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Boron Chemistry 2021: A Themed Issue Dedicated to the 90th Anniversary of Academician N.T. Kuznetsov

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

Deadline for manuscript submissions: closed (1 November 2021) | Viewed by 6332

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Special Issue Editor

Prof. Dr. Konstantin Yu Zhizhin

E-Mail Website1 Website2
Guest Editor

1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, 119991 Moscow, Russia
2. MIREA-Russian Technological University (RTU MIREA), Moscow, Russia
Interests: chemistry and application of boron cluster anions; BNCT; coordination chemistry

Special Issue Information

Dear Colleagues,

As a metalloid element, boron is closely related to human life. There has been a considerable investment in materials science and inorganic chemistry behind boron, e.g., glass fiber, porcelain products, bleacher, detergents, etc. Boron is also widely used in organic chemistry; organoboron compounds are making significant headway in medicinal chemistry, as either stalwart synthons or as biologically active materials. Boron plays an increasingly important role in organic synthesis, sensors, medicinal, natural products, materials science, and inorganic chemistry.

We are pleased to announce that this Special Issue is dedicated to the 90th anniversary of academician N.T. Kuznetsov, a prominent scientist in the field of the chemistry of boron and its compounds.

Academician RAS Nikolay Timofeevich Kuznetsov is a prominent scientist in inorganic and coordination chemistry, physical chemistry and technology of inorganic materials. He is the Head of a large scientific school in inorganic chemistry and chemical materials science; among his students, we can note 10 Doctors of Science and 35 PhDs in Chemistry. He was awarded the title of Honorary Doctor of the University of Genoa and several Russian Universities.

N.T. Kuznetsov was born on the Khoroshevsky farm (now the Tatsinsky district of the Rostov region, Russia). In 1954, he graduated from the Chemistry Department of the Moscow State University. The long-term scientific and scientific-organizational activity of N. T. Kuznetsov is mainly associated with the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Science (RAS), where he passed all the way from graduate student to Director of the Institute.

N.T. Kuznetsov made a significant contribution to the chemistry and technology of hydride compounds and materials based on them. The fundamental and theoretical studies of academician Kuznetsov in the chemistry of cluster borohydrides [BnHn]2- (n = 6-12) are widely known. In these works, for the first time in inorganic chemistry, the presence of spatial aromaticity and regioselectivity of substitution processes was established and experimentally proved. He discovered and studied a fundamentally new class of cluster borohydrogen compounds—“superelectron-deficient” borohydrogen structures; the coordination chemistry of cluster borohydride structures as ligands in complexes of transition and non-transition elements has since been widely developed. On the basis of these works, a large and important cycle of research is being carried out on the creation of drugs for the diagnosis and treatment of oncological diseases.

N.T. Kuznetsov and his colleagues carried out a large number of fundamental and applied works in the chemistry and physical chemistry of transition metal hydrides, alloys, and intermetallic compounds. With his participation, a large number of new hydrides were obtained, including those with a record volumetric hydrogen content. Based on their fundamental research, reversible hydrogen accumulators, selective catalysts, etc. have been developed.

In recent years, N.T. Kuznetsov and his co-workers have actively and successfully developed fundamental and applied research on the development of technology and the study of the structure and properties of high-temperature ceramic materials, mainly carbides and oxides, including those in the ultradispersed and nanocrystalline state.

Academician N.T. Kuznetsov is the author of several monographs and dozens of patents and copyright certificates for inventions, textbooks, handbooks, reference books, and over 800 scientific articles.

It is a pleasure to invite you to submit a manuscript to this Special Issue; regular articles, communications, as well as reviews are all welcome.

Prof. Dr. Konstantin Yu Zhizhin
Guest Editor

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Keywords

Boranes
Carboranes
Metallaboranes
Metallacarboranes
Transition metal–boron complexes
Boron-based Lewis acids
Aminoboranes
Boronic acids
Boron-based materials
Boron-based drugs
Boron neutron capture therapy

Published Papers (3 papers)

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Research

13 pages, 1934 KiB

Open AccessArticle

Nucleophilic Substitution Reactions in the [B₃H₈]⁻ Anion in the Presence of Lewis Acids

by Alexandra T. Shulyak, Evgeniy O. Bortnikov, Nikita A. Selivanov, Mikhail S. Grigoriev, Alexey S. Kubasov, Andrey P. Zhdanov, Alexander Y. Bykov, Konstantin Y. Zhizhin and Nikolai T. Kuznetsov

Molecules 2022, 27(3), 746; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27030746 - 24 Jan 2022

Cited by 1 | Viewed by 2380

Abstract

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph₃P, Ph₂P-(CH₂)₂-PPh₂ (dppe), Ph₃As, Et₃N, PhNH₂, C₅H₅ [...] Read more.

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph₃P, Ph₂P-(CH₂)₂-PPh₂ (dppe), Ph₃As, Et₃N, PhNH₂, C₅H₅N, CH₃CN, Ph₂CHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [B₃H₇Nu] are obtained. It is found that the use of TiCl₄, AlCl₃, ZrCl₄, HfCl₄, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [B₃H₇-HMXn_x], which was detected by NMR spectroscopy. The structures of [Ph₃P·B₃H₇] and [PhNH₂·B₃H₇] were determined by X-ray diffraction. Full article

(This article belongs to the Special Issue Boron Chemistry 2021: A Themed Issue Dedicated to the 90th Anniversary of Academician N.T. Kuznetsov)

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16 pages, 3451 KiB

Open AccessArticle

Anharmonic Vibrational Frequencies of Water Borane and Associated Molecules

by Brent R. Westbrook and Ryan C. Fortenberry

Molecules 2021, 26(23), 7348; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26237348 - 03 Dec 2021

Cited by 4 | Viewed by 1678

Abstract

Water borane (BH

_{3}

_{2}

) and borinic acid (BH

_{2}

Water borane (BH

_{3}

_{2}

) and borinic acid (BH

_{2}

OH) have been proposed as intermediates along the pathway of hydrogen generation from simple reactants: water and borane. However, the vibrational spectra for neither water borane nor borinic acid has been investigaged experimentally due to the difficulty of isolating them in the gas phase, making accurate quantum chemical predictions for such properties the most viable means of their determination. This work presents theoretical predictions of the full rotational and fundamental vibrational spectra of these two potentially application-rich molecules using quartic force fields at the CCSD(T)-F12b/cc-pCVTZ-F12 level with additional corrections included for the effects of scalar relativity. This computational scheme is further benchmarked against the available gas-phase experimental data for the related borane and HBO molecules. The differences are found to be within 3 cm

^{- 1}

for the fundamental vibrational frequencies and as close as 15 MHz in the

B_{0}

and

C_{0}

principal rotational constants. Both BH

_{2}

OH and BH

_{3}

_{2}

have multiple vibrational modes with intensities greater than 100 km mol

^{- 1}

, namely

ν_{2}

and

ν_{4}

in BH

_{2}

OH, and

ν_{1}

ν_{3}

ν_{4}

ν_{9}

, and

ν_{13}

in BH

_{3}

_{2}

. Finally, BH

_{3}

_{2}

has a large dipole moment of 4.24 D, which should enable it to be observable by rotational spectroscopy, as well. Full article

(This article belongs to the Special Issue Boron Chemistry 2021: A Themed Issue Dedicated to the 90th Anniversary of Academician N.T. Kuznetsov)

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Figure 1

13 pages, 1490 KiB

Open AccessArticle

Synthesis of 3-Aryl-ortho-carboranes with Sensitive Functional Groups

by Sergey A. Anufriev, Akim V. Shmal’ko, Kyrill Yu. Suponitsky and Igor B. Sivaev

Molecules 2021, 26(23), 7297; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26237297 - 01 Dec 2021

Cited by 3 | Viewed by 1644

Abstract

A simple and efficient method was developed for the one-pot synthesis of 3-aryl derivatives of ortho-carborane with sensitive functional groups using 3-iodo-ortho-carborane and aryl zinc bromides that were generated in situ. A series of 3-aryl-ortho-carboranes, including those containing nitrile and ester groups, 3-RC₆H₄-1,2-C₂B₁₀H₁₁ (R = p-Me, p-NMe₂, p-OCH₂OMe, p-OMe, o-CN, p-CN, o-COOEt, m-COOEt, p-COOEt) was synthesized using this approach. The solid-state structures of 3-RC₆H₄-1,2-C₂B₁₀H₁₁ (R = p-OMe, o-CN, and p-CN) were determined by single crystal X-ray diffraction. The intramolecular hydrogen bonding involving the ortho-substituents of the aryl ring and the CH and BH groups of carborane was discussed. Full article

(This article belongs to the Special Issue Boron Chemistry 2021: A Themed Issue Dedicated to the 90th Anniversary of Academician N.T. Kuznetsov)

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Boron Chemistry 2021: A Themed Issue Dedicated to the 90th Anniversary of Academician N.T. Kuznetsov

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