Review
Multidisciplinary Sciences
Kyoko Nozaki
Summary: This short review article summarizes our latest studies on catalyst development for the copolymerization of non-vinyl polar monomers with ethylene and the properties of the resulting copolymers.
PROCEEDINGS OF THE JAPAN ACADEMY SERIES B-PHYSICAL AND BIOLOGICAL SCIENCES
(2022)
Review
Chemistry, Organic
Yanlin Zong, Qiankun Li, Hongliang Mu, Zhongbao Jian
Summary: The review provides a comprehensive summary of various palladium(II) catalysts used for the copolymerization of carbon monoxide with different olefinic monomers. It also discusses the influence of important factors, such as solvents and counterions, on specific copolymerization processes. The aim is to inspire the design of new Pd catalysts with improved properties and the development of new polyketone materials.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Keisuke Hayashi, Arihiro Kanazawa, Sadahito Aoshima
Summary: The cationic copolymerization ofo-phthalaldehyde with various styrene derivatives and vinyl ethers was investigated, with a focus on the relationship between the structure and reactivity of vinyl monomers and the copolymerization behavior. The existence of alpha or beta-substituents on the vinyl group was found to be essential for efficient crossover reactions with styrene derivatives, while various vinyl ethers underwent copolymerization with o-phthalaldehyde. The use of vinyl monomers with both large steric hindrance and highly reactive beta-carbon was effective in achieving an alternating-like copolymerization. Additionally, degradable copolymers were successfully obtained from styrene derivatives.
Review
Chemistry, Inorganic & Nuclear
Xin-Lei Li, Tie-Qi Xu
Summary: In this paper, the research progress of stereoselective polymerization catalysts for aromatic polar vinyl monomers in recent years is reviewed. The influence of ligand structure, electronic effect of substituents, spatial site resistance effect, central rare earth metal species, and polymerization solvents on the activity and stereoselectivity of polymerization reactions are discussed in detail, as well as the possible mechanism of polymerization reaction.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Hongliang Mu, Guanglin Zhou, Xiaoqiang Hu, Zhongbao Jian
Summary: This review summarizes the major progress in copolymerization of olefins with various polar monomers using state-of-the-art nickel catalysts, focusing on ligand modifications and catalyst designing strategies.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Ningning Zhu, Tao Liang, Yongshuang Huang, Wenmin Pang, Min Chen, Chen Tan
Summary: Phosphinecarbonylpalladium and -nickel catalysts with various substituents on the ligand backbone exhibited high activities and molecular weights in both ethylene polymerization and copolymerization with polar monomers. The electron-donating group and cyclic backbone structure can impact catalytic activities and polymer molecular weights. Installation of a pyridyl moiety in the ligand backbone enhances catalytic activities and responsiveness to Lewis acids.
INORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Yehor Polunin, Bohdan Domnich, Sandip Tiwari, Sagar Thorat, Mukund Sibi, Andriy Voronov
Summary: In this study, the behavior of several biobased aromatic vinyl monomers in the polymerization process was investigated using chemical structure as an evaluation criterion. The results showed that these monomers can undergo post-polymerization reactions and can be copolymerized with other vinyl monomers. They can also be used in the formulation of thermoset polymer coatings.
EUROPEAN POLYMER JOURNAL
(2023)
Review
Polymer Science
Nicole Ziegenbalg, Lada Elbinger, Ulrich S. Schubert, Johannes C. Brendel
Summary: The large variety of available functional groups, their versatility, and the various polymerization techniques have made vinyl monomers the prevalent source for preparation of polymers. Interestingly, among this wide variety of applied structures S-vinyl monomers have remained a niche for the last decades despite their unique set of properties and early reports on their reactivities. Access to these compounds on a technical scale has been limited, but recent developments in sulfur chemistry and the need for more diverse reactivities might lead to a renewed interest in S-vinyl monomers. The different variations of sulfur moieties and their corresponding diversity of properties make these compounds increasingly attractive for fundamental research and applications. However, the detailed understanding and control of their polymerization behavior is still a challenge, as S-vinyl compounds may be susceptible to side reactions depending on the applied reactions. This review intends to provide a comprehensive overview of reported polymerization techniques, their challenges and limitations with regard to sulfur compounds, and the resulting reactivities of the corresponding monomers in homopolymerizations as well as copolymerizations with various other vinyl monomers.
Article
Chemistry, Inorganic & Nuclear
Yanan Zhao, Huashu Li, Shixuan Xin, Hao Li, Yi Luo, Shengbao He
Summary: Computational evidence shows that the polymerization of polar monomers can be achieved without the use of masking reagents or bulky protective substituents when specific titanium and zirconium complexes are employed.
Article
Polymer Science
Zhaohe Liu, Bo Liu, Zhongfu Zhao, Dongmei Cui
Summary: The study utilizes different metal catalysts for the coordination polymerization of polar divinyl styrenyl monomers, resulting in atactic or syndiotactic polymer products with high selectivity for different monomers, including copolymers. The reasons behind the polymerization behaviors were investigated using DFT calculations.
Article
Chemistry, Physical
Chen Zou, Daohong Liao, Wenmin Pang, Min Chen, Chen Tan
Summary: Asymmetric PO-type ligands have been demonstrated to be versatile platforms for palladium and nickel catalyzed ethylene polymerization and copolymerization reactions. By introducing electron-donating substituents, higher polymer molecular weights can be achieved in the palladium catalytic system, while less electronic donating substituents in the nickel catalysts lead to increased catalytic activities. These results highlight the importance of ligand electronic effects in tuning the properties of nickel and palladium catalysts in ethylene polymerization and copolymerization reactions.
JOURNAL OF CATALYSIS
(2021)
Article
Polymer Science
Huijun Fan, Yudan Liao, Shengyu Dai
Summary: The effects of aryl substituents and backbones of alpha-diimine Pd(II) catalysts on propylene polymerization and copolymerization were studied. It was found that the cyclopentyl substituents resulted in the highest molecular weight and activity in homopolymerization, as well as the highest activity, incorporation ratio, and molecular weight in copolymerization.
Article
Materials Science, Multidisciplinary
Fuxing Shi, Xiaochuan Ren, Haohao Wang, Min Pu, Li Liu, Ming Lei
Summary: In this study, the density functional theory method was used to investigate the copolymerization reaction of ethylene and 2-methoxystyrene catalyzed by a palladium phosphine-sulfonate complex. The results revealed insights into the reaction mechanism and pathway selection at different stages.
ACS APPLIED POLYMER MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Wasim Ullah Khan, Hassam Mazhar, Farrukh Shehzad, Mamdouh A. Al-Harthi
Summary: The synthesis of polar functionalized polyolefin (PFP) improves mixing properties, polymer surface, and rheological properties for upgraded polyolefins. Metal-based catalyzed olefin copolymerization with polar comonomers offers an energy-efficient and upfront methodology, with late transition metal-based catalysts making progress in recent years. The development of nickel-based catalysts for PFP synthesis has shown rigorous progress in the past half-decade. This review summarizes the research trends in both early and late transition metal-based catalyst development and highlights the influence of transition metal-based catalysts on polymer properties.
Article
Polymer Science
Fei Wang, Li Pan, Vladislav A. Tuskaev, Svetlana Ch. Gagieva, Yue-Sheng Li
Summary: This study develops a nickel-based catalyst for the efficient copolymerization of olefin with polar monomers, which has been a longstanding challenge in the field.
CHINESE JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Koichiro Masada, Shuhei Kusumoto, Kyoko Nozaki
Summary: In this study, a novel method for synthesizing metallabenzenes by replacing the phosphorus atom in an aromatic phosphinine ring with transition metal fragments was reported. Iridabenzene and rhodabenzene were successfully synthesized by triggering the replacement of the phosphorus atom with iridium and rhodium fragments, respectively. The aromaticity of the newly synthesized metallabenzenes was evaluated experimentally and theoretically.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Falk William Seidel, Kyoko Nozaki
Summary: Access to boryl ligands and complexes for catalysis remains limited, but this study presents an optimized synthesis of a novel borane/phosphine ligand and its Ni-0 sigma-borane complex, enabling an unprecedented oxidative dehydrochloroborylation. The research suggests that B/P ligands can facilitate nickel-catalyzed ethylene polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qiang-Qiang Li, Yosuke Hamamoto, Germain Kwek, Bengang Xing, Yongxin Li, Shingo Ito
Summary: By imparting high solubility/hydrophilicity to polycyclic aromatic molecules, breakthroughs have been made in the research field, showing potential for applications in organic electronics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Chang-Sheng Wang, Ploypailin Siew Ling Tan, Wei Ding, Shingo Ito, Naohiko Yoshikai
Summary: This method efficiently synthesizes beta-iodo(III)enol carboxylates, phosphates, and tosylates through regio- and stereoselective iodo(III) functionalization of alkynes, which can be further used for the synthesis of multisubstituted alkenes.
Article
Chemistry, Multidisciplinary
Weifan Wang, Fiona Hanindita, Richard D. Webster, Shingo Ito
Summary: Buckybowl molecules, with their unique structure and chemical properties, have garnered significant attention across scientific disciplines. The fusion of buckybowl molecules offers a new strategy to expand the pi-surface of polycyclic aromatic compounds, although fusion of heteroatom-embedded buckybowls remains uncommon.
Article
Chemistry, Multidisciplinary
Weifan Wang, Fiona Hanindita, Yusei Tanaka, Kotaro Ochiai, Hiroyasu Sato, Yongxin Li, Takuma Yasuda, Shingo Ito
Summary: Sulfur-embedded polycyclic aromatic compounds have been widely used in the construction of organic semiconductors, but investigations on aromatic compounds containing thiepine, a sulfur-containing seven-membered-ring arene, have been limited. This study presents the synthesis and properties of pi-extended pyrrole-fused thiepine and oxepine compounds. A pi-extended pyrrole-fused thiepine exhibited a tilted pi-stacking structure in the crystal and demonstrated a high charge carrier mobility of up to 1.0 cm(2) V-1 s(-1) in single-crystal field-effect transistors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kang Yuan, Yukari Yamazaki, Xiongjie Jin, Kyoko Nozaki
Summary: A tungsten- and zirconium-oxide-supported platinum catalyst was developed for the hydrogenolysis of esters to alkanes at low temperatures and ambient pressure. The catalyst showed high activity, selectivity, and could be reused multiple times without significant loss.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Takuya Higashi, Shuhei Kusumoto, Kyoko Nozaki
Summary: We report a vanadium(I) complex of cyclopentadienone, a low-valent early transition metal, which shows electron transfer from the metal to the ligand. The complex exhibits catalytic transformations and elementary reactions, known as metal-ligand cooperation.
Article
Chemistry, Inorganic & Nuclear
Koichiro Masada, Shuhei Kusumoto, Kyoko Nozaki
Summary: This article discusses the structure and reactivity of novel Ag(I) complexes with tridentate phosphabenzene ligands. An equilibrium between the dimer and the monomer was observed for the lambda 3-phosphabenzene Ag(I) complex in the solution state. The lambda 3-phosphabenzene Ag(I) complex can be oxidized by PhI(OAc)2 to afford lambda 5-phosphabenzene species while maintaining coordination to the metal center. The photochemical properties of the Ag(I) complexes were also investigated, and the emission of the lambda 3-phosphabenzene Ag(I) complex showed solvatochromic behavior.
Article
Polymer Science
Kazuki Tsuge, Kate Lau, Yuko Hirooka, Takanori Iwasaki, Katsuyuki Yokomizo, Kyoko Nozaki
Summary: In this study, copolymerization of ethylene or propylene with norbornenes functionalized with polar groups using various palladium catalysts was reported. The structural analyses of the copolymers and evaluation of their thermal properties were conducted. This work also demonstrated the coordination-insertion copolymerization of propylene with disubstituted polar olefins for the first time.
Article
Multidisciplinary Sciences
Takanori Iwasaki, Kazuki Tsuge, Naoki Naito, Kyoko Nozaki
Summary: This study reports an Ir catalyst for the selective hydrogenolysis of urea derivatives, achieving the transformation of less reactive carbonyl compounds in the presence of more reactive ones. The proposed catalyst showed tolerance to highly reactive carbonyl groups such as ester, amide, and carbamate, and exhibited high chemoselectivity towards urea. This research provides a new strategy for the chemical recycling of polyurea resins.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kakeru Saito, Shuhei Kusumoto, Kyoko Nozaki
Summary: A novel cyclic bis(carbodiphosphorane) ligand was prepared and coordinated with group 13 elements, B, Al, and Ga. The ligand formed dinuclear adducts with Al and Ga, but formed a monomeric dicationic three-coordinate boron species with boron trichloride. X-ray crystallography revealed that the boron center in the dicationic compound had a strained trigonal geometry enforced by the cyclic structure. Theoretical investigation suggested the presence of tricationic two-coordinate boron resonance structure supported by the CDP ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Shuma Sasaki, Jun Kikuchi, Shingo Ito, Naohiko Yoshikai
Summary: In this study, a method for preparing stereodefined enolates by leveraging the stereoselective oxyfunctionalization of unactivated alkynes and their reaction with aldehydes to form γ,δ-unsaturated β-diketones was described.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Koichiro Masada, Kiyosumi Okabe, Shuhei Kusumoto, Kyoko Nozaki
Summary: Bimetallic complexes with bridging ligands enable precise control of catalysis. This study prepared a dinuclear Rh(-i)/Rh(i) complex bridged by tridentate phosphine-phosphinine-phosphine ligands using reduction. X-ray analysis and DFT calculations showed that the phosphinine ligands adopted an unsymmetric bridging mode, accepting d-electrons from one Rh center and donating lone pairs to the other Rh center.
Article
Chemistry, Multidisciplinary
Yuki Ito, Akiya Adachi, Kohsuke Aikawa, Kyoko Nozaki, Takashi Okazoe
Summary: This paper discloses the palladium-catalyzed aminofluorination of styrenes using novel N-fluorobenzenesulfonimide (NFSI) derivatives with deprotectable substituents, and the selective deprotection and transformation of the resulting products into amines under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2023)
