Нифантьев Илья Эдуардович
Базовая кафедра нефтехимии и полимеров Института нефтехимического синтеза им А.В. Топчиева РАН
Профессиональные интересы
Должности
- Профессор — Базовая кафедра нефтехимии и полимеров Института нефтехимического синтеза им А.В. Топчиева РАН
Био
- · Начал работать в НИУ ВШЭ в 2013 году.
Образование
- 1993 · Доктор наук
- 1985 · Специалитет: Московский государственный университет им. М.В. Ломоносова, специальность «Химия», квалификация «Химик»
Опыт работы
- · 2004: с года по н.в. занимает должность профессора по кафедре органической химии в МГУ имени М.В.Ломоносова, химический факультет
- · 2010: В году (по н.в.) поступил по совместительству на работу в ИНХС РАН на позицию заведующего Лабораторией металлоорганического катализа (№8)
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)
- · Лучший преподаватель — 2023
Гранты и проекты
- — · на соискание учёной степени кандидата наук
Идентификаторы исследователя
- ORCID:
0000-0001-9151-1890 - ResearcherID:
O-1872-2013 - Google Scholar: https://scholar.google.com/citations?user=Crz3AmUAAAAJ&hl=en
- Scopus AuthorID:
6701810372
Публикации (41)
Heterocene Catalysts and Reaction Temperature Gradient in Dec-1-ene Oligomerization for the Production of Low Viscosity PAO Base Stocks
2023 · ARTICLE · en
Hydrogenated oligomers of higher α-olefins (primarily,dec-1-ene) with uniform structure represent high-quality poly-α-olefin oil (PAO) base stocks. High yields of lightweight dec-1-ene oligomers (DPn = 3−4) can be achieved by using 5,10-dihydroindeno[1,2-b]indole-based zirconium ansa-complexes,“heterocenes”. Unusual catalytic behavior of heterocenes served as a starting point for the present study, during which new, more synthetically available and active heterocene precatalysts were synthesized, and a novel oligomerization method, based on a reaction temperature gradient, was developed. A gradual decrease of the oligomerization temperature as dec-1-ene was consumed resulted in decreased dimer formation (down to 10%) and increased oligomer yields (up to 84%). After hydrogenation, low- and medium-viscosity PAO base oils with uniform structure and high viscosity indexes were obtained.
Cyclopentadienyl lanthanide borohydrides derived from the unsubstituted cyclopentadienyl ligand. Unprecedented structural diversity and ε-caprolactone polymerization
2022 · ARTICLE · en
A series of mono-, bis and tris(cyclopentadienyl) complexes of La, Nd and Tb with borohydride ligands were synthesized and structurally characterized. Various structural types of complex anions and cations containing cyclopentadienyl and borohydride ligands in the coordination sphere of Ln3+ have been studied by single-crystal X-ray diffraction. Five different structural types of Cp-lanthanide borohydrides were found for neodymium: {CpNd(BH4)2} in [(CpNd(BH4)2(THF)2] (2Nd); {Cp2Nd(BH4)2}- in [Cp2Nd(BH4)2][Na(18-crown-6)(THF)2] (3Nd); {Cp2Nd(BH4)} in [Cp2Nd(BH4)(THF)] (4Nd); {CpNd(18-crown-6)(BH4)}+ in [Cp2Nd(BH4)2]2[CpNd(18-crown-6)(BH4)][Na(18-crown-6)(THF)2] (6Nd); {Cp3Nd(BH4)}- in [Cp3Nd(BH4)][Na(18-crown-6)(THF)2] (8Nd). Complex anions {Cp2Nd(BH4)2}- and {Cp3Nd(BH4)}- are able to replace each other in the crystal lattice. Mono- and bis(cyclopentadienyl)borohydride complexes of neodymium effectively initiate ε-caprolactone polymerization.
Luminescence sensitization of the Nd3+ ion in diphenyl(9-antnracenyl)cyclopentadienyl complexes containing antenna-ligand with extended π-system
2022 · ARTICLE · en
Mono-3,4-diphenyl(9-anthracenyl)cyclopentadienyl dichloride complexes {[CpAntLn(thf)]2(µ2-Cl)2(µ3-Cl)3K(thf)}2 Ln = Nd, Gd, Tb, CpAnt = Ph2(C14H9)C5H2 were synthesized and structurally characterized. All the complexes were obtained in the form of tetranuclear ate complexes consisting of two [CpAntLn(thf)]2(µ2-Cl)2(µ3-Cl)3K(thf) units connected via two K–Cl bonds. In ]the Tb complex, anthracene fragments from two different molecules participate in the stacking interactions with a high degree of π-system overlap. Characteristic luminescence of the Nd3+ ion was obtained for the first time for the Nd-cyclopentadienyl complex. Energies of singlet and triplet states for CpAnt ligand were estimated.
Synthesis, molecular structure and catalytic performance of heterocycle-fused cyclopentadienyl-amido CGC of Ti (IV) in ethylene (co)polymerization: The formation and precision rheometry of long-chain branched polyethylenes
2022 · ARTICLE · en
Long-chain branching is an efficient tool to design and produce polyolefins with enhanced mechanical characteristics, physical properties, and processability. In the synthesis of long-chain branched polyethylene (LCB PE), constrained geometry complexes (CGCs) of Ti (IV) [(η5-C5Me4)SiMe2NtBu]TiX2 (X = Cl, Ti1; X = alkyl) are highly effective at elevated temperatures. However, further development of polyolefin technologies requires new catalytic approaches to provide LCB formation in broad temperature interval. In the present study, a series of CGCs of Ti (IV) of general formula [Cp#SiMe2NtBu]TiCl2 derived from heterocycle-fused cyclopentadienes Cp# (Ti2–Ti5) were synthesized and characterized by NMR spectroscopy and by X-ray diffraction analysis (XRD). New complexes Ti2–Ti5 along with benchmark precatalysts (n-BuC5H4)2ZrCl2 (Zr1) and Ti1 were supported on MMAO-12/silica and investigated in ethylene homopolymerization and ethylene/hex-1-ene copolymerization. In contrast to benchmark complexes Ti1 and Zr1, Ti2–Ti5 catalyzed formation of LCB PEs even at 80 °C, as confirmed by precision rheology studies of ethylene/hex-1-ene copolymers. The complex Ti2, derivative of 5-methyl-5,10-dihydroindeno[1,2-b]indole, demonstrated the best set of properties.
A competetive way to low-viscosity PAO base stocks via heterocene-catalyzed oligomerization of dec-1-ene
2022 · ARTICLE · en
Hydrogenated oligomers of higher α-olefins (primarily, dec-1-ene) represent base stocks for high-quality polyolefin oils (PAOs), transmission fluids, lubricants and greases. Competitive advantages of zirconocene catalysts in oligomerization of α-olefins have been already demonstrated and industrially implemented for higher oligomers. However, the problem of the selective synthesis of α-olefin oligomers that have degree of polymerization (DPn) 3 and 4, remains unresolved. A series of –CH2CH2– bridged ansa-zirconocenes derived from 5,10-dihydroindeno[1,2-b]indole, 'heterocenes' Zr4–Zr6, were synthesized and characterized by NMR spectroscopy and X-ray diffraction (XRD) analysis. New complexes Zr4–Zr6 and known –SiMe2– bridged ansa-heterocenes Zr1–Zr3 were investigated in oligomerization of dec-1-ene using MMAO-12 or [PhNMe2H][B(C6F5)4] activators. In the atmosphere of molecular hydrogen, at [dec-1-ene]/[Zr] ratios up to 4·105, rac-forms Zr4r–Zr6r provided more than 85% yields of dec-1-ene oligomers without skeletal rearrangements. In some experiments, at least 50% yields of lightweight oligomers (DPn=3–4) were achieved. After activation of Zr6r by TIBA and [PhNMe2H][B(C6F5)4] and completion of dec-1-ene oligomerization, we isolated new cationic complex Zr6r-Al containing Zr-(μ-Cl)2-Al fragment, as confirmed by XRD. Zr6r-Al alone was inactive against dec-1-ene, but after addition of TIBA oligomerization started. Due to uniform molecular structure of oligomers, complete catalytic hydrogenation of oligo(dec-1-ene)s was conducted using Ni/Al2O3 catalyst under mild conditions (150°C, 3 h, 20 bar). Hydrogenated dec-1-ene oligomers turned out to be high-quality PAO base stocks far exceeding industrial dec-1-ene PAOs in terms of viscosity characteristics.
Chain-End Functionalization of Poly(ε-caprolactone) for Chemical Binding with Gelatin: Binary Electrospun Scaffolds with Improved Physico-Mechanical Characteristics and Cell Adhesive Properties
2022 · ARTICLE · en
Composite biocompatible scaffolds, obtained using the electrospinning (ES) technique, are highly promising for biomedical application thanks to their high surface area, porosity, adjustable fiber diameter, and permeability. However, the combination of synthetic biodegradable (such as poly(ε-caprolactone) PCL) and natural (such as gelatin Gt) polymers is complicated by the problem of low compatibility of the components. Previously, this problem was solved by PCL grafting and/or Gt cross-linking after ES molding. In the present study, composite fibrous scaffolds consisting of PCL and Gt were fabricated by the electrospinning (ES) method using non-functionalized PCL1 or NHS- functionalized PCL2 and hexafluoroisopropanol as a solvent. To provide covalent binding between PCL2 and Gt macromolecules, NHS-functionalized methyl glutarate was synthesized and studied in model reactions with components of spinning solution. It was found that selective formation of amide bonds, which provide complete covalent bonding of Gt in PCL/Gt composite, requires the presence of weak acid. With the use of the optimized ES method, fibrous mats with different PCL/Gt ratios were prepared. The sample morphology (SEM), hydrolytic resistance (FT-IR), cell adhesion and viability (MTT assay), cell penetration (fluorescent microscopy), and mechanical characteristics of the samples were studied. PCL2-based films with a Gt content of 20 wt% have demonstrated the best set of properties.
Synthesis and Structural Diversity of Gadolinium 1-(o-Methoxyphenyl)-3,4-diphenylcyclopentadienyl Complexes
2022 · ARTICLE · en
Abstract: The reaction of 1-(o-methoxyphenyl)-3,4-diphenylcyclopentadienyl potassium with gadolinium chloride tetrahydrofuranate gives, depending on the stoichiometry, either tetranuclear complex [{[η5-(Ph2(o-CH3OC6H4)C5H2)Gd(Thf)]2(µ2-Cl)2(µ3-Cl)3K(Thf)}2] (I) or mononuclear complex [(Ph2(o-CH3OC6H4)C5H2)2GdCl] (II) (CIF files CCDC nos. 2116742 (I), 2116741 (II)). In complex I, the oxygen atom of the methoxy group is not coordinated to the gadolinium cation, whereas in complex II, the Gd3+ cation is coordinated to the oxygen atoms of both methoxy groups. Complex II crystallizes in the chiral space group P41212. © 2022, The Author(s).
Ligand-to-ligand charge transfer state in lanthanide complexes containing π-bonded antenna ligands
2022 · ARTICLE · en
To design luminescent lanthanide complexes containing both p- and s-bonded antenna ligands in the coordination sphere, we synthesized 2,2'-bipyridine complexes of Nd, Tb and Gd with tri- and tetraphenyl substituted cyclopentadienyl ligands: [CpPh3LnCl2(bipy)(THF)] (CpPh3 = 1,2,4-triphenylcyclopenta- dienyl, bipy = 2,2'-bipyridine) and [CpPh4LnCl2(bipy)(THF)] (CpPh4 = tetraphenylcyclopentadienyl). Their crystal structures were determined by X-ray diffraction analysis. Optical spectro scopic and crystallographic data indicate the presence of a ligand-to-ligand charge transfer state. © 2022
Crystal Structure of Decakis(μ-chloro)-tetrakis(1,2,4-triphenylcyclopentadienyl)-hexakis(tetrahydrofuran)-di-potassium-tetra-neodymium(III) Tetrahydrofuran Trisolvate
2021 · ARTICLE · en
The crystal structure of decakis(μ-chloro)-tetrakis(1,2,4-triphenylcyclopentadienyl)-hexakis(tetrahydrofuran)- di-potassium-tetra-neodymium(III) tetrahydrofuran trisolvate, 1, is reported. The centrosymmetric complex 1 has a rare tetranuclear core [Ln4K2Cl10] and crystalizes in triclinic space group (P̄1 ) with unit cell parameters: a = 11.9858(3) Å, b = 14.0698(3) Å, c = 19.8129(4) Å, α = 74.1120(4)°, β = 81.2073(4)°, γ = 83.9521(4)° and Z = 1. The catalytic system based on 1 and nBuMg(O-2,6-tBu2-4-MeC6H2) exhibits moderate activity in coordinative chain transfer polymerization of ethylene. In case of the system 1/nBu2Mg, oligomerisation of ethylene was not detected. Graphic
Heterocycle-fused cyclopentadienyl metal complexes: Heterocene synthesis, structure and catalytic applications
2021 · ARTICLE · en
Metallocenes of the group 4 metals have attracted great attention as precursors of single-site catalysts forthe production of advanced polyolefins. The annelation of a cyclopentadienyl ring with a heterocyclicfragment fundamentally changes the electronic and structural characteristics ofg5-coordinated ligandsand provides new dimensions for the design of novel and effective catalysts. Heterocycle-fused half-sandwich and sandwich metal complexes, called heterocenes, have been extensively studied since theearly 2000s. This review describes the different synthetic strategies employed in the preparation ofheterocycle-fusedg1-g5andg5-g5ansa-ligand precursors, and further, discusses the synthesis, molec-ular structure, and catalytic applications of heterocenes.
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