Ананьев Иван Вячеславович
Базовая кафедра элементоорганической химии Института элементоорганических соединений им. А.Н. Несмеянова РАН
Профессиональные интересы
Должности
- Профессор — Базовая кафедра элементоорганической химии Института элементоорганических соединений им. А.Н. Несмеянова РАН
Био
- · Начал работать в НИУ ВШЭ в 2019 году.
- · Научно-педагогический стаж: 14 лет.
Образование
- 2024 · Доктор физико-математических наук
- 2013 · Кандидат наук
- 2010 · Специалитет: Российский химико-технологический университет им. Д.И. Менделеева, специальность «Химия», квалификация «Химик»
Опыт работы
- · 2022 - н.в.: Институт общей и неорганической химии РАН им. Н.С. Курнакова:
- · ведущий научный сотрудник, заведующий лабораторией
- · 2010 - н.в.: Институт элементоорганических соединений им. А.Н. Несмеянова:
- · старший научный сотрудник
Награды и поощрения
- · Надбавка за публикацию в журнале из Списка А (и приравненном к нему научном издании) (2025–2026, 2024–2025, 2023–2024)
- · Надбавка за публикацию в международном рецензируемом научном издании (2022–2023, 2021–2022, 2019–2021)
- · Лучший преподаватель — 2020–2023
Гранты и проекты
- — · на соискание учёной степени кандидата наук
Идентификаторы исследователя
- ORCID:
0000-0001-6867-7534 - ResearcherID:
M-1918-2015 - SPIN РИНЦ:
3476-2887 - Google Scholar: https://scholar.google.com/citations?user=Ey7Zm-EAAAAJ&hl=ru
- Scopus AuthorID:
6508039780
Публикации (51)
Structure-directing sulfur center dot center dot center dot metal noncovalent semicoordination bonding
2020 · ARTICLE · en
The abundance and geometric features of nonbonding contacts between metal centers and `soft' sulfur atoms bound to a non-metal substituent R were analyzed by processing data from the Cambridge Structural Database. The angular arrangement of M, S and R atoms with angle(R-S center dot center dot center dot M) down to 150 degrees was a common feature of the late transition metal complexes exhibiting shortened R-S center dot center dot center dot M contacts. Several model nickel(II), palladium(II), platinum(II) and gold(I) complexes were chosen for a theoretical analysis of R-S center dot center dot center dot M interactions using the DFT method applied to (equilibrium) isolated systems. A combination of the real-space approaches, such as Quantum Theory of Atoms in Molecules (QTAIM), noncovalent interaction index (NCI), electron localization function (ELF) and Interacting Quantum Atoms (IQA), and orbital (Natural Bond Orbitals, NBO) methods was used to provide insights into the nature and energetics of R-S center dot center dot center dot M interactions with respect to the metal atom identity and its coordination environment. The explored features of the R-S center dot center dot center dot M interactions support the trends observed by inspecting the CSD statistics, and indicate a predominant contribution of semicoordination bonds between nucleophilic sites of the sulfur atom and electrophilic sites of the metal. A contribution of chalcogen bonding (that is formally opposite to semicoordination) was also recognized, although it was significantly smaller in magnitude. The analysis of R-S center dot center dot center dot M interaction strengths was performed and the structure-directing role of the intramolecular R-S center dot center dot center dot M interactions in stabilizing certain conformations of metal complexes was revealed.
Novel Cobalt Bis(dicarbollide) Based on Terminal Alkynes and Their Click‐Reactions
2020 · ARTICLE · en
Novel cobalt bis(dicarbollide) terminal alkynes with charge‐compensated group were synthesized by the cleavage reactions of oxonium derivatives of cobalt bis(dicarbollide) with N,N‐dimethylprop‐2‐yn‐1‐amine. The solid‐state molecular structures of alkynes prepared from 1,4‐dioxane and tetrahydropyran derivatives of cobalt and iron bis(dicarbollide) were determined by single‐crystal X‐ray diffraction. A series of zwitterionic conjugates of cobalt/iron bis(dicarbollide) with cholesterol were prepared using the copper(I)‐catalyzed azide–alkyne cycloaddition reaction.
Interatomic exchange-correlation interaction energy from a measure of quantum theory of atoms in molecules topological bonding: A diatomic case
2020 · ARTICLE · en
The potential relations between the measure of topological interatomic bonding—integrals of electron density with respect to internuclear axis over the corresponding quantum theory of atoms in molecules (QTAIM)‐defined interatomic surface (IAS)—and interatomic exchange‐correlation contributions from the interacting quantum atoms approach are discussed. The quantum chemical computations of 38 equilibrium diatomic systems at different levels of theory (HF, MP2, MP4SDQ, and CCSD) are invoked to support abstract considerations. Parameters of excellent correlations between IAS integrals and interatomic exchange‐correlation energy are found by the optimization. The performance of these trends depends on the accuracy of the electronic correlation treatment. The resulting trends are a unique feature of equilibrium states, whereas more complicated dependencies are explored for several systems at non‐equilibrium conditions. The relations of established trends with other IAS‐based estimations of strength of bonding interactions between topological atoms and issues explored for multiatomic systems are briefly discussed.
СИНТЕЗ И СТРУКТУРНОЕ РАЗНООБРАЗИЕ ТРИФЕНИЛАЦЕТАТНЫХ КОМПЛЕКСОВ ЛАНТАНА И НЕОДИМА С ТРИМЕТИЛТРИАЗАЦИКЛОГЕКСАНОМ И КРАУН-ЭФИРОМ
2020 · ARTICLE · ru
Взаимодействие трифенилацетатов лантана и неодима с полидентатными 6- и 18-членными N- и O- гетероциклическими лигандами приводит к образованию различных типов трифенилацетатных мо- ноядерных комплексов, содержащих вспомогательный полидентатный лиганд (нейтральныx либо ка- тионныx и анионныx): [Nd(Ph3CCOO)3(Me3TACH)] ∙ CHCl3 (II), [La(Ph3CCOO)4(Me3TACH)]–- [NH4Me]+ (III), [La(Ph3CCOO)3(18-краун-6)] (IV), [Nd(Ph3CCOO)2(18-краун-6)]+[Nd(Ph3CCOO)4]– (V), а также биядерного [La2(Ph3CCOO)3(Me3TACH)] ∙ 2С6H5СH3 (I) (CIF files CCDC № 1968815 (I), 1968813 (II), 1968814 (III), 1968812 (IV), 1968816 (V)). Минимальное изменение ионного радиуса на примере перехода от La к Nd приводит к изменению характера координационного окружения. Мак- роциклические полидентатные лиганды позволяют проследить за такими изменениями.
Divergent Synthesis of Five-Membered Nitrogen Heterocycles via Cascade Reactions of 4-Arylfuroxans
2020 · ARTICLE · en
A novel method for the synthesis of a diverse series of functionally substituted five-membered heterocyclic compounds via atom-economic, regio-, and diastereoselective one-pot reaction cascade was developed. This approach involves a ring opening in 4-arylfuroxans to alpha-oximinoarylacetonitrile oxides followed by [3+2] cycloaddition to various dipolarophiles to afford multisubstituted isoxazoles and isoxazolines. Subsequent azole-azole rearrangement of (oximino)isoxazolines/-isoxazoles, which can be conducted in a one-pot manner, results into functionally substituted furazans formation. The developed protocol is operationally simple, proceeds in mild conditions and with high yields of target heterocyclic systems. Overall, this study represents a new mode of isoxazole and 1,2,5-oxadiazole functionalization strategy, which is useful in medicinal and materials chemistry.
Pushing the Energy-Sensitivity Balance with High-Performance Bifuroxans
2020 · ARTICLE · en
Several energy-rich bifuroxans incorporating nitro and azido functionalities have been synthesized and thoroughly characterized by IR and multinuclear NMR spectroscopy, elemental analyses, single-crystal X-ray diffraction, and differential scanning calorimetry. N-oxide regiochemistry was employed to design the tunable azido(nitro)bifuroxans with different physicochemical and energetic properties. All synthesized compounds have high enthalpies of formation (449-777 kJ mol(-1)) and attractive performances, as evidenced by the high detonation velocities (8.95-9.75 km s(-1)) and Champan-Jouguet pressures (35-45 GPa). The most powerful energetic material in this series is 4,4'-dinitro-3,3'-bifuroxan. This hydrogen-free molecule (C4N6O8) exhibits an outstanding heat of explosion value of 15.3 kJ cm(-1), far exceeding the top energetic material hexanitrohexaazaisowurtzitane CL-20. At the same time, the impact and friction sensitivities of 4,4'-dinitro-3,3'-bifuroxan were deemed acceptable for practical use. Overall, 4,4'-dinitro-3,3'-bifuroxan breaks a general trend called the "energy-sensitivity rule", which describes a linear increase of the mechanical sensitivity with a growth of the energetic content of the molecule, and, thus, offers great promise for future applications.
Straightforward Access to the NO-Donor Azasydnone Scaffold by Cascade Reactions of Amines
2019 · ARTICLE · en
A novel one-pot cascade method for the assembly of valuable NO-donor azasydnone scaffold has been developed. This construction strategy involves a diazotization/azo coupling/elimination/double rearrangement cascade sequence of readily available amines. The current protocol enables the generation of a diverse array of azasydnones, including previously hardly accessible heteroaryl substituted azasydnones (25 examples, 70-97% yield) with a good functional group tolerance under very mild conditions. Preliminary NO-releasing studies revealed an ability of azasydnones to produce NO in a wide range of concentrations. This method provides a new approach to nitrogen-oxygen heterocycles with potential applications in medicine and material science.
Renaissance of 1,2,5-Oxadiazolyl Diazonium Salts: Synthesis and Reactivity
2019 · ARTICLE · en
A new approach for the synthesis and reactivity of the 1,2,5-oxadiazolyl diazonium salts is represented. A simple and direct protocol to previously inaccessible furoxanyl and furazanyl diazonium salts was developed for the first time. Azo coupling reactions of thus obtained diazonium salts with a series of structurally diverse CH-acids have been also successfully performed. Therefore, this study reveals new horizons for the use of furoxanyl and furazanyl diazonium salts in organic chemistry.
Internlay of noncovalent interactions in antiseptic quaternary ammonium surfactant Miramistin
2019 · ARTICLE · en
The molecular and crystal structure of the widely used antiseptic benzyldimethyl-{3-[(1-oxo tetradecyl) amino] propyl} ammonium chloride monohydrate (Miramistin, MR), C26H47N2O+center dot Cl-center dot H2O, was determined by a single-crystal X-ray diffraction study and analyzed in the framework of the QTAIM (quantum theory of atoms in molecules) approach using both periodic and molecular DFT (density functional theory) calculations. The various noncovalent intermolecular interactions of different strengths were found to be realized in the hydrophilic parts of the crystal packing (i.e. O-H center dot center dot center dot Cl, N-H center dot center dot center dot Cl, C-H center dot center dot center dot Cl, C-H center dot center dot center dot O and C-H center dot center dot center dot pi). The hydrophobic parts are built up exclusively by van der Waals H center dot center dot center dot H contacts. Quantification of the interaction energies using calculated electron-density distribution revealed that the total energy of the contacts within the hydrophilic and hydrophobic regions are comparable in value. The organic MR cation adopts the bent conformation with the head group tilted back to the long-chain alkyl tail in both the crystalline and the isolated state due to stabilization of this geometry by several intramolecular C-H center dot center dot center dot pi, C-H center dot center dot center dot N and H center dot center dot center dot H interactions. This conformation preference is hypothesized to play an important role in the interaction of MR with biomembranes.
Assembly of Tetrazolylfuroxan Organic Salts: Multipurpose Green Energetic Materials with High Enthalpies of Formation and Excellent Detonation Performance
2019 · ARTICLE · en
A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen-rich cations were synthesized by simple, efficient, and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR (H-1, C-13, N-14, N-15) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt consisting of an azidotetrazolylfuroxan anion and a 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazolium cation was confirmed by single-crystal X-ray diffraction. The synthesized compounds exhibit good experimental densities (1.57-1.71 g cm(-3)), very high enthalpies of formation (818-1363 kJ mol(-1)), and, as a result, excellent detonation performance (detonation velocities 7.54-8.26 kms(-1) and detonation pressures 23.4-29.3 GPa). Most of the synthesized energetic salts have moderate sensitivity toward impact and friction, which makes them promising candidates for a variety of energetic applications. At the same time, three compounds have impact sensitivity on the primary explosives level (1.5-2.7 J). These results along with high detonation parameters and high nitrogen contents (66.0-70.2 %) indicate that these three compounds may serve as potential environmentally friendly alternatives to lead-based primary explosives.
Курсы (3)
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Теоретическая неорганическая химия и химия элементов · 2 раза
2023/2024, 2022/2023 · Бакалавриат · рус
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Квантовая химия
2022/2023 · Бакалавриат · рус
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Теоретическая неорганическая химия
2021/2022 · Бакалавриат · рус