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Special Issue "Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: 31 December 2021.

Special Issue Editors

Dr. Andrea Rossin
E-Mail Website
Guest Editor
National Research Council, Institute of Chemistry of Organometallic Compounds (ICCOM), via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy
Interests: B/N-based lightweight inorganic hydrides; hydrogen storage; metal-organic frameworks; CO2 storage and utilization
Special Issues, Collections and Topics in MDPI journals
Dr. Igor Golub
E-Mail Website
Guest Editor
Institute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), 1348 Louvain-la-Neuve, Belgium
Interests: energetic materials; batteries; hydrogen storage; metal hydrides; main group hydrides; non-covalent interactions; ab initio simulations; DFT; molecular spectroscopy; X-ray radiation
Prof. Dr. Vladimir Bregadze
E-Mail Website
Guest Editor
A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Moscow, Russia
Interests: chemistry of polyhedral boron compounds, especially carboranes and their derivatives of main group metals, metallacarboranes of transition metals, study of their reactivity and application in medicine (antitumour activity, boron-neutron capture therapy) and for design of materials; development of new synthetic methods for organic and inorganic derivatives of gallium, indium, thallium, arsenic, selenium and tellurium, study of their reactivity and application as precursors for preparation of semi- conductor materials by organometallic chemical vapor deposition

Special Issue Information

Dear Colleagues,

Today, the chemistry of hydrides is an actively developing area of inorganic and organometallic chemistry, which is associated with their extensive use as energetic materials and their role in homogeneous and heterogeneous catalysis and in redox processes. In recent decades, there has been a renaissance of hydride materials for energy applications such as batteries and hydrogen storage. Lightweight hydride materials are used for the development of efficient and reliable systems of renewable energy storage, both for stationary and for mobile applications—what is known to be the main challenge for the implementation of “green energy”, and ultimately the transition to a fossil fuel free society. Another important aspect is the participation of metal hydrides as a catalyst or catalytic intermediates in a wide variety of homogeneous and heterogeneous catalytic processes, the most significant of which are hydrogenation, hydroformylation, as well as processes occurring with the activation of E–H bonds (E = H, C, Si, B, P, N, etc.) and catalytic dehydrocoupling. Finally, metal alumo- and borohydrides are play an undeniable role in selective reduction processes in thin organic synthesis and pharmaceutical production.

This Special Issue aims to present recent advances in hydride chemistry, from the development of new synthetic approaches, determination of crystal structure, the study of their properties (electronic, spectroscopic, optic, etc.), and investigation of their reactivity toward small molecules and bond activation to their use in a broad range of fields, including energetic materials, organometallic chemistry, homogeneous and heterogeneous catalysis, etc. Contributions to this issue could be in the form of communications, full research articles, and reviews on topics related to these fields. Scientific productions of both experimental and computational nature are welcome; mechanistic studies that offer new insights into catalytic processes or chemical reactions are particularly welcome.

Dr. Andrea Rossin
Dr. Igor Golub
Prof. Dr. Vladimir Bregadze
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Synthesis
  • Crystal structure
  • Non-covalent interactions
  • Boranes
  • Hydrogen storage
  • Energetic materials
  • Bond activation
  • Catalysis

Published Papers (3 papers)

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Research

Article
Synthesis of Zwitter-Ionic Conjugate of Nido-Carborane with Cholesterol
Molecules 2021, 26(21), 6687; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26216687 - 05 Nov 2021
Viewed by 318
Abstract
9-HC≡CCH2Me2N-nido-7,8-C2B9H11, a previously described carboranyl terminal alkyne, was used for the copper(I)-catalyzed azide-alkyne cycloaddition with azido-3β-cholesterol to form a novel zwitter-ionic conjugate of nido-carborane with cholesterol, bearing a 1,2,3-triazol fragment. [...] Read more.
9-HC≡CCH2Me2N-nido-7,8-C2B9H11, a previously described carboranyl terminal alkyne, was used for the copper(I)-catalyzed azide-alkyne cycloaddition with azido-3β-cholesterol to form a novel zwitter-ionic conjugate of nido-carborane with cholesterol, bearing a 1,2,3-triazol fragment. The conjugate of nido-carborane with cholesterol, containing a charge-compensated group in the linker, can be used as a precursor for the preparation of liposomes for BNCT (Boron Neutron Capture Therapy). The solid-state molecular structure of a nido-carborane derivative with the 9-Me2N(CH2)2Me2N-nido-7,8-C2B9H11 terminal dimethylamino group was determined by single-crystal X-ray diffraction. Full article
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Article
The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-closo-hexaborate Dianion
Molecules 2021, 26(12), 3754; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26123754 - 20 Jun 2021
Cited by 1 | Viewed by 656
Abstract
The mechanism of the consecutive halogenation of the tetrahydroborate anion [BH4] by hydrogen halides (HX, X = F, Cl, Br) and hexahydro-closo-hexaborate dianion [B6H6]2− by HCl via electrophile-induced nucleophilic substitution (EINS) was established [...] Read more.
The mechanism of the consecutive halogenation of the tetrahydroborate anion [BH4] by hydrogen halides (HX, X = F, Cl, Br) and hexahydro-closo-hexaborate dianion [B6H6]2− by HCl via electrophile-induced nucleophilic substitution (EINS) was established by ab initio DFT calculations [M06/6-311++G(d,p) and wB97XD/6-311++G(d,p)] in acetonitrile (MeCN), taking into account non-specific solvent effects (SMD model). Successive substitution of H by X resulted in increased electron deficiency of borohydrides and changes in the character of boron atoms from nucleophilic to highly electrophilic. This, in turn, increased the tendency of the B–H bond to transfer a proton rather than a hydride ion. Thus, the regularities established suggested that it should be possible to carry out halogenation more selectively with the targeted synthesis of halogen derivatives with a low degree of substitution, by stabilization of H2 complex, or by carrying out a nucleophilic substitution of B–H bonds activated by interaction with Lewis acids (BL3). Full article
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Article
Ti Group Metallocene-Catalyzed Synthesis of 1-Hexene Dimers and Tetramers
Molecules 2021, 26(9), 2775; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26092775 - 08 May 2021
Viewed by 560
Abstract
1-Hexene transformations in the catalytic systems L2MCl2–XAlBui2 (L = Cp, M = Ti, Zr, Hf; L = Ind, rac-H4C2[THInd]2, M = Zr; X = H, Bu i) and [Cp2 [...] Read more.
1-Hexene transformations in the catalytic systems L2MCl2–XAlBui2 (L = Cp, M = Ti, Zr, Hf; L = Ind, rac-H4C2[THInd]2, M = Zr; X = H, Bu i) and [Cp2ZrH2]2-ClAlR2 activated by MMAO-12, B(C6F5)3, or (Ph3C)[B(C6F5)4] in chlorinated solvents (CH2Cl2, CHCl3, o-Cl2C6H4, ClCH2CH2Cl) were studied. The systems [Cp2ZrH2]2-MMAO-12, [Cp2ZrH2]2-ClAlBui2-MMAO-12, or Cp2ZrCl2-HAlBui2-MMAO-12 (B(C6F5)3) in CH2Cl2 showed the highest activity and selectivity towards the formation of vinylidene head-to-tail alkene dimers. The use of chloroform as a solvent provides further in situ dimer dimerization to give a tetramer yield of up to 89%. A study of the reaction of [Cp2ZrH2]2 or Cp2ZrCl2 with organoaluminum compounds and MMAO-12 by NMR spectroscopy confirmed the formation of Zr,Zr-hydride clusters as key intermediates of the alkene dimerization. The probable structure of the Zr,Zr-hydride clusters and ways of their generation in the catalytic systems were analyzed using a quantum chemical approach (DFT). Full article
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Boron hydrogen compounds: from hydrogen storage to battery applications
Authors: Hans-Rudolf Hagemann
Affiliation: Dépt. de Chimie Physique, Université de Genève, 30, quai E. Ansermet, CH1211 Geneva 4 Switzerland
Abstract: About 25 years ago, Bogdanovic and Schwickardi (B. Bogdanovic, M. Schwickardi: J. Alloys Compd. 1–9, 253 (1997) discovered the catalyzed release of hydrogen from NaAlH4. This discovery stimulated a vast research effort on light hydrides as hydrogen storage materials, in particular boron hydrogen compounds. In the following years, many new metal borohydrides such as Mx(BH4)y and MxM’y(BH4)z were prepared and characterized. However, it appeared that reaction kinetics and reversibility are not very favorable for the pure compounds, and potential catalysts were explored to improve the performance. The discovery of high ionic conductivity in the high temperature phase of LiBH4 opened a new research direction, and very recently a all-solid-state 4V Na battery prototype using a Na4(CB11H12)2(B12H12) solid electrolyte has been demonstrated. In this review, we present the current knowledge of possible reaction pathways involved in the successive hydrogen release reactions from BH4- to B12H122-, as well as a discussion of relevant properties necessary for high ionic conduction materials.

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