Article
Chemistry, Multidisciplinary
Sourav Kar, Subhash Bairagi, Jean-Francois Halet, Sundargopal Ghosh
Summary: Although Lipscomb predicted in 1977 that supra-icosahedral boron clusters would be viable, their synthesis has been hindered by the lack of suitable synthetic methodologies. This study reports the first examples of open 16-vertex oblato-hypotitanaborane clusters [(Cp*Ti)(2)B14H17R] (1: R = H; 2: R = Me) with a non-Wadean 19-skeletal-electron-pair count. Interestingly, these clusters exhibit a six-membered [Ti2B4] open face, which could potentially lead to the formation of closo-19-vertex clusters.
CHEMICAL COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Fatou Diaw-Ndiaye, Pablo Sanz Miguel, Ricardo Rodriguez, Ramon Macias
Summary: The octahydridotriborate anion plays a crucial role in polyhedral boron chemistry, and it has been used in the synthesis of alkylborates and transition metal complexes. In this study, a novel rhodatetraborane dihydride complex was successfully synthesized and extensively characterized. The complex exhibits intriguing fluxional behavior and reacts with pyridine and dimethylphenylphosphine to form borane adducts. Additionally, new cationic hydride complexes have been characterized, including the octahydridotriborate salt.
Article
Chemistry, Inorganic & Nuclear
Artiom Gaina-Gardiuta, Alexandru Lupan, R. Bruce King
Summary: Density functional theory studies suggest that high-spin triplet and quintet structures are energetically favorable for dimanganaboranes of first-row manganese, while flattened singlet structures are preferred for dimetallaboranes of third-row rhenium. The different peference might be attributed to the ligand field splittings in complexes of manganese and rhenium.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Manjur O. Akram, John R. Tidwell, Jason L. Dutton, Caleb D. Martin
Summary: The synthesis of a single site neutral Lewis superacid, tris(ortho-carboranyl)borane (BoCb(3)), was achieved in one pot from commercially available materials. It was confirmed to be a Lewis superacid due to its high fluoride ion affinity (FIA), and exhibited stronger Lewis acidity compared to widely used fluorinated aryl boranes, as evidenced by the Gutmann-Beckett method and adducts with Lewis bases. The unusually high Lewis acidity can be rationalized by the electron-withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO. Catalytic studies demonstrated that BoCb(3) is a superior catalyst for promoting C-F bond functionalization reactions compared to tris(pentafluorophenyl)borane [B(C6F5)(3)].
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Inorganic & Nuclear
I. B. Sivaev
Summary: The review summarized the data on the functional group directed B-H activation reactions of polyhedral boron hydrides by transition metal complexes from the early 1980s to the most recent advances. The formation of complexes of transition metals with M center dot center dot center dot H-B and M-B bonds and their use in the synthesis of various organic derivatives of (car)boranes were discussed.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zi-Yu Zhang, Jie Ren, Ming Zhang, Xiu-Fang Xu, Xiao-Chen Wang
Summary: This study reports the synthesis of N-heterocycles using borane-catalyzed dehydrogenative cyclization of 2-cyclopropyl-N,N-dimethylanilines. The key steps include borane-mediated cyclopropane ring-opening and borane-mediated hydride abstraction from the N-methyl group. The substituent at the cyclopropyl unit greatly influences the reaction pathway and determines the major reaction product.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
R. Bruce King
Summary: The anion [Au@Ru-5(CO)(15)(mu-CO)(4)](-) has a pentagonal wheel structure derived from a hypothetical pentagonal ruthenium carbonyl cluster by inserting a gold atom in the center. This structure exhibits similarities to aromatic sextet and deltahedral borane anion B7H72-. Similarly, hexagonal wheel complexes Ni@P6R6 and Pd@Pd-6(mu-N=CtBu(2))(6) can be derived from a hexagonal bipyramid. A reasonable chemical bonding model for the hexagonal wheel complexes has three-fold symmetry with 3c-2e bonds, analogous to the C=C double bonds in a Kekule structure of benzene.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Mario Bakardjiev, Josef Holub, Zdenka Ruzickova, Ales Ruzicka, Jindrich Fanfrlik, Bohumil Stibr, Michael L. McKee, Drahomir Hnyk
Summary: Mutual rearrangements in the series of seven bicapped-square antiprismatic closo-C2B8H10 were studied using high-quality computations, which disprove the earlier postulated dsd mechanism and propose a new Z-mechanism for these isomerizations. Experimentally observed thermal rearrangements indirectly support these refined computations.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Yingying Wang, Hui Han, Jia-Xin Kang, Jiamin Peng, Xiongxiong Lu, Hou-Ji Cao, Zhenxing Liu, Xuenian Chen
Summary: An efficient method for synthesizing 6-substituted decaboranyl ethers and sulfides has been developed using trimethylsilyl trifluoromethanesulfonate as the mediator at room temperature. The reaction shows excellent regioselectivity and high yields of the products.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Joseph Bedard, Saurabh S. Chitnis
Summary: The relationship between monomer structure and polymer properties is crucial in materials science. This article discusses the concept of monomer dimensionality, including 1-dimensional chains, 2-dimensional rings, and 3-dimensional cages, in inorganic polymers. It highlights ring-containing systems and classical 3-dimensional inorganic monomers, as well as the development of phosphorus-nitrogen (PN) cages into polymerizable synthons for accessing linear or networked inorganic materials. The article also summarizes the major obstacles in the field and identifies areas for impactful discoveries.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Amr A. A. Attia, Alexandru Lupan, R. Bruce King
Summary: The structures and energetics of the neutral B n-1H n-1Fe(CO)( x ) (x = 4,3) and the dianions [B n-1H n-1Fe(CO)(3)](2-) (n = 6-14) were studied. The dianions [B n-1H n-1Fe(CO)(3)](2-) have closo deltahedral structures, while the neutral tricarbonyls B n-1H n-1Fe(CO)(3) have capped deltahedra or isocloso deltahedra structures. Carbonyl migration occurs in the tetracarbonyls B( n-1)H( n-1)Fe(CO)(4), resulting in different structures.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Inorganic & Nuclear
Xi-Meng Chen, Xing-Chao Yu, Jing-Xian Chi, Yi Jing, Hongju Wang, Na Zhang, Chen Zhang, Yi-Wen Ge, Xuenian Chen
Summary: An efficient method for synthesizing M2B10H14 has been developed, and two possible formation mechanisms of the B10H142- anion have been proposed. The intermediates B10H13- and B10H15- were also detected.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Fangxiang Sun, Shuaimin Tan, Hou-Ji Cao, Chang-sheng Lu, Deshuang Tu, Jordi Poater, Miquel Sola, Hong Yan
Summary: This study reports three types of tricyclic compounds based on the fusion of three-dimensional aromatics and hydrocarbons, which can be used to prepare various functional molecules. These new compounds can be easily synthesized using Pd-catalyzed B-H activation and the cascade heteroannulation reaction. Computational results show that the newly generated rings have weak aromaticity, but they possess high thermal stability and photoluminescence efficiency.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Shouhu Li, Yichun Zhang, Yiming Ma, Pengtao Qiu, Xuenian Chen
Summary: The derivatives of [CHB9H9] (-) anion have attracted attention in catalysis and superionic conductivity materials. A facile synthetic method based on the Brellochs method has been developed, avoiding cation exchange for oxidation cluster closure and enabling almost quantitative conversion of positional isomerism.
Article
Chemistry, Multidisciplinary
Yi Jing, Xinghua Wang, Hui Han, Xin-Ran Liu, Xing-Chao Yu, Xi-Meng Chen, Donghui Wei, Lai-Sheng Wang, Xuenian Chen
Summary: This study reports highly selective and efficient synthetic methods for the salts of B11H14- and B12H122- anions using commercially available and inexpensive starting materials. Through theoretical and experimental investigations, the researchers elucidated the nature of the B-H bond condensation and the general formation mechanisms of polyhedral boranes. This finding not only provides more effective synthetic methods for polyhedral boranes, but also facilitates their wide application.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Md. Mamdudur Rahman, Mark D. Smith, Jose A. Amaya, Thomas M. Makris, Dmitry V. Peryshkov
INORGANIC CHEMISTRY
(2017)
Article
Chemistry, Inorganic & Nuclear
Eric V. Bukovsky, Dmitry V. Peryshkov, Hui Wu, Wei Zhou, Wan Si Tang, W. Matthew Jones, Vitalie Stavila, Terrence J. Udovic, Steven H. Strauss
INORGANIC CHEMISTRY
(2017)
Review
Chemistry, Inorganic & Nuclear
Bennett J. Eleazer, Dmitry V. Peryshkov
COMMENTS ON INORGANIC CHEMISTRY
(2018)
Article
Chemistry, Inorganic & Nuclear
Mohammad Jahirul Islam, Mark D. Smith, Dmitry V. Peryshkov
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Bennett J. Eleazer, Mark D. Smith, Alexey A. Popov, Dmitry V. Peryshkov
Article
Chemistry, Inorganic & Nuclear
Md. Mamdudur Rahman, Mark D. Smith, Dmitry V. Peryshkov
Article
Chemistry, Inorganic & Nuclear
Matthew R. Lacroix, Eric V. Bukovsky, Matic Lozinsek, Travis C. Folsom, Brian S. Newell, Yong Liu, Dmitry V. Peryshkov, Steven H. Strauss
INORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Gayathri B. Gange, Amanda L. Humphries, Dmitry E. Royzman, Mark D. Smith, Dmitry Peryshkov
Summary: The metal-free bond activation by carboranyl diphosphine 1-(PBu2)-Bu-t-2-(PPr2)-Pr-i-C2B10H10 involves the formal oxidation of phosphine groups and concomitant reduction of the boron cage in reactions with main group hydrides and alcohols. This new approach is driven by the cooperation between electron-donating exohedral substituents and electron-accepting cluster, and is reminiscent of oxidative addition to transition metal centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Bennett J. Eleazer, H. D. A. Chathumal Jayaweera, Gayathri B. Gange, Mark D. Smith, Corey R. Martin, Kyoung Chul Park, Alexey A. Popov, Dmitry Peryshkov
Summary: The synthesis of well-defined heterometallic complexes is a challenging frontier in inorganic chemistry. A new approach involving sequential insertion of electrophilic metal fragments into electron-rich Ru-B bonds has been reported, leading to the selective preparation of bimetallic and trimetallic complexes. Structural and theoretical analysis of chemical bonding features within Ru-B-B-Cu and Ru-B-B-Pd fragments were presented.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Gayathri B. Gange, Amanda L. Humphries, Mark D. Smith, Dmitry V. Peryshkov
Summary: In this study, we report the reactivity of carboranyl diphosphine with terminal alkynes, resulting in the formation of boron-containing phosphacycles. The reaction combines the activation of electron-deficient alkynes by phosphine groups and the redox behavior of carborane clusters, leading to the formation of a fused product of alkenylphosphonium cycle and reduced carborane cluster.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Mohammad Jahirul Islam, Kyoung Chul Park, Olivia M. M. Manley, Mark D. D. Smith, Thomas M. M. Makris, Dmitry V. V. Peryshkov
Summary: We describe the synthesis and characterization of a nickel(II) complex with a dicarboranyl CNC dianionic pincer ligand, which can activate acetonitrile through C-C bond cleavage. By deprotonating the relatively acidic C-H bond of coordinated acetonitrile with potassium t-butoxide, a C-bound cyanomethylene ligand is formed at the metal center. Unlike most previously characterized Ni(II) cyanoalkyls, this complex can rapidly transform under aerobic conditions at room temperature to form CNC-ligated nickel(II) cyanide, indicating facile cleavage of the C-CN bond. The cyanoalkyl and cyanide complexes were isolated in excellent yields and characterized by NMR spectroscopy and single-crystal X-ray diffraction.
Article
Chemistry, Multidisciplinary
Bryce C. Nussbaum, Amanda L. Humphries, Gayathri B. Gange, Dmitry V. Peryshkov
Summary: Icosahedral closo-dodecaboranes have the ability to accept two electrons, transforming into a dianionic nido-cluster. This transformation can be used for electron storage, bond activation, or altering coordination to metal cations. In this feature article, we present cases demonstrating the redox activity of carborane leading to unique products. We emphasize the impact of exohedral substituents on reactivity and product stability through conjugation with the cluster.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Brandon K. Redden, Robert W. Clark, Ziyuan Gong, Md Mamdudur Rahman, Dmitry Peryshkov, Sheryl L. Wiskur
Summary: The mechanism of the asymmetric silylation of alcohols with isothiourea catalysts was studied using reaction progress kinetic analysis, revealing the significance of silyl chloride in the reaction. The findings contribute to understanding the catalytic mechanism of the reaction and offer insights for further research.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
H. D. A. Chathumal Jayaweera, Md Mamdudur Rahman, Perry J. Pellechia, Mark D. Smith, Dmitry Peryshkov
Summary: This work presents the synthesis and structural characterization of the free ortho-carboranyl [C2B10H11](-) and the doubly deprotonated 1,1'-bis(o-carborane) anion [C2B10H10](2)(2-), which are important intermediates in carborane chemistry. The study represents the first examples of a stable, discrete C(H)-deprotonated carborane anion and a discrete molecular dicarbanion, respectively. These findings contribute to the understanding of carbon vertex chemistry in carborane clusters.
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
