Review
Chemistry, Inorganic & Nuclear
Paulina Guerrero-Almaraz, Manuel Quiroz, Joseph H. Reibenspies, Marcetta Y. Darensbourg
Summary: Two synthetic approaches were used to install metallodithiolate ligands on molybdenum centers, resulting in a trimetallic dication, CoMoCo', with unique structure and characteristics, including bisnitrosylation and the generation of unpaired electrons.
INORGANIC CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Dmitrii Semenok, Ivan A. Troyan, Anna G. Ivanova, Alexander G. Kvashnin, Ivan A. Kruglov, Michael Hanfland, Andrey Sadakov, Oleg A. Sobolevskiy, Kirill S. Pervakov, Igor S. Lyubutin, Konstantin Glazyrin, Nico Giordano, Denis N. Karimov, Alexander L. Vasiliev, Ryosuke Akashi, Vladimir M. Pudalov, Artem R. Oganov
Summary: Through high-pressure synthesis, a series of lanthanum-yttrium ternary hydrides were discovered, including novel compounds such as cubic hexahydride (La,Y)H6 and decahydrides (La,Y) H-10 with high critical temperature and magnetic field. The critical current density in (La,Y)H-10 is comparable to that of commercial superconducting wires. These findings represent the first examples of ternary high-Tc superconducting hydrides and demonstrate a new method for stabilizing hydrides.
Article
Chemistry, Inorganic & Nuclear
Zhiwei Peng, Shu Li, Ao Li, Jiaming Liao, Yiman Wang, Xudong Li, Wei Meng, Jian Zhang
Summary: This article describes the synthesis of an enantiomeric pair of 3d-3d heterometallic clusters in an aqueous solution without heating. The crystal structures reveal a five-layered core structure with a slightly distorted tetradecahedron composed of Mn and Cu ions. Magnetic measurements show that these clusters exhibit slow relaxation of their magnetization vectors.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Xunxiang Hu, Kurt A. Terrani
Summary: This paper reports the properties of unirradiated bulk yttrium hydride as a function of hydrogen concentration, providing a baseline measurement for further neutron irradiation response studies. It suggests the recommended empirical treatment of the data and discusses other properties that need to be investigated.
JOURNAL OF ALLOYS AND COMPOUNDS
(2021)
Article
Chemistry, Multidisciplinary
Gabriele Hierlmeier, Paolo Tosatti, Kurt Puentener, Paul J. J. Chirik
Summary: This study reports a new molybdenum ligand for catalyzing the hydrogenation of benzene, which is formed by the coordination of phosphino(imino)pyridine and cyclooctadiene. The experimental results indicate that the ligand can selectively generate cyclohexane catalyst in the presence of benzene, and the formation of the insertion product is a key step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marti Garcon, Andreas Phanopoulos, Andrew J. P. White, Mark R. Crimmin
Summary: Reaction of a hexagonal planar palladium complex with H-2 leads to the formation of a new tetrahydride species and a magnesium hydride co-product. Similar complexes with analogues metals could be isolated and characterized through independent syntheses. Computational analysis suggests a square planar structure with marginal metal-metal interactions, and DFT calculations support a ligand-assisted oxidative addition mechanism for H-2 activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mami Miyairi, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda
Summary: Improved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s using MoCl5- and WCl4-based catalytic systems have been developed. MoCl5 induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph4Sn and (ArSnBu3)-Bu-n to produce cis-stereoregular linear poly(diphenylacetyelene)s with high molecular weights. On the other hand, WCl4 induces ring expansion polymerization of diphenylacetylenes in the presence of Ph4Sn or reducing reagents to produce cis-stereoregular cyclic poly(diphenylacetylene)s with high molecular weights. Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Thomas E. Shaw, Charlotte L. Stern, Alfred P. Sattelberger, Titel Jurca
Summary: Group 5 and 6 metal chlorides can be easily and controllably reduced by stoichiometric PhMe2SiH, yielding PhMe2SiCl and H2 as the byproducts. The addition of varying amounts of PhMe2SiH to toluene solutions of MClx leads to stepwise uncoordinated reduction products, which can be further derivatized and used as desired inorganic synthons.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Harry Peirson, Juncheng Pan, Yizhe Li, David A. Hall, Andy P. Brown, Rik M. Drummond-Brydson, Steven J. Milne
Summary: An unfilled tungsten bronze-structured ferroelectric ceramic, Ca0.28Ba0.72Nb2O6 (CBN28), was doped with Y3+ to create ceramics with various compositions (Ca0.28Ba0.72)1-3w/2YwNb2O6 [0 <= w <= 0.05]. The substitution of Y3+ for Ca2+/Ba2+ resulted in a minor reduction of the lattice parameter and unit cell volume. Doped ceramics showed changes in permittivity, polarization, and temperature stability, indicating potential for high temperature dielectrics.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Materials Science, Multidisciplinary
Eui Seon Lee, Youn Ji Heo, Young In Lee, Young Keun Jeong, Sung Tag Oh
Summary: An optimum route to fabricate the dense W-base composite with homogenous dispersion of nano-sized La2O3 particles and increased mechanical property is investigated. The wet chemical method combined with spray pyrolysis and polymer solution is a promising way to synthesize the W-based composites with homogeneous dispersion of fine oxide particles and enhanced mechanical properties.
JOURNAL OF MATERIALS SCIENCE
(2022)
Article
Green & Sustainable Science & Technology
Fan Guo, Xiaoli Xi, Liwen Ma, Zuoren Nie
Summary: This study proposes a recyclable clean separation technology for tungsten and molybdenum using a porous amine resin. The resin exhibited a high sorption capacity and good cycle performance, and the separation of tungsten and molybdenum was achieved through ion exchange and chemical binding. This technology has significant implications for waste recovery.
JOURNAL OF CLEANER PRODUCTION
(2022)
Article
Chemistry, Multidisciplinary
Sylvain Sudan, Farzaneh Fadaei-Tirani, Kay Severin
Summary: A penta-stranded helicate was synthesized by combining [Pd(CH3CN)(4)](BF4)(2) with La(NO3)(3) and a polydentate ligand. The helicate exhibited low symmetry in both solution and solid state. By adjusting the metal-to-ligand ratio, a dynamic interconversion between the penta-stranded helicate and a symmetrical, four-stranded helicate was achieved.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Shingo Machida, Ken-ichi Katsumata, Kei Maeda, Atsuo Yasumori
Summary: This study investigated the effect of vanadium oxide on the crystallization of CaO-Al2O3-SiO2 (CAS) glasses. It was found that the addition of vanadium oxide controlled the aspect ratio of layered crystals in the glass and a new nucleation agent for the precipitation of metastable CaAl2Si2O8 in CAS glass was developed. The results showed that the addition of a relatively small content of vanadium oxide increased the aspect ratio of metastable CaAl2Si2O8 particles and no crystallization occurred without metallic Mo particles.
Article
Chemistry, Multidisciplinary
Zhujun Huang, Zhe Chen, Yuan Jiang, Ning Li, Shicheng Yang, Guowei Wang, Xiangcheng Pan
Summary: This study presents a metal-free visible-light-driven hydrosilylation polymerization method for both electron-rich and electron-deficient dienes with bis(silane)s, achieving controlled step-growth polymerizations. The approach provides the opportunity to produce a wide range of polycarbosilanes with high molecular weight, excellent thermal stability, and tunable architectures by tuning the concentration of dienes and the ratio of bis(silane)s.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Jiahao Rao, Shicheng Dong, Chengbo Yang, Qing Liu, Xuebing Leng, Dongyang Wang, Jun Zhu, Liang Deng
Summary: Tuning the spin state of metal carbynes is a challenging task in chemistry. We have synthesized the first triplet metal terminal carbyne, which exhibits unique reactivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qingde Zhuo, Jimin Yang, Zhenbo Mo, Xiaoxi Zhou, Takanori Shima, Yi Luo, Zhaomin Hou
Summary: The reaction of N2 with CO2 in a dititanium dihydride framework has been reported for the first time, resulting in N-C bond formation and cleavage of N-N and C-O bonds. The selectivity of the reaction products was found to be influenced by temperature. Mechanistic details were clarified through isotope-labeling experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Lei Jiang, Yinran Wang, Hanyang Sun, Tingting Fu, Zhaomin Hou, Fang Guo
Summary: This study successfully achieved the coordination polymerization of diphenylphosphinostyrene and its copolymerization with styrene, resulting in a new series of phosphine functionalized syndiotactic polystyrene with excellent thermal stability and chemical resistance. The combination of triphenylphosphine and syndiotactic polystyrene allowed for the stable immobilization of metal nanoparticles to form highly robust nanocatalysts, showing high efficiency as a heterogeneous catalyst for the synthesis of quinoline derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Polymer Science
Fen You, Xiaohui Kang, Masayoshi Nishiura, Jingjing Zhai, Suting Xu, Jixing Wang, Xiaochao Shi, Zhaomin Hou
Summary: This study reports the living and highly 3,4-isoselective polymerization of biobased monomer beta-farnesene using a phosphine-functionalized fluorenyl-ligated yttrium catalytic system. The coordination of the phosphine group plays a pivotal role in the regio- and stereoselectivity of the polymerization. Block copolymers with specific properties were successfully prepared. This research is important for reducing petrochemical dependency.
Article
Chemistry, Multidisciplinary
Haobing Wang, Yang Yang, Masayoshi Nishiura, You-lee Hong, Yusuke Nishiyama, Yuji Higaki, Zhaomin Hou
Summary: The synthesis of self-healing polymers from simple commodity dienes, such as isoprene, using catalyst-controlled polymerization has shown to produce excellent self-healing elastomers. The self-healability is attributed to nanoscale heterogeneities formed by microphase separation of hard 3,4-segments from a flexible cis-1,4-segment matrix.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Wenxuan Xu, Xuefeng Cong, Kun An, Shao-Jie Lou, Zhenghua Li, Masayoshi Nishiura, Tetsuro Murahashi, Zhaomin Hou
Summary: In this study, the intermolecular regio- and diastereoselective formal [2+2] cycloaddition of allenes with amino-functionalized alkenes was achieved using half-sandwich rare-earth catalysts. The reaction proceeded through an allene C(sp(2))-H activation mechanism, leading to the synthesis of a new family of cyclobutane and cyclobutene derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Masanori Takimoto, Mingyu Liu, Masayoshi Nishiura, Zhaomin Hou
Summary: A regioselective benzylic C-H alumination method has been developed for various symmetrical and nonsymmetrical 2,6-alkylpyridines. The resulting alkylaluminum species can be transformed to the corresponding alcohols by oxidation. Additionally, Cu-catalyzed allylation and benzylation reactions, as well as Pd-catalyzed arylation reactions, can be applied to the alkylaluminum species to obtain α-mono-allylated, α-mono-benzylated, and α-mono-arylated 2-alkylpyridine derivatives.
Article
Chemistry, Physical
Aniket Mishra, Ping Wu, Xuefeng Cong, Masayoshi Nishiura, Gen Luo, Zhaomin Hou
Summary: This study reports the exo-selective, regiospecific annulation of a wide range of functionalized aromatic substrates with 1,1-disubstituted alkenes through C(sp2)-H and benzylic C(sp3)-H activation by half-sandwich rare-earth catalysts. It provides a straightforward and atom-efficient method for the synthesis of indane and tetralin derivatives bearing an all-carbon quaternary stereocenter that were previously difficult to access by other catalysts. The reaction mechanism has been elucidated using deuterium-labeling experiments and DFT calculations.
Review
Chemistry, Multidisciplinary
Qingde Zhuo, Xiaoxi Zhou, Takanori Shima, Zhaomin Hou
Summary: This review focuses on N-2 activation and addition to unsaturated substrates mediated by transition metal complexes, which resulted in various N-C bond formation products. The emphasis is on the reaction modes and mechanisms. It is hoped that this work will inspire further explorations in this challenging field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Xuefeng Cong, Lin Huang, Zhaomin Hou
Summary: This Perspective focuses on recent advances in C-H functionalization with alkenes, allenes, and alkynes by half-sandwich rare-earth catalysts, including asymmetric transformations. The reaction generally proceeds through formal C-H addition to unsaturated C-C bonds, thus constituting a 100% atom-efficient route for the construction of new C-C bonds. Future outlooks in related areas are also described.
Article
Chemistry, Multidisciplinary
Aniket Mishra, Xuefeng Cong, Masayoshi Nishiura, Zhaomin Hou
Summary: Multisubstituted chiral 1-aminoindanes are important components in pharmaceuticals and bioactive molecules. The synthesis of chiral 1-aminoindanes is of great interest and importance, and the asymmetric[3 + 2] annulation of aldimines with alkenes through C-H activation is a promising method. This study reports the enantioselective [3 + 2] annulation of aromatic aldimines and alkenes via ortho-C(sp(2))-H activation using chiral half-sandwich scandium catalysts, which provides a straightforward route for the synthesis of multisubstituted chiral 1-aminoindanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yat-Ming So, Ching Tat To, Murali Mohan Guru, Takanori Shima, Zhaomin Hou
Summary: Carbon-carbon bond formation via coupling of two organic components is an important chemical transformation. In this study, a hydrodeoxygenative coupling of aromatic aldehydes was achieved to form bibenzyls by a titanium imide/hydride complex. The complex also demonstrated the ability to activate and functionalize N-2, as well as providing a platform for C-C bond formation using carbonyl compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Masanori Takimoto, Zhaomin Hou
Summary: An efficient protocol for the carbozincation of allenamides has been developed using dialkylzinc reagents catalyzed by an NHC Cu complex. This method allows for regio- and stereoselective introduction of alkyl and zinc groups to the allenamides, leading to the formation of alkenylzinc species. These species can further undergo C-C bond-forming reactions, resulting in the synthesis of multi-substituted enamides.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Aniket Mishra, Ping Wu, Xuefeng Cong, Masayoshi Nishiura, Gen Luo, Zhaomin Hou
Summary: In this study, we report the exo-selective, regiospecific annulation of a wide range of functionalized aromatic substrates with 1,1-disubstituted alkenes through C(sp(2))-H and benzylic C(sp(3))-H activation using half-sandwich rare-earth catalysts. This protocol provides a straightforward and atom-efficient route for synthesizing indane and tetralin derivatives bearing an all-carbon quaternary stereocenter that were previously difficult to access using other catalysts. The reaction mechanism has been elucidated through deuterium-labeling experiments and DFT calculations.
Article
Chemistry, Multidisciplinary
Wei Zhou, Xuefeng Cong, Masayoshi Nishiura, Zhaomin Hou
Summary: The ortho-selective benzylic C(sp(3))-H alkenylation of 2-methyl tertiary anilines with internal alkynes has been achieved for the first time by using a half-sandwich scandium catalyst. This protocol provides a straightforward route for the synthesis of a new family of 2-allylaniline derivatives, featuring broad substrate scope, 100% atom-efficiency, high yields, and high chemo-, regio-, and stereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)