Peter Schwerdtfeger
Summary: In this study, an indirect approach was developed to accurately calculate the absolute Gibbs energies of solid and liquid phases of Group 12 elements using a relativistic Hamiltonian, resulting in precise determination of melting and boiling points. The calculated mean absolute deviation for melting and boiling points was only 5% and 1% respectively, with confirmation of liquid aggregate state of Cn. Additionally, the results indicated that periodic trends in this group are primarily influenced by relativistic effects.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Sagar Ghorai, Raghavendra Meena, Anju P. Joseph, Eluvathingal D. Jemmis
Summary: The theoretical analysis indicates that the difference in donor-acceptor capabilities of isocyanide and CO ligands controls the product distributions in the reductive coupling reactions mediated by Cr-Cr quintuple bonded complex and B-B multiple bonded complexes. The reactions follow different potential energy surfaces based on the pi-back bonding possibility of CO and isocyanide, leading to products with different spin multiplicities. The reactions also involve changing the oxidation state of boron centers from +I to +II, in contrast to classical main group mediated reactions where stable oxidation states are preserved. This donor-acceptor bonding interaction dominated main group chemistry is more likely to exhibit transition metal behavior.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Review
Chemistry, Multidisciplinary
Matthew M. D. Roy, Alvaro A. Omana, Andrew S. S. Wilson, Michael S. Hill, Simon Aldridge, Eric Rivard
Summary: This review discusses recent advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides, with a particular focus on their emerging use in Main Group element-mediated catalysis. The review specifically highlights research published in the open literature since 2001.
Editorial Material
Chemistry, Inorganic & Nuclear
Shigeyoshi Inoue, Rebecca L. Melen, Sjoerd Harder
Summary: The development in the field of main group catalysis has led to a better understanding of main group compounds and rational design of their reactivity. Ongoing research has led to the discovery of new classes of more environmentally friendly, cheap, and abundant main group catalysts as alternatives to transition metal catalysts.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Zhongtao Feng, Shuxuan Tang, Yuanting Su, Xinping Wang
Summary: This review presents the recent advances in the synthesis, characterization, reactivity and physical properties of isolable main group element radicals. The unique chemical bonding and novel physicochemical properties of these radicals play significant roles in modern chemistry and materials science.
CHEMICAL SOCIETY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
Lisa Wirtz, Andre Schafer
Summary: Metallocenes with interlinked cyclopentadienide ligands, also known as ansa-metallocenes or metallocenophanes, can have drastically different properties than their unbridged parent compounds. This concept is not limited to transition metals, but can also be applied to many main-group elements. This review focuses on recent advances in synthesis, structure, and properties of metallocenophanes based on group 2, group 13, group 14, and group 15 main-group elements.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Eva Blokker, Xiaobo Sun, Jordi Poater, J. Martijn van der Schuur, Trevor A. Hamlin, F. Matthias Bickelhaupt
Summary: In this study, quantum chemical analysis was conducted on element-element bonds of HnX-YHn molecules using density functional theory. The results revealed new trends in chemical bonding that are not solely determined by electronegativity differences, but also influenced by effective atom size and orbital interactions. This highlights the importance of analyzing bonding mechanisms as a function of bond distance.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Shenglai Yao, Artetuis Saddington, Yun Xiong, Matthias Driess
Summary: In this study, a series of compounds containing low-valent central atoms were successfully synthesized using bis(NHSi) ligands with electronically and spatially different spacers. The chemical reactions and electronic structures of these compounds were investigated. By controlling the Si–Si distance, a variety of low-valent compounds of Si, Ge, and Sn elements were synthesized, and the o-carborane-based bis(NHSi) ligand enabled the oxidation of Si and Ge as well as the isolation of new compounds. Furthermore, future research directions were proposed, such as applying bis(NHSi) ligands to other main-group elements and developing acyclic silylene ligands.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Mirjam J. Krahfuss, Radius Udo
Summary: The reactivity of the N-heterocyclic silylene Dipp(2)NHSi towards various Lewis acids, halides and other compounds was investigated, resulting in the formation of specific adducts and insertion products. However, frustrated Lewis pair reactivity was not observed in the tested adducts, indicating potential limitations of their small organic molecule activation abilities.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Pascal Vermeeren, Marco Dalla Tiezza, Michelle van Dongen, Israel Fernandez, F. Matthias Bickelhaupt, Trevor A. Hamlin
Summary: Various weakly interacting Lewis acids across the periodic table can catalyze the Diels-Alder cycloaddition reaction by lowering the reaction barrier and increasing the asynchronicity of the reaction, demonstrating the generality of the Pauli repulsion-lowering catalysis concept. The reactivity can be further enhanced with a stronger binding to the dienophile, as shown when transitioning from a Period 3 to a Period 5 Lewis acid.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Xueying Guo, Zhenyang Lin
Summary: Due to the empty p orbital and lone pair of electrons on the Si center, silylene exhibits reactivity similar to transition metal systems, capable of activating H-2/C-H bonds and small molecules. Through density functional theory calculations, the reactions of an acyclic silylene with CO, CO2, and N2O were systematically investigated, leading to a detailed understanding of its single-site ambiphilic reactivity.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Linxing Zhang, Kun An, Yi Wang, Yun-Dong Wu, Xinhao Zhang, Zhi-Xiang Yu, Wei He
Summary: This study elucidates the reaction pathway and a more efficient catalyst for C-H silylation through a combination of computational and experimental methods, providing a foundation for further research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Kai Wang, Ziye Liu, Guangyang Xu, Ying Shao, Shengbiao Tang, Ping Chen, Xinhao Zhang, Jiangtao Sun
Summary: Asymmetric carbene insertion reactions are crucial for constructing carbon-heteroatom bonds, but high enantioselectivity typically requires the use of donor-acceptor diazo compounds with an ester group. This study presents the first chemo and enantioselective formal N-H insertion of 2-pyridones using enynones as donor-donor carbene precursors, with DFT calculations revealing an unprecedented enantioselective 1,4-proton transfer from O to C. The rhodium catalyst's chiral pocket, along with steric repulsion and pi-pi interactions of the propeller ligand, play essential roles in determining the selectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Engineering, Environmental
Bei Ye, Ziye Liu, Xiaoqin Zhu, Hanjing Wu, Zifan Liang, Wenlong Wang, Qianyuan Wu, Hongying Hu, Xinhao Zhang
Summary: Chlorination is a widely used method for water disinfection, and ammonia/chlorine co-exposure can have a synergistic effect on the degradation of atrazine (ATZ), involving the formation of hydroxyl radicals (OH) and reactive chlorine species.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Siqi Liu, Yong-Liang Su, Tian-Yu Sun, Michael P. Doyle, Yun-Dong Wu, Xinhao Zhang
Summary: The study focuses on the addition of halomethyl radicals to form bioactive molecules, with an emphasis on understanding the reactivity and selectivity of carbon radicals in hydrogen atom transfer and halogen atom transfer reactions. Through the emerging data-driven strategy, correlations were explored, revealing that predicted selectivities align with experimental determinations. This work highlights the potential applications of informatic workflow in mining reaction rules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Zhanfeng Hou, Yuena Wang, Chuan Wan, Lijuan Song, Rui Wang, Xiaochun Guo, Dongyan Yang, Yaping Zhang, Xuan Qin, Ziyuan Zhou, Xinhao Zhang, Feng Yin, Zigang Li
Summary: In this study, the first Cu-free click reaction between alkynyl sulfonium and azide at ambient temperatures in aqueous media is reported. DFT computations reveal that the sulfonium group plays a key role in enhancing reactivity by stabilizing LUMO+1 and influencing the charge distribution of the triple bond. Sulfonium alkynes can be easily synthesized and scaled up, and most of them are biocompatible. Candidate molecules were prepared and their potential use in various biological applications was tested.
Article
Chemistry, Multidisciplinary
Yun-Xuan Tan, Shijia Li, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: The first geminal hydroborative cyclization of enynes is disclosed in this study. Unlike known hydroborative cyclizations, this reaction adds hydrogen and boron to the same position, leading to a new reaction mode. By using a specific catalyst, a variety of gem-hydroborated bicyclic products with a cyclopropane unit can be rapidly formed from simple enyne substrates. Control experiments and calculations provide important insights into the reaction mechanism. Notably, two competing pathways may operate, depending on the substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Guangyang Xu, Meirong Huang, Tao Zhang, Ying Shao, Shengbiao Tang, He Cao, Xinhao Zhang, Jiangtao Sun
Summary: In this study, an enantioselective insertion of a carbene into the Csp2-H bond of anisole derivatives was achieved using a chiral gold complex and a chiral phosphoric acid as the catalytic system, offering a novel approach for the synthesis of chiral α,α-diarylacetates.
Article
Chemistry, Multidisciplinary
Qiang Feng, Shijia Li, Zhiyang Li, Qiaolin Yan, Xiangfeng Lin, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: The study introduced a new reaction mode of ynones leading to the formation of novel products vinyl alpha-hydroxylboronates under mild ruthenium-catalyzed hydroboration conditions. It exhibited high efficiency, broad scope, and complete chemo-, regio-, and stereoselectivity, providing insights for developing new synthetic strategies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhicheng Bao, Meirong Huang, Yan Xu, Xinhao Zhang, Yun-Dong Wu, Jianbo Wang
Summary: Bisborylalkanes are versatile bifunctional reagents in organic synthesis, with the ability to selectively convert their two boron moieties into other functional groups. This study presents a new strategy for synthesizing bisborylalkanes through the reaction of N-trisylhydrazones with diboronates, resulting in the transformation of bis(boryl) methane into 1,2-bis(boronates) through formal carbene insertion. This practical synthesis method allows for the broad substrate scope of 1,2-diboronates by readily deriving N-trisylhydrazones from corresponding aldehydes. Mechanistic studies uncover an unusual neighboring group effect of 1,1-bis(boronates) that explains the observed regioselectivity when unsymmetric 1,1-diboronates are utilized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yong Wang, Yuxuan Li, Lei Wang, Shengtao Ding, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: In this study, a new method for efficient construction of gem-diboryl compounds with hetero-substituted carbon centers was developed. This method involves the alpha-dihydroboration of heteroalkynes and is a practical and atom-economic alternative to the conventional multistep synthetic strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ke Liao, Cho Ying Chan, Siqi Liu, Xinhao Zhang, Jiean Chen, Yong Huang
Summary: Functionalizing molecules through selective cleavage of carbon-carbon bonds is a promising approach, but the selective cleavage of inert C-sp3-C-sp3 bonds in hydrocarbon feedstocks remains challenging. This article presents a straightforward protocol for cleavage and functionalization of C(sp3)-C-sp3 bonds in alkylbenzenes using photoredox catalysis. Our method utilizes two distinct bond scission pathways depending on the nature of the benzylic substituents. This strategy provides a practical means of cleaving inert C-sp3-C-sp3 bonds in molecules without heteroatoms, generating various radical species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Linxing Zhang, Ping Chen, Xue-Peng Zhang, Chengxi Yang, Tian-Yu Sun, Xinhao Zhang, Yun-Dong Wu
Summary: The Catellani-type palladium/norbornene-cocatalyzed ortho-amination of aryl halides is widely used, but some key issues remain unresolved. Mass spectrometry and theoretical studies reveal the presence of a Cs-containing Pd-IV complex, the reactivity difference between 2-iodotoluene and morpholine-OBz, the coordination preference of Cs2CO3, the favored formation of Pd-IV intermediate with involvement of Cs2CO3, and the lower yield when using K2CO3 as a base.
Article
Engineering, Marine
Xinhao Zhang, Meng Zhou
Summary: This study proposes a method to build a general CNN model that can reconstruct images in unfamiliar areas. The model uses a more flexible U-net architecture to improve generality and was trained on images of different shapes to enhance performance. Results show that the model outperforms traditional interpolation methods when reconstructing for unfamiliar areas.
JOURNAL OF MARINE SCIENCE AND ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Yimeng Du, Yuqing Zhang, Meirong Huang, Shushu Wang, Jianzheng Wang, Kongke Liao, Xiaojun Wu, Qiang Zhou, Xinhao Zhang, Yun-Dong Wu, Tao Peng
Summary: This study identified an efficient N-p-methoxybenzyl homoallylamine moiety for developing fluorescent probes for sensitive and selective detection of formaldehyde. The probes were successfully used to visualize endogenous formaldehyde in live mouse brain tissues and elevated levels in a mouse model of breast cancer, providing new chemical tools for studying formaldehyde in living systems.
Article
Chemistry, Organic
Haowen Ma, Jiajie Feng, Wei Zhou, Chen Chen, Zhuoji Deng, Fengtao Zhou, Yifan Ouyang, Xinhao Zhang, Qian Cai
Summary: Utilizing ureas as co-catalysts, a cooperative catalytic strategy has been developed for copper-catalyzed asymmetric intramolecular C-arylation reaction. By forming hydrogen bonds with 1,3-dicarbonyl structures, ureas activate the substrates, stabilize the intermediates and products, and improve reactivity and enantioselectivities.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
