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Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications
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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: closed (30 June 2022) | Viewed by 20660

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

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Keywords

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

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Published Papers (7 papers)

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Research

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12 pages, 1072 KiB  
Article
Synthesis and Antibacterial Activity Studies of the Conjugates of Curcumin with closo-Dodecaborate and Cobalt Bis(Dicarbollide) Boron Clusters
by Anna A. Druzina, Natalia E. Grammatikova, Olga B. Zhidkova, Natalia A. Nekrasova, Nadezhda V. Dudarova, Irina D. Kosenko, Mikhail A. Grin and Vladimir I. Bregadze
Molecules 2022, 27(9), 2920; https://doi.org/10.3390/molecules27092920 - 3 May 2022
Cited by 11 | Viewed by 2700
Abstract
A series of novel conjugates of cobalt bis(dicarbollide) and closo-dodecaborate with curcumin were synthesized by copper(I)-catalyzed azide-alkyne cycloaddition. These conjugates were tested for antibacterial activity. It was shown that all derivatives are active when exposed to Bacillus cereus ATCC 10702 and are [...] Read more.
A series of novel conjugates of cobalt bis(dicarbollide) and closo-dodecaborate with curcumin were synthesized by copper(I)-catalyzed azide-alkyne cycloaddition. These conjugates were tested for antibacterial activity. It was shown that all derivatives are active when exposed to Bacillus cereus ATCC 10702 and are not active against Gram-negative microorganisms and Candida albicans at the maximum studied concentration of 1000 mg/L. The conjugate of alkynyl-curcumin with azide synthesized from the tetrahydropyran derivative of cobalt bis(dicarbollide) exhibited activity against Gram-positive microorganisms: Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212 and the clinical isolate MRSA 17, that surpassed curcumin by 2–4 times. Full article
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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11 pages, 1940 KiB  
Article
Hydrolysis of the Borohydride Anion BH4−: A 11B NMR Study Showing the Formation of Short-Living Reaction Intermediates including BH3OH−
by Eddy Petit, Fabrice Salles, Damien Alligier and Umit B. Demirci
Molecules 2022, 27(6), 1975; https://doi.org/10.3390/molecules27061975 - 18 Mar 2022
Cited by 8 | Viewed by 2347
Abstract
In hydrolysis and electro-oxidation of the borohydride anion BH4−, key reactions in the field of energy, one critical short-living intermediate is BH3OH−. When water was used as both solvent and reactant, only BH3OH− [...] Read more.
In hydrolysis and electro-oxidation of the borohydride anion BH4−, key reactions in the field of energy, one critical short-living intermediate is BH3OH−. When water was used as both solvent and reactant, only BH3OH− is detected by 11B NMR. By moving away from such conditions and using DMF as solvent and water as reactant in excess, four 11B NMR quartets were observed. These signals were due to BH3-based intermediates as suggested by theoretical calculations; they were DMF·BH3, BH3OH−, and B2H7− (i.e., [H3B−H−BH3]− or [H4B−BH3]−). Our results shed light on the importance of BH3 stemming from BH4− and on its capacity as Lewis acid to interact with Lewis bases such as DMF, OH−, and BH4−. These findings are important for a better understanding at the molecular level of hydrolysis of BH4− and production of impurities in boranes synthesis. Full article
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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10 pages, 1470 KiB  
Article
Synthesis of Zwitter-Ionic Conjugate of Nido-Carborane with Cholesterol
by Anna A. Druzina, Olga B. Zhidkova, Nadezhda V. Dudarova, Natalia A. Nekrasova, Kyrill Yu. Suponitsky, Sergey V. Timofeev and Vladimir I. Bregadze
Molecules 2021, 26(21), 6687; https://doi.org/10.3390/molecules26216687 - 5 Nov 2021
Cited by 6 | Viewed by 2307
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
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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17 pages, 2498 KiB  
Article
The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-closo-hexaborate Dianion
by Igor E. Golub, Oleg A. Filippov, Natalia V. Belkova, Lina M. Epstein and Elena S. Shubina
Molecules 2021, 26(12), 3754; https://doi.org/10.3390/molecules26123754 - 20 Jun 2021
Cited by 10 | Viewed by 2566
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
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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16 pages, 1583 KiB  
Article
Ti Group Metallocene-Catalyzed Synthesis of 1-Hexene Dimers and Tetramers
by Pavel V. Kovyazin, Almira Kh. Bikmeeva, Denis N. Islamov, Vasiliy M. Yanybin, Tatyana V. Tyumkina and Lyudmila V. Parfenova
Molecules 2021, 26(9), 2775; https://doi.org/10.3390/molecules26092775 - 8 May 2021
Cited by 7 | Viewed by 2255
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
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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Review

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39 pages, 8824 KiB  
Review
Dynamic Processes of Rhenium Polyhydride Complexes
by Datta V. Naik and Gregory A. Moehring
Molecules 2022, 27(15), 5017; https://doi.org/10.3390/molecules27155017 - 7 Aug 2022
Cited by 2 | Viewed by 2118
Abstract
Studies have demonstrated that high-coordination-number rhenium polyhydride complexes are precursors to catalysts that transform a variety of organic molecules. While rhenium polyhydride complexes lead to active catalysts, little has been reported on the mechanisms for the transformations. High-coordination-number rhenium polyhydride complexes exhibit several [...] Read more.
Studies have demonstrated that high-coordination-number rhenium polyhydride complexes are precursors to catalysts that transform a variety of organic molecules. While rhenium polyhydride complexes lead to active catalysts, little has been reported on the mechanisms for the transformations. High-coordination-number rhenium polyhydride complexes exhibit several dynamic processes that make characterizations of the chemical properties for individual atoms difficult, at best, for room-temperature solutions. This review describes what is known of the dynamic processes that occur at high-coordination-number rhenium polyhydride complexes and how that knowledge may lead to the design of catalytic precursors in which the chemical properties of individual atoms can be more readily identified in room-temperature solutions. Full article
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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14 pages, 1299 KiB  
Review
Boron Hydrogen Compounds: Hydrogen Storage and Battery Applications
by Hans Hagemann
Molecules 2021, 26(24), 7425; https://doi.org/10.3390/molecules26247425 - 7 Dec 2021
Cited by 33 | Viewed by 4647
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 [...] Read more.
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. Mg(BH4)2, with a hydrogen content of 14.9 wt %, has been extensively studied, and recent results shed new light on intermediate species formed during dehydrogenation. The chemistry of B3H8−, which is an important intermediate between BH4− and B12H122−, is presented in detail. The discovery of high ionic conductivity in the high-temperature phases of LiBH4 and Na2B12H12 opened a new research direction. The high chemical and electrochemical stability of closo-hydroborates has stimulated new research for their applications in batteries. Very recently, an all-solid-state 4 V 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−, and a discussion of relevant necessary properties for high-ionic-conduction materials. Full article
(This article belongs to the Special Issue Transition Metal and Main Group Hydrides: Structure, Reactivity, and Applications)
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