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Ананьев Иван Вячеславович

Базовая кафедра элементоорганической химии Института элементоорганических соединений им. А.Н. Несмеянова РАН

Профиль на hse.ru ↗ тел.: 23531
Публикаций
51
Языков
1
Наград
3
Конференций
0
Профиль Публикации (51) Курсы (3)

Профессиональные интересы

квантовая химияфизическая химиярентгеноструктурный анализ

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

Публикации (51)

Different coordination modes of trans-2-{[(2-meth-oxyphenyl)imino]methylionenoxide in rare-earth complexes: influence of the metal cation radius and the number of ilgands on steric congestion and ligand coordination modes

2018 · ARTICLE · en

A simple and effective synthetic route to homo- and heteroleptic rare-earth (Ln = Y, La and Nd)complexes with a tridentate Schiff base anion has been demonstrated using exchange reactions of rare-earth chlorides with in-situ-generated sodium (E)-2-{[(2-methoxyphenyl)imino]methyl}phenoxide in different molar ratios in absolute methanol. Five crystal structures have been determined and studied, namely tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato-kappa O-3(1), N, O-2)lanthanum, [La(C14H12NO2)(3)], (1), tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato-kappa O-3(1), N, O-2)neodymium tetrahydrofuran disolvate, [La(C14H12NO2)(3)]center dot 2C(4)H(8)O, (2)center dot 2THF, tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato)-kappa O-3(1), N, O-2 kappa O-3(1), N, O-2, kappa O-3(1), N, O-2, O-1-yttrium, [Y(C14H12NO2)(3)], (3), dichlorido-1 kappa Cl ,2 kappa Cl-mu-methanolato-1:2 kappa O-2 : O-methanol-2 kappa O -(mu-2-{[(2-methoxyphenyl)imino]methyl}phenolato-1 kappa O-3(1), N , O-2:2 kappa O-1)bis(2-{[(2-methoxyphenyl)imino]methyl}phenolato)-1 kappa O-3(1), N, O-2;2 kappa O-3(1), N, O-2-diyttrium-tetrahydrofuran-methanol (1/1/1), [Y-2 (C14H12NO2)(3) (CH3O)Cl-2 (CH4O)]center dot CH4 O center dot C4H8O, (4)center dot MeOH center dot THF, and bis(mu-2-{[(2-methoxyphenyl)imino]methyl}phenolato-1 kappa O-3(1), N, O-2 :2 kappa O-1)bis(2-{[(2-methoxyphenyl)imino]methyl}phenolato-2 kappa O-3(1), N, O-2)sodiumyttrium chloroform disolvate, [NaY(C14H12NO2)(4)]center dot 2CHCl(3), (5)center dot 2CHCl(3). Structural peculiarities of homoleptic tris(iminophenoxide)s (1)-(3), binuclear tris(iminophenoxide) (4) and homoleptic ate tetrakis(iminophenoxide) (5) are discussed. The nonflat Schiff base ligand displays mu(2)-kappa O-3(1), N, O-2 :kappa O-1 bridging, and kappa O-3(1), N, O-2 and kappa N-2, O-1 terminal coordination modes, depending on steric congestion, which in turn depends on the ionic radii of the rare-earth metals and the number of coordinated ligands. It has been demonstrated that interligand dihedral angles of the phenoxide ligand are convenient for comparing steric hindrance in complexes. (4)center dot MeOH has a flat Y2O2 rhomboid core and exhibits both inter- and intramolecular MeO-H center dot center dot center dot Cl hydrogen bonding. Catalytic systems based on complexes (1)-(3) and (5) have demonstrated medium catalytic performance in acrylonitrile polymerization, providing polyacrylonitrile samples with narrow polydispersity.

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Tandem Condensation/Rearrangement Reaction of 2-Aminohetarene N-Oxides for the Synthesis of Hetaryl Carbamates

2018 · ARTICLE · en

A new approach to hetaryl carbamates through a tandem condensation/rearrangement reaction of 2-aminohetarene N-oxides was developed. The developed reaction is suitable for both five- and six-membered heterocycles and proceeds through the condensation of 2-aminohetarene N-oxide with trimethyl orthoformate followed by intramolecular N-oxide oxygen transfer. For five-membered hetarene N-oxides (furoxans), the intramolecular rearrangement is catalyzed by a cyanide anion, while for six-membered hetarene N-oxides (azines), Lewis acid catalysis is sufficient. The developed protocol is characterized by operational simplicity and high efficiency, resulting in carbamoyl derivatives in good and high yields.

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Estimations of energy of noncovalent bonding from integrals over interatomic zero-flux surfaces: Correlation trends and beyond

2018 · ARTICLE · en

Bonding energies of 50 associates composed by neutral molecules (atoms) and bounded by various weak noncovalent interactions are calculated within the DFT framework using the PBE0/aug-cc-pVTZ combination. The electronic virial and electron density values at bond critical points together with their integrals over interatomic surfaces are tested to check their ability to estimate bonding energies. Two correlations schemes dealing with integrals over interatomic surface are suggested to estimate bonding energy of any noncovalent interaction. The physical meaning of explored and several known correlations is discussed. Methods to estimate interatomic surface integrals of electronic virial and electron density are proposed.

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(2R,3R)-1,4-Dioxaspiro[4.4]nonane-2,3-dicarboxylic and (2R, 3R)-1,4-dioxaspiro[4.5]decane-2,3-dicarboxylic acids

2018 · ARTICLE · en

The title compounds, C9H12O6 and C10H14O6, were formed by careful hydrolysis of the corresponding diethyl esters. Their single crystals were grown from an ethyl acetate/hexane mixture. Crystals of both compounds have monoclinic (P2(1)) symmetry with a single molecule in the asymmetric unit. Both crystal structures are very similar and display four -CO-OH center dot center dot center dot O=C(OH)-hydrogen bonds, forming a two-dimensional double-layered framework.

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The truth is out there: the metal-pi interactions in crystal of Cr(CO)(3) (pcp) as revealed by the study of vibrational smearing of electron density

2018 · ARTICLE · en

The vibrational smearing of electron density was studied in the crystal of complex of Cr(CO)(3) with [2.2]paracyclophane. The combination of theoretical and experimental methods, including periodic calculations and screening of DFT calculated and multipole-decomposed electron densities, was utilized to reveal the vibrational smearing of electron density and its influence on the multipole-constructed electron density. The multipole model, commonly used to treat the high-resolution X-ray diffraction data, was shown to be rather inaccurate in description of electron density and its vibrational smearing in metal-pi complex where the interchange between diatomic interactions can occur. Namely, some bond critical points can be hidden while analyzing multipole-decomposed electron density with proved effects of vibrational smearing even if the deconvolution problem is overcome by using the invariom approach. On the contrary, the recently proposed "clouds of critical point variation" (CCPV) approach is demonstrated as the route to gather all reasonable bonding trends and to reconstruct static electron density pattern in metal-pi complexes.

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Electrophilic-Nucleophilic Dualism of Nickel(II) toward Ni center dot center dot center dot l Noncovalent Interactions: Semicoordination of Iodine Centers via Electron Belt and Halogen Bonding via sigma-Hole

2017 · ARTICLE · en

The nitrosoguanidinate complex [Ni{NH=C(NMe2)-NN(O)}(2).] (1) was cocrystallized with I-2 and sym-trifluorotriiodo-benzene (FIB) to give associates 1.2I(2) and 1.2FIB. Structures of these solid species were studied by XRD followed by topological analysis of the electron density distribution within the framework of Bader's approach (QTAIM) at the M06/DZP-DKH level of theory and Hirshfeld surface analysis. Our results along with inspection of XRD (CCDC) data, accompanied by the theoretical calculations, allowed the identification of three types of contacts. The Ni center dot center dot center dot I semicoordination of the electrophilic nickel(II) center with electron belt of 12 was observed in 1.2I(2), the metal -involving halogen bonding between the nucleophilic nickel(II)-d(z)(2) center and sigma-hole of iodine center was recognized and confirmed theoretically in the structure of [FeNi(CN)(4)(IPz)(H(2)0)](n) (IPz = 4-N-coordinated 2-I-pyrazine), whereas the arrangement of FIB in 1.2FIB provides a boundary case between the semicoordination and the halogen Ni center dot center dot center dot I bondings. In 1.2I(2) and 1.2FIB, noncovalent interactions were studied by variable temperature XRD detecting the expansion of noncovalent contacts with preservation of covalent bond lengths upon the temperature increase from 100 to 300 K. The nature and energies of all identified types of the Ni center dot center dot center dot I noncovalent interactions in the obtained (1.2I(2) and 1.2FIB) and in the previously reported ([FeNi(CN)(4)(IPz)(H2O)](n) [NiL2](I-3)(2)center dot 2I(2) (L = o-phenylene-bis(dimethylphosphine),[NiL]I-2 (L = 1,4,8,11-tetra-azacydotetradecane), Ni(en)(2)](n)[AgI2](2n) (en = ethylenediamine), and [NiL] (ClO4) (L = 4-iodo-2-(2-(2-(2-pyridyl)ethylsulfanypethylimino)methyl)-phenolate)) structures were studied theoretically. The estimated strengths of these noncovalent contacts vary from 1.6 to 4.1 kcal/mol and, as expected, become weaker on heating. This work is the first emphasizing electrophilic nucleophilic dualism of any metal center toward noncovalent interactions.

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Isomorphous rare-earth bis[bis(2,6-diisopropyl-phenyl)phosphate] complexes and their selfassembly into two-dimensional frameworks by intramolecular hydrogen bonds

2017 · ARTICLE · en

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl) phosphato-kappa O] chloridotetrakis( methanol-kappa O) neodymium methanol disolvate, [Nd(C24H34O4P)Cl( CH4O)(4)]center dot 2CH(3)OH, (1), and of the lutetium, [Lu(C24H34O4P) Cl(CH4O)(4)]center dot-2CH(3)OH, (2), and yttrium, [Y(C24H34O4P) Cl(CH4O)(4)]center dot 2CH(3)OH,(3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)-phosphate and LnCl(3)(H2O)(6) (in a 2:1 ratio) in methanol. Compounds (1)-(3) crystallize in the C2/c space group. Their crystal structures are isomorphous. The molecule possesses C-2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl) phosphate ligands all display a kappa O-1-monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O2P(O-2,6-(Pr2C6H3)-Pr-i)(2)}(2)Cl(CH3OH)(4)] molecular unit exhibits two intramolecular O-H center dot center dot center dot O hydrogen bonds, forming six-membered rings, and two intramolecular O-H center dot center dot center dot Cl interactions, forming four-membered rings. Intermolecular O-H . . . O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two-dimensional hydrogen-bond network. Crystals of bis[bis(2,6-diisopropylphenyl) phosphato-kappa O] tetrakis(methanol-kappa O)(nitrato-kappa(2) O, O ') neodymium methanol disolvate, [Nd(C24H34O4P)(NO3)(CH4O)(4)]center dot 2CH(3)OH, (4), have been obtained in an analogous manner from NdCl3(H2O)(6). Compound (4) also crystalizes in the C2/c space group. Its crystal structure is similar to those of (1)-(3). The kappa(2) O, O '-bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CNNd = 8). Unlike (1)-(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO3- ligand. The structure of (4) displays intra- and intermolecular O-H center dot center dot center dot O hydrogen bonds similar to those in (1)-(3). Compounds (1)-(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl) phosphate] rare-earth complexes.

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Toward a Rigorous Definition of a Strength of Any Interaction Between Bader's Atomic Basins

2017 · ARTICLE · en

Strength of interaction between Baders atomic basins, enclosed by zero-flux surfaces of electron distribution, was proposed to be a measure of elastic deformation of an interaction. The set containing 53 atomic aggregate and covering all range of interaction strength (from van der Waals interactions to triple covalent bonds) was calculated by DFT and perturbation theory methods. Further analysis was performed to seek correlations between various local quantities based on electron density and effective force constants of stretching diatomic vibrations. The linear trend between effective force constants and the potential energy density at the (3, -1) critical point of electron distribution was found. This correlation was improved by the integration of the potential energy density over an interbasin zero-flux surface of electron density. Simple mechanical explanation of established trends is presented. The correlations can be further used to at least semiquantitatively compare any pair of interactions between Baders atomic basins.

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Fluorinated Unsymmetrical N,N-Diaryl Imidazolium SaltsNew Functionalized NHC-Ligand Precursors

2017 · ARTICLE · en

An efficient and scaled-up synthesis of the imidazol-2-ylidene-based unsymmetrical NHC precursors bearing the sterically demanding hexafluoroisopropylalkoxy group [(CF3)(2)(OR)C-] at the ortho position of the N-aryl substituent was developed. The key step of the method involved the transformation of a Mes-substituted oxazolinium tetrafluoroborate salt through the reaction with the corresponding binucleophilic fluoroalkyl-substituted aniline. The subsequent post-modification of the resulting hydroxyl-containing salt through a simple one-step O-alkylation protocol provided access to a new family of unsymmetrical fluorinated NHC precursors. These compounds were successfully utilized for the preparation of several novel metal complexes. The molecular structures of some NHC precursors and their metal complexes have been unambiguously characterized by single-crystal X-ray diffraction analysis. A preliminary evaluation of the catalytic activity of the palladium complexes was performed on a Buchwald-Hartwig amination reaction. As a result, two PEPPSI-type (PEPPSI=pyridine-enhanced pre-catalyst preparation stabilization and initiation) Pd complexes have demonstrated promising activity in alkane solvents.

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H2C(X)- X center dot center dot center dot X- (X = CI, Br) Halogen Bonding of Dihalomethanes

2017 · ARTICLE · en

The dihalomethane-halide H2C(X)-X center dot center dot center dot X- (X = Cl, Br) halogen bonding was detected in a series of the cis [PdX(CNCy){C(NHCy)=NHC6H2Me2TH2}] X center dot CH2X2 (X = Cl, Br) associates by single-crystal XRD followed by DFT calculations. Although ESP calculations demonstrated that the a-hole of dichloromethane is the smallest among all halo methane solvents (the maximum electrostatic potential is only 2.6 kcal/mol), the theoretical DFT calculations followed by Bader's QTAIM analysis (MO6/DZP-DICH level of theory) confirmed the H2C(X)-X center dot center dot center dot X- halogen bond in both the solid-state and gas-phase optimized geometries. The estimated bonding energy in H2C(X)-X center dot center dot center dot X- is in the 1.9-2.8 kcal/mol range.

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Курсы (3)