Article
Chemistry, Inorganic & Nuclear
Takahiro Iwamoto, Kyoka Saito, Takuya Mitsubo, Takuya Kuwabara, Youichi Ishii
Summary: P- and S-substituted vinylidene complexes were found to be active for retro-vinylidene rearrangements, leading to reversible systems of vinylidene/alkyne isomerization. Isotope labeling experiments revealed that P-substituents selectively migrated in PO(OMe)2- and POPh2- substituted complexes, while both SPh and R groups served as migrating groups in SPh-substituted complex, though the migration of SPh group was still the major reaction path. These findings deepen our mechanistic understanding of alkyne/vinylidene rearrangements of heteroatom-substituted internal alkynes.
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Zhaowen Dong, Paul Varava, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Laura Piveteau, Kay Severin
Summary: This study reports the preparation and structural characterization of vanadium complexes with N-heterocyclic vinylidene ligands, enabled by utilizing diazoolefins as ligand precursors. Structural and theoretical analysis show that N-heterocyclic vinylidenes can act as strong 6e(-) donor ligands, forming strong metal-carbon interactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Andres Alguacil, Franco Scalambra, Antonio Romerosa
Summary: In this study, a series of complexes were synthesized and characterized, and their crystal structures, including a previously published complex, were reported. The behavior of two ligands, PTA and dmoPTA, in terms of protonation and coordination, was discussed based on 15N nuclear magnetic resonance data. The construction of a library of 15N chemical shifts shed light on important features regarding the coordination of PTA and its derivatives.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Nasir A. Rajabi, Claire L. McMullin
Summary: Density Functional Theory (DFT) was used to study the mechanism of alkyne-to-vinylidene isomerisation reaction mediated by [Rh(PXNXP)](+) complexes. The calculations suggest that the reaction proceeds through the slippage of pi-bound alkyne at the Rh center into a Rh-alkyne sigma(C-H) complex followed by an indirect 1,2-H shift to give the Rh-vinylidene species.
Article
Chemistry, Applied
Masanori Tayu, Ryuta Watanabe, Satoshi Isogi, Nozomi Saito
Summary: Treatment of ynamides with a catalytic amount of TpRuCl(PPh3)(2) leads to the construction of indole scaffolds known as privileged structure motifs. This reaction involves a cascade of 1,2-rearrangement and cyclization carrying out C-C bond formation via a ruthenium vinylidene intermediate, as revealed by deuterium-labeling experiments. Furthermore, the transformation of multi-functionalized ynamide, derived from a practical drug molecule, demonstrates the high functional group tolerance of this reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Ismail Warad
Summary: Three novel neutral Ru(II) complexes were synthesized and characterized by various techniques to study their structures and interactions. The hemilability phenomena of the diether-phosphine ligand played a crucial role in monitoring the completeness of the reaction process. The study demonstrated that chlorinated solvents can regulate the isomerization process of the complexes.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Multidisciplinary
Bart Herle, Georg Spaeth, Lucas Schreyer, Alois Fuerstner
Summary: This study demonstrates a novel approach to synthesizing a large estate of 16-membered macrolide antibiotics using a unified method. Key building blocks were prepared through an asymmetric vinylogous Mukaiyama aldol reaction, leading to the creation of two structurally distinct series of antibiotic targets. Notable late-stage maneuvers included rare catalytic reactions and the underutilized possibility of forging complex macrolactone rings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Jessica Margalef, Maria Biosca, Pol de la Cruz Sanchez, Jorge Faiges, Oscar Pamies, Montserrat Dieguez
Summary: The success of phosphine-oxazoline ligands has led to advancements in P-oxazoline ligand families, resulting in diverse structures and more efficient ligands for asymmetric transformations. Through proper design, these heterodonor bidentate ligand families exhibit superior catalytic performance in a variety of asymmetric reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Marcus Korb, Stephen A. Moggach, Paul J. Low
Summary: An unusual 1,2-ferrocenyl migration was observed after reactions of [Ru(dppe)Cp][BAr4F] with diferrocenylacetylene, expanding the scope of group rearrangments beyond methyl and phenyl entities. Bimetallic bis(vinylidene) complexes were formed from ferrocene-containing bis(alkynes) following two consecutive rearrangements.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Xiaoxiao Xie, Sanliang Li, Qiaoyu Chen, Hao Guo, Junfeng Yang, Junliang Zhang
Summary: This article presents a novel method for the synthesis of chiral phosphorus ligands, and demonstrates their potential applications in catalytic asymmetric reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Gaurav Dahiya, Mukesh Pappoppula, Aaron Aponick
Summary: The systematic variation of atropisomeric C-1-symmetric P,N ligands to adjust the position of groups within the chiral pocket incrementally without changing their steric parameters has been investigated in this study. This approach has been successfully demonstrated in catalytic enantioselective transformations, leading to the identification of a P,N ligand for highly enantioselective synthesis of organoboranes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kangkang Li, Jin-Feng Li, Bing Yin, Fanlong Zeng
Summary: A family of air- and moisture-stable NNN pincer ruthenium(II) complexes with a pendant OH were developed, which exhibit unprecedented high reactivity and selectivity in N-monomethylation of amines and nitroarenes using methanol. The investigation reveals adopting the combination of 1H-pyrazole-1-yl and 3,5-dimethyl-4-hydroxyethyl-1H-pyrazol-1-yl as the two assistant arms of the pyridyl-backbone is a suitable choice. The mechanism study discloses that, during the catalytic cycle, dehydrogenation of methanol to form formaldehyde is a fast and reversible step.
Review
Chemistry, Inorganic & Nuclear
Pengcheng Gao, Michal Szostak
Summary: The catalytic addition of water to unsaturated C-C or C-N p bonds is an important and environmentally sustainable method for forming C-O bonds. Traditional acid-catalyzed hydration requires strong acids or toxic mercury salts, limiting its practical applications and posing safety and environmental concerns. Transition-metal-catalyzed hydration with NHC ligands has gained significant attention and has achieved major progress. This review provides a comprehensive overview of hydration reactions catalyzed by transition metal-NHC complexes and their applications in catalytic hydration.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Organic
Jiawei Qiu, Makoto Sako, Tomoyuki Tanaka, Tsuyoshi Matsuzaki, Tsunayoshi Takehara, Takeyuki Suzuki, Shohei Ohno, Kenichi Murai, Mitsuhiro Arisawa
Summary: The developed one-iridium-catalyst system efficiently transforms 1,7-enynes into substituted indole derivatives, providing a straightforward synthetic approach to valuable indoles with vinyl and silylmethyl groups at specific positions.
Article
Chemistry, Multidisciplinary
Emmanuelle Remond, Jean-Alain Fehrentz, Laure Lienart, Sebastien Clement, Jean-Louis Baneres, Florine Cavelier
Summary: The study demonstrates a new method of synthesizing fluorescent P-hydroxybinaphtylphosphole-oxide or -sulfide for labeling biomolecules, particularly for characterizing GHSR ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Deng-Yuan Li, Ying Wang, Xiao-Yu Hou, Yin-Ti Ren, Li-Xia Kang, Fu-Hua Xue, Ya-Cheng Zhu, Jian-Wei Liu, Mengxi Liu, Xing-Qiang Shi, Xiaohui Qiu, Pei-Nian Liu
Summary: In this study, we report a novel [1+1+1] cycloaddition reaction for the synthesis of aza[3]radialenes on the Ag(111) surface, where the steric hindrance of the chlorine substituents guides the selective and orientational assembling of the isocyanide precursors. The atomic structure of the produced aza[3]radialenes is determined by combining scanning tunneling microscopy, non-contact atomic force microscopy, and time-of-flight secondary ion mass spectrometry. Furthermore, density functional theory calculations propose two reaction pathways, including synergistic and stepwise, revealing the role of the chlorine substituents in the activation of the isocyano groups via electrostatic interaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Parvej Alam, Tsz Shing Cheung, Nelson L. C. Leung, Jianyu Zhang, Jing Guo, Lili Du, Ryan T. K. Kwok, Jacky W. Y. Lam, Zebing Zeng, David Lee Phillips, Herman H. Y. Sung, Ian D. Williams, Ben Zhong Tang
Summary: Long-persistent luminescence (LPL), also known as afterglow, is a phenomenon where a material continues to emit light after the excitation source is turned off. It has attracted much interest due to its fundamental nature and potential in developing new functional materials. Most current LPL materials are complex inorganic systems that require harsh synthetic procedures and rare-earth metals. However, metal-free organic long-persistent luminescence (OLPL) has gained interest as it overcomes some of the disadvantages of inorganic systems. The most successful method to generate OLPL systems is through binary donor-acceptor exciplex systems, but the ratios of the binary systems can complicate reproducibility and large-scale production. Therefore, simpler OLPL systems are needed for easier design and production.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yan He, Heng Wang, Li Xu, Deng-Yuan Li, Ji-Hong Ge, Da-Fu Feng, Wei Feng, Gang Zou, Pei-Nian Liu
Summary: The study presents a step-economic strategy for the direct synthesis of bridged polycyclic skeletons by merging oxidative C-H annulation and cascade cycloaddition, achieving the one-pot construction of multiple carbon centers and carbon-carbon bonds. Mechanistic investigations revealed a cascade ring-opening, 1,5-sigmatropic rearrangement, and [4 + 2] cycloaddition process.
Article
Chemistry, Multidisciplinary
Ying Yu, Hao Xing, Zhicong Zhou, Junkai Liu, Herman H. -Y. Sung, Ian D. Williams, Jonathan E. Halpert, Zheng Zhao, Ben Zhong Tang
Summary: The study synthesizes three red luminogens with subtle structural variation and investigates the influence of molecular interactions on their luminescent behavior in solution and aggregate states. Strong pi-pi and D-A interactions cause a redshift in emission, while weak interactions enhance the quantum yield. This work provides insights into the complicated influence of various molecular interactions on luminescent behavior.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ying Yu, Hao Xing, Dan Liu, Mengying Zhao, Herman H. -Y. Sung, Ian D. Williams, Jacky W. Y. Lam, Guohua Xie, Zheng Zhao, Ben Zhong Tang
Summary: This study reports an electron-deficient acceptor, BSM, based on dithiafulvalene and benzothiadiazole, which can produce highly efficient NIR emitters with aggregation-induced emission (AIE) property. The solution-processed OLEDs achieved outstanding external quantum efficiency, and the efficiency could further improve with optimized configuration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Wei Wei, Xin Xu, Herman H. Y. Sung, Ian D. Williams, Zhenyang Lin, Guochen Jia
Summary: In this study, the first structurally characterized Dewar metallabenzenes were isolated and characterized. These compounds were synthesized through unprecedented reactions of metallacyclobutadienes with aminoalkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Guo Zou, Shanrong Zhang, Shishi Feng, Qihuan Li, Bo Yang, Yi Zhao, Kaijun Luo, Ting-Bin Wen
Summary: In this study, a series of new half-disc-shaped platinum(II) complexes with concise structures were designed and synthesized. These complexes exhibited tunable emission colors and liquid crystal properties, and some of them showed improved carrier mobility behaviors in the liquid crystal states.
INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Jianyu Zhang, Parvej Alam, Siwei Zhang, Hanchen Shen, Lianrui Hu, Herman H. Y. Sung, Ian D. Williams, Jianwei Sun, Jacky W. Y. Lam, Haoke Zhang, Ben Zhong Tang
Summary: Researchers have designed clusteroluminogens that exhibit multiple emissions and white-light emission in the crystalline state by manipulating through-space interactions. The intensity ratio of these emissions can be easily controlled by changing the halide atom and excitation wavelength.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiujuan Shi, Jun Zhang, Junkai Liu, Xueqian Zhao, Haoran Wang, Peifa Wei, Xiaodong Zhang, Xin-Long Ni, Herman H-Y Sung, Ian D. Williams, Wai Kit Ng, Kam Sing Wong, Jacky W. Y. Lam, Lin Wang, Honglin Jin, Ben Zhong Tang
Summary: In this study, a hierarchical supramolecular self-assembly method was proposed for the fabrication of fluorescent multiblock microcolumns containing 1 to 7 blocks using CB[8], NaBr, and AIEgen guests.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Crystallography
Keyao Li, Monalisa Roy, Madiha Nisar, Lawrence W-Y Wong, Herman H-Y Sung, Richard K. Haynes, Ian D. Williams
Summary: This study demonstrates the formation of different types of cocrystals using different seeds, while also showing the role of halogen bonds in discriminating between different polymorphic types.
Article
Chemistry, Multidisciplinary
Zixuan Zhang, Zhiyu Wang, Herman H. -Y. Sung, Ian D. Williams, Zhi-Gang Yu, Haipeng Lu
Summary: The macroscopic origin of chiroptical activity in chiral metal-halide semiconductors (MHS) is unveiled, and design principles for obtaining high anisotropic factors for future chiral optoelectronic applications are provided.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Jie Wang, Qing -Yang Li, Shan -Shan Wang, Xin-Yan Wu, Xingguang Li, Pei-Nian Liu
Summary: We have reported a novel rhodium-catalyzed rearrangement reaction involving N-substituted 2-thiopyridones and diazoesters. This reaction proceeds through the rhodium-catalyzed formation of sulfur ylides, followed by a direct C-N bond cleavage, achieving N-to-C 1,4-pyridyl migration. The protocol can be used to synthesize various thiopyridines with tetrasubstituted carbon stereocenters in moderate to excellent yields, expanding the transformation pattern of sulfur ylide intermediates in rearrangement reactions.
Article
Chemistry, Inorganic & Nuclear
Dandan Lu, Weidong Lin, Feng Su, Kongchuan Wu, Ting-Bin Wen, Hui-Jun Zhang
Summary: In this study, a series of SPO-RhIII complexes relevant to RhIII-catalyzed C-H phosphorylation were isolated and characterized. The research on their reactivities in C-H rhodation revealed the crucial role of a suitable base in reducing RhIII deactivation by SPOs. Finally, an efficient RhIII-catalyzed aryl C-H phosphorylation with diarylphosphine oxides was developed using silver carbonate as both a base and an oxidant.
Article
Chemistry, Multidisciplinary
Gucheng Zhu, Yashi Jiang, Ying Wang, Bing-Xin Wang, Yuqiang Zheng, Yufeng Liu, Li-Xia Kang, Zhanbo Li, Dandan Guan, Yaoyi Li, Hao Zheng, Canhua Liu, Jinfeng Jia, Tao Lin, Pei-Nian Liu, Deng-Yuan Li, Shiyong Wang
Summary: A group of nitrogen-doped nanographenes (N-NGs) with atomic precision are fabricated on Au(111) through a combination of reactions, and the presence of collective quantum magnetism in N-NGs is revealed through high-resolution scanning probe microscopy measurements. The mechanism of magnetic exchange interaction of N-NGs is also compared with their pure hydrocarbon counterparts. These findings demonstrate the possibility of bottom-up synthesis of ordered quantum phases through the utilization of N-NGs to fabricate low-dimensional extended graphene nanostructures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Qiang Cao, Ping Wang, Yuanting Cai, Yuhui Hua, Shaohui Zheng, Xu Cheng, Guomei He, Ting-Bin Wen, Jiangxi Chen
Summary: The first rhena[10]annulyne, a ten-membered metallacycle with a single metal center, is reported. DFT calculation studies suggest a thermodynamic origin for its conversion.
INORGANIC CHEMISTRY FRONTIERS
(2022)
