Boron Chemistry: Fundamentals and Applications

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (31 December 2023) | Viewed by 10545

Special Issue Editors


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Guest Editor
Laboratory for Innovative Key Materials and Structures—LINK (UMI/IRL 3629), CNRS—Saint Gobain—NIMS International Collaboration Center, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Japan
Interests: chemical bonding; molecular quantum chemistry; solid-state quantum chemistry; inorganic chemistry; molecular electronics; thermoelectric materials

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Guest Editor
Institut des Sciences Chimiques de Rennes (ISCR), UMR-CNRS 6226, Université de Rennes 1, CEDEX, Rennes, France
Interests: organic/organometallic boron chemistry; B–H bond activation and BN bond engineering; polyaminoboranes

Special Issue Information

Dear Colleagues,

Boron chemistry, which is unique in many aspects, features in numerous fields, including organic, organometallic, inorganic, and medicinal chemistries with various applications in polymers and materials. On the occasion of the 17th International Meeting on Boron Chemistry, we cordially invite you to submit a review or research paper to this Special Issue of Inorganics entitled “Boron Chemistry: Fundamentals and Applications”. This Special Issue focuses on the latest advances made in boron chemistry associated with the development of novel synthetic methodologies, structural elucidations, bonding analysis, and also possible applications in all fields of boron chemistry. The collection of contributions should provide a forum that will allow for a wide dissemination of results in diverse research areas of boron chemistry that may inspire future research directions.

Prof. Dr. Jean-François Halet
Prof. Dr. Gilles Alcaraz
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

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Keywords

  • boron in catalysis
  • boron in organometallic chemistry
  • boron in materials science
  • boron in medicine
  • boron in synthesis and organic chemistry
  • bonding analysis of boron compounds
  • cluster boron chemistry

Published Papers (6 papers)

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Research

13 pages, 3419 KiB  
Article
Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters
by Alaka Nanda Pradhan, Shippy Jaiswal, Marie Cordier, Jean-François Halet and Sundargopal Ghosh
Inorganics 2024, 12(1), 7; https://doi.org/10.3390/inorganics12010007 - 23 Dec 2023
Viewed by 1332
Abstract
The synthesis and structural characterization of a series of heterotrimetallic ruthenaborane clusters are reported. The photolytic reaction of nido-[(Cp*Ru)2(µ-H)2B3H7] (nido-1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with [M(CO)5·THF] (THF [...] Read more.
The synthesis and structural characterization of a series of heterotrimetallic ruthenaborane clusters are reported. The photolytic reaction of nido-[(Cp*Ru)2(µ-H)2B3H7] (nido-1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with [M(CO)5·THF] (THF = tetrahydrofuran, M = Mo and W) yielded the heterotrimetallic clusters pileo-[(Cp*Ru)2{M(CO)3}(µ-CO)(µ-H)(µ3-BH)B2H5], M = Mo (2), W (3) and the known arachno ruthenaboranes [1,2-(Cp*Ru)(Cp*RuCO)(µ-H)B3H8] (I) and [{Cp*Ru(CO)}2B2H6] (II). In an attempt to synthesize the Mn-analog of 2 and 3, we performed a similar reaction of nido-1 with [Mn2(CO)10], which afforded the heterotrimetallic pileo-[(Cp*Ru){Mn(CO)3}(µ-H)2(µ3-BH)B2H5] (4) cluster along with the reported trimetallic hydrido(hydroborylene) species [(Cp*Ru)2{Mn(CO)3}(µ-H)(µ-CO)3(µ-BH)] (III). Ruthenaboranes 2, 3 and 4 are isoelectronic and isostructural. The geometry of 24 can be viewed as a triangle face-fused square pyramidal and tetrahedral geometry, in which the apical vertex of the tetrahedron is occupied by a µ3–BH moiety. All of these pileo ruthenaborane clusters obey Mingos’ fusion formalism. Clusters 24 were characterized using multinuclear NMR, IR spectroscopies and electrospray ionization mass spectrometry. The single-crystal X-ray diffraction studies of clusters 2 and 4 confirmed their structures. Further, density functional theory (DFT) studies of these pileo ruthenaboranes have been carried out to investigate the nature of bonding, fusion and electronic structures. Full article
(This article belongs to the Special Issue Boron Chemistry: Fundamentals and Applications)
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21 pages, 3243 KiB  
Article
Hexafluoroisopropylboranes and -Borates
by Ludwig Zapf and Maik Finze
Inorganics 2023, 11(12), 471; https://doi.org/10.3390/inorganics11120471 - 04 Dec 2023
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Abstract
Novel hexafluoroisopropylboranes (CF3)(CF2H)CFBH2·L and -borate anions [(CF3)(CF2H)CFBH2X] with Lewis basic heterocyclic ligands L and the anionic substituents X = F and CN were obtained. The syntheses [...] Read more.
Novel hexafluoroisopropylboranes (CF3)(CF2H)CFBH2·L and -borate anions [(CF3)(CF2H)CFBH2X] with Lewis basic heterocyclic ligands L and the anionic substituents X = F and CN were obtained. The syntheses were accomplished by substitution reactions of the dimethyl sulfide adduct (CF3)(CF2H)CFBH2·SMe2, which was synthesized on a large scale. The hexafluoroisopropylboranes and -borates were characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the thermal and electrochemical stabilities were investigated by DSC measurements and cyclic voltammetry and selected experimental data and trends are compared with theoretical ones. Full article
(This article belongs to the Special Issue Boron Chemistry: Fundamentals and Applications)
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11 pages, 3419 KiB  
Article
The Structures and Bonding of Bismuth-Doped Boron Clusters: BiB4 and BiB5
by Hyun Wook Choi, Wei-Jia Chen, G. Stephen Kocheril, Dao-Fu Yuan and Lai-Sheng Wang
Inorganics 2023, 11(10), 405; https://doi.org/10.3390/inorganics11100405 - 14 Oct 2023
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Abstract
We present an investigation on the structures and chemical bonding of two Bi-doped boron clusters BiBn (n = 4, 5) using photoelectron spectroscopy and theoretical calculations. The electron affinities of BiB4 and BiB5 are measured to be 2.22(2) [...] Read more.
We present an investigation on the structures and chemical bonding of two Bi-doped boron clusters BiBn (n = 4, 5) using photoelectron spectroscopy and theoretical calculations. The electron affinities of BiB4 and BiB5 are measured to be 2.22(2) eV and 2.61(2) eV, respectively. Well-resolved photoelectron spectra are obtained and used to compare with theoretical calculations to verify the structures of BiB4 and BiB5. Both clusters adopt planar structures with the Bi atom bonded to the periphery of the planar Bn moiety. Chemical bonding analyses reveal that the Bn moiety maintains σ and π double-aromaticity. The Bi atom is found to induce relatively small structural changes to the Bn moiety, very different from transition metal-doped boron clusters. Full article
(This article belongs to the Special Issue Boron Chemistry: Fundamentals and Applications)
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20 pages, 5484 KiB  
Article
Complexation of Boron and Aluminum with a Bidentate Hydroxy-BN-naphthalene Ligand
by Yannik Appiarius, Pim Puylaert, Julius Werthschütz, Tim Neudecker and Anne Staubitz
Inorganics 2023, 11(7), 295; https://doi.org/10.3390/inorganics11070295 - 12 Jul 2023
Cited by 1 | Viewed by 1326
Abstract
The isoelectronic relationship of 1,2-azaborinine (B=N structural motif) and benzene (C=C) is well documented. Upon deprotonation of the former, the anionic 1,2-azaboratabenzene is obtained, which is isosteric with pyridine (C=N) and has a similar capability as an aromatic N-donor. We present the [...] Read more.
The isoelectronic relationship of 1,2-azaborinine (B=N structural motif) and benzene (C=C) is well documented. Upon deprotonation of the former, the anionic 1,2-azaboratabenzene is obtained, which is isosteric with pyridine (C=N) and has a similar capability as an aromatic N-donor. We present the complexation of boron and aluminum precursors with a κ2-N,O-donating 8-hydroxy-BN-naphthalene ligand (H2(BQ), 1). Six chelate complexes with 1:1 and 2:1 stoichiometries were isolated and characterized by X-ray diffraction analysis and NMR spectroscopy. Comparing the isosteric dimethylaluminum complexes of H2(BQ) and an 8-hydroxyquinoline (HQ’, 2) as a reference allowed us to quantify the influence of a formal substitution of carbon by boron on the structure and the electronic properties: While the structural parameters of the ligands were similar, the electropositive boron atom affected the electron density distributions within the complexes substantially. As the consequence, the Al–N bond was significantly shortened, and the aluminum atom showed a different coordination geometry than in the quinoline analog. Moreover, strong hypsochromic shifts of both the absorption and the emission were observed. The results highlight that the differences between CN and BN polyaromatic complexes are more distinct than between equally charged BN and CC congeners. Full article
(This article belongs to the Special Issue Boron Chemistry: Fundamentals and Applications)
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19 pages, 4140 KiB  
Article
A Boron-Containing Analogue of Acetaminophen Induces Analgesic Effect in Hot Plate Test and Limited Hepatotoxicity
by Melvin Nadir Rosalez, Eunice D. Farfán-García, Jesús Badillo-Romero, Ricardo Iván Córdova-Chávez, José G. Trujillo-Ferrara, José A. Morales-González, Marvin A. Soriano-Ursúa and Marlet Martínez-Archundia
Inorganics 2023, 11(6), 261; https://doi.org/10.3390/inorganics11060261 - 20 Jun 2023
Viewed by 1621
Abstract
Acetaminophen is the most sold drug to treat pain. The TRPV1 channel is among its main targets. Due to its over-the-counter availability, its use is known as the main cause of acute liver failure induced by drugs. In addition, boron-containing compounds (BCC) have [...] Read more.
Acetaminophen is the most sold drug to treat pain. The TRPV1 channel is among its main targets. Due to its over-the-counter availability, its use is known as the main cause of acute liver failure induced by drugs. In addition, boron-containing compounds (BCC) have shown higher efficiency, potency, and affinity than their carbon counterparts. The present study explored the potential analgesic effect and hepatotoxicity of a BCC with a similar chemical structure to acetaminophen. Docking studies were carried out on the TRPV1 channel. In addition, a hot plate test was carried out with three doses of acetaminophen (APAP) and equimolar doses of 4-acetamidophenylboronic acid (4APB) in C57bl/6 mice. These same mice were submitted to a partial hepatectomy and continued compound administration, then they were sacrificed at day seven of treatment to analyze the liver histology and blood chemistry markers. From the in silico assays, it was observed that APAP and 4APB shared interactions with key residues, but 4APB showed a higher affinity on the orthosteric site. Mice administered with 4APB showed a higher latency time than those administered with their equimolar dose of APAP and the control group, with no motor pathway affected. The 4APB groups did not show an increase in hepatic enzyme activity while the APAP did show an increase in activity that was dose-dependent. Although all the experimental groups did show necrosis and inflammation, all APAP groups showed a greater cellular damage than their 4APB counterparts. In addition, the LD50 of 4APB is 409 mg/kg (against APAP-LD50 of 338 mg/kg). Thus, in the current evaluation, 4APB was a better analgesic and safer than APAP. Full article
(This article belongs to the Special Issue Boron Chemistry: Fundamentals and Applications)
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17 pages, 2597 KiB  
Article
Oxidoborates Templated by Cationic Nickel(II) Complexes and Self-Assembled from B(OH)3
by Mohammed A. Altahan, Michael A. Beckett, Simon J. Coles and Peter N. Horton
Inorganics 2021, 9(9), 68; https://doi.org/10.3390/inorganics9090068 - 31 Aug 2021
Cited by 2 | Viewed by 2665
Abstract
Several oxidoborates, self-assembled from B(OH)3 and templated by cationic Ni(II) coordination compounds, were synthesized by crystallization from aqueous solution. These include the ionic compounds trans-[Ni(NH3)4(H2O)2][B4O5(OH)4]. [...] Read more.
Several oxidoborates, self-assembled from B(OH)3 and templated by cationic Ni(II) coordination compounds, were synthesized by crystallization from aqueous solution. These include the ionic compounds trans-[Ni(NH3)4(H2O)2][B4O5(OH)4].H2O (1), s-[Ni(dien)2][B5O6(OH)4]2 (dien = N-(2-aminoethyl)-1,2-ethanediamine (2), trans-[Ni(dmen)2(H2O)2] [B5O6(OH)4]2.2H2O (dmen = N,N-dimethyl-1,2-diaminoethane) (3), [Ni(HEen)2][B5O6(OH)4]2 (HEen = N-(2-hydroxyethyl)-1,2-diaminoethane) (4), [Ni(AEN)][B5O6(OH)4].H2O (AEN = 1-(3-azapropyl) -2,4-dimethyl-1,5,8-triazaocta-2,4-dienato(1-)) (5), trans-[Ni(dach)2(H2O)2][Ni(dach)2] [B7O9(OH)5]2.4H2O (dach = 1,2-diaminocyclohexane) (6), and the neutral species trans-[Ni(en)(H2O)2{B6O7(OH)6}].H2O (7) (en = 1,2-diaminoethane), and [Ni(dmen)(H2O){B6O7(OH)6}].5H2O (8). Compounds 1–8 were characterized by single-crystal XRD studies and by IR spectroscopy and 2, 4–7 were also characterized by thermal (TGA/DSC) methods and powder XDR studies. The solid-state structures of all compounds show extensive stabilizing H-bond interactions, important for their formation, and also display a range of gross structural features: 1 has an insular tetraborate(2-) anion, 2–5 have insular pentaborate(1-) anions, 6 has an insular heptaborate(2-) anion (‘O+’ isomer), whilst 7 and 8 have hexaborate(2-) anions directly coordinated to their Ni(II) centers, as bidentate or tridentate ligands, respectively. The Ni(II) centers are either octahedral (1–4, 7, 8) or square-planar (5), and compound 6 has both octahedral and square-planar metal geometries present within the structure as a double salt. Magnetic susceptibility measurements were undertaken on all compounds. Full article
(This article belongs to the Special Issue Boron Chemistry: Fundamentals and Applications)
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