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Natalia V. Belkova
Personal Info
Academic Degree
Prof RAS, 2016
D.Sc. (Chem.), A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 2011
Ph. D. (Chem.), A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 1997.
M. Sc., Department of Chemistry, M. V. Lomonosov Moscow State University, 1993.
D.Sc. (Chem.), A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 2011
Ph. D. (Chem.), A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 1997.
M. Sc., Department of Chemistry, M. V. Lomonosov Moscow State University, 1993.
Experience
2012 - present - Professor, Leading Researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
2005 - 2012 - Senior Researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
1999 - 2004 - Researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
1998 - 1999 - Postdoctoral fellow, Pharmaceutical Sciences, St. Jude Children's Research Hospital, Memphis (TN), USA
1997 - 1998 - Junior researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
1993-1997 - Post-graduate student, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
2005 - 2012 - Senior Researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
1999 - 2004 - Researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
1998 - 1999 - Postdoctoral fellow, Pharmaceutical Sciences, St. Jude Children's Research Hospital, Memphis (TN), USA
1997 - 1998 - Junior researcher, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
1993-1997 - Post-graduate student, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
Scientific Interests
Transition-metal complexes and hydrides, structure-reactivity relationships. Intermolecular interactions, hydrogen bonding and proton transfer. Reaction mechanisms. Molecular spectroscopy. Theoretical calculations.
Awards
Soros post-graduate student fellowships, 1995-1997.
Russian Federation State Young Scientist fellowship, 1996.
Yu. T. Struchkov Award, Annual Young Scientists' Competition at the A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 1996.
Academia Europeae Award for young scientists from NIS, 1997.
1st prize at Annual Scientific Conference-Competition at the A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 2004.
Russian Science Support Foundation fellowships, 2004-2005.
Russian Federation State Young Scientist fellowship, 1996.
Yu. T. Struchkov Award, Annual Young Scientists' Competition at the A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 1996.
Academia Europeae Award for young scientists from NIS, 1997.
1st prize at Annual Scientific Conference-Competition at the A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 2004.
Russian Science Support Foundation fellowships, 2004-2005.
Additional
70 papers in Russian and international scientific journals (an average 21.3 citations per paper, H index = 20) and ca. 200 presentations at international and national chemical meetings; chapters in “Recent Advances in Hydride Chemistry”, (Eds: M. Peruzzini, R. Poli), Elsevier, 2001, “Spectroscopic Properties of Inorganic and Organometallic Compounds: Techniques, Materials and Applications”, (Eds: J. Yarwood, R. Douthwaite, S. Duckett), RSC, 2012, “Advances in Organometallic Chemistry: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book”, First Edition. Ed.: A. J. L. Pombeiro. John Willey & Sons, Inc. 2014.
CURRENT WORK includes variable temperature spectroscopic and theoretical studies of
- mechanism of proton transfer to late transition metal hydrides,
- transition metal hydrides as proton donors in hydrogen bond as compared to CH, NH, OH donors
- bonding between two hydride complexes working as proton donor and proton acceptor
- non-specific (polarity) and specific (hydrogen bonding) solvent effects on these reactions
- Ir based catalytic hydrogenation/dehydrogenation aiming the understanding of mechanism and improving the catalyst performance.
Publications
2024
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Russian Journal of Coordination Chemistry, 2024, 50(5), 316-325Isonitrile Coordination to Pincer Iridium Hydrido Chlorides
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Electrocatalytic Radical Degradation of 2-Aminoethanol by Nickel, Palladium and Platinum Complexes Bearing Non-Innocent Diarylamido/bis(Phosphine) Pincer Ligand
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Russian Journal of Coordination Chemistry, 2024, 50(5), 343-348Half-Sandwich Iminophosphonamide Rhodium Complexes as Highly Efficient Catalysts for Dehydrogenation of Dimethylamine-Borane
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Synergism of primary and secondary interactions in a crystalline hydrogen peroxide complex with tin
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Stepwise carbon dioxide hydrosylilation catalyzed by bimetallic complexes [CpM(CO)2(μ-CO)···Pd(But PCP)]
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Electrochemical generation and in situ EPR- and UV–vis- observation of aminyl-radical diarylamido/bis(phosphine) pincer complexes of Ni, Pd and Pt
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Two active species from a single metal halide precursor: a case study of highly productive Mn-catalyzed dehydrogenation of amine-boranes via intermolecular bimetallic cooperation
2023
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Role of Non-Covalent Interactions in the Reactions between Palladium Hydrido Complex with Amidoarylphosphine Pincer Ligand and Brønsted Acids
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Reactivity of heterobimetallic ion pairs in formic acid dehydrogenation
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The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes
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Activation of dinitrogen by group 6 metal complexes
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Basicity and hydride-donating ability of palladium(II) hydride complex with diarylamido-bis-phosphine pincer ligand
2022
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Versatile Reactivity of Half-Sandwich Rhodium(III) Iminophosphonamide Complexes
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Halogen or Arene: Complexation of 4,4'-Dibromobiphenyl with a Three-Membered Silver(I) Macrocycle
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Cyclometalated (NNC)Ru(ii) complex catalyzed β-methylation of alcohols using methanol
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The role of weak intermolecular interactions in photophysical behavior of isocoumarins on the example of their interaction with cyclic trinuclear silver(I) pyrazolate
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Fac-to-mer isomerization triggers hydride transfer from Mn(I) complex fac-[(Ph2PCH2PPh2)Mn(CO)3H]
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Amine-boranes reactions promoted by lanthanide(ii) ions
2021
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Nickel(II) dihydrogen and hydride complexes as the intermediates of H2 heterolytic splitting by nickel diazadiphosphacyclooctane complexes
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The mechanism of halogenation of decahydro-closo-decaborate dianion by hydrogen chloride
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The reaction of hydrogen halides with tetrahydroborate anion and hexahydro-closo-hexaborate dianion
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Iinfluence of phosphine (pincer) ligands on the transition metal hydrides reactivity
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Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”
2020
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Regioselective Isomerization of Terminal Alkenes Catalyzed by a PC(sp3)P Pincer Complex with a Hemilabile Pendant Arm
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Dichotomous Si–H Bond Activation by Alkoxide and Alcohol in Base-Catalyzed Dehydrocoupling of Silanes
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Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes
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Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides
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Dehydrogenation of amine–boranes catalyzed by a PCsp3P pincer iridium complex
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Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes
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Stereoisomerism as an Origin of Different Reactivity of Ir(III) PC(sp3)P Pincer Catalysts
2019
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Synthesis, Structural Properties and Reactivity of Ruthenocene-based Pincer Pd(II) Tetrahydroborate
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Non-covalent interactions in stoichiometric and catalytic reactions of iridium pincer complexes
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Ligands effect on the Lewis acidity of the metal and the N-bases binding to iridium pincer complexes
2018
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Macrocyclic Copper(I) and Silver(I) Pyrazolates: Principles of Supramolecular Assemblies with Lewis Bases
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Ruthenium p-cymene iminophosphonamide complexes: activation under basic conditions and transfer hydrogenation catalysis
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Steric and Acidity Control in Hydrogen Bonding and Proton Transfer to trans-W(N2)2(dppe)2
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Z-H bond activation in (di)hydrogen bonding as a way to proton/hydride transfer and H2 evolution
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Hydride donating abilities of the tetracoordinated boron hydrides
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Comprehensive Insight into Hydrogen Bonding of Silanes
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Amine Boranes Dehydrogenation Mediated by an Unsymmetrical Iridium Pincer Hydride: (PCN) vs (PCP) Improved Catalytic Performance
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The Origin of the MNXN Metallacycle Flexibility in the Chelate Iminophosphonamide and Amidinate Transition Metal Complexes
2017
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Catalytic Redox Isomerization of Allylic Alcohols with Rhodium and Iridium Complexes with Ferrocene Phosphine-Thioether Ligands
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Mechanism of Dimethylamine–Borane Dehydrogenation Catalyzed by an Iridium(III) PCP-Pincer Complex
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Mild activation of Ir-Cl bond upon the interaction of pincer iridium hydride (tBuPCP)IrH(Cl) with acids and bases
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Ammonia Borane Dehydrogenation Catalyzed by (κ4‑EP3)Co(H) [EP3 = E(CH2CH2PPh2)3; E = N, P] and H2 Evolution from Their Interaction with NH Acids
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The interplay of proton accepting and hydride donor abilities in the mechanism of step-wise boron hydrides alcoholysis
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Competition between the Hydride Ligands of Two Types in Proton Transfer to [{κ3-P-CH3C(CH2CH2PPh2)3}RuH(η2-BH4)]
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Coordinatively labile 18-electron arene ruthenium iminophosphonamide complexes
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Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(2-BH4)2] Dichloromethane Solvate
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Ir(III)-PC(sp3)P Bifunctional Catalysts for Production of H2 by Dehydrogenation of Formic Acid: Experimental and Theoretical Study
2016
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Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides
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PCP Pincer Iridium Chemistry: Coordination of Pyridines to (tBuPCP)IrH(Cl)
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Dihydrogen Bonding and Proton Transfer from MH vs OH acids to Group 10 Metal Hydrides (tBuPCP)MH [tBuPCP = 3-2,6-(tBu2PCH2)2C6H3; M = Ni, Pd]
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Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]
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The Role of Weak Interactions in Strong Intermolecular M•••Cl Complexes of Coinage Metal Pyrazolates: Spectroscopic and DFT Study
2015
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Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene
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Dihydrogen Bond Intermediated Alcoholysis of Dimethylamine-Borane in Non-Aqueous Media
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Hydrogen bonds, coordination isomerism, and catalytic dehydrogenation of alcohols with the bifunctional iridium pincer complex (HOCH2)2(PCsp3P)IrHCl
2014
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Advances in Organometallic Chemistry, 2014, First Edition. Ed.: A. J. L. Pombeiro. John Willey & Sons, Inc. chapt. 8, 97-109. (book chapter)The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book. Weak Interactions and M-H Bond Activation
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Dihydrogen bonding in complex (PP3)RuH(η1-BH4) featuring two proton-accepting hydride sites: experimental and theoretical studies
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Dihydrogen bonding formed by (hydrido)[hydrotris(pyrazolyl)borato]ruthenium. The effect of ligands on the proton-withdrawing ability of ruthenium complexes
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Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents
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Transition metal hydride M—H bond activation upon the formation of complexes with acids and bases
2013
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Chemistry of boron hydrides orchestrated by dihydrogen bonds
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Z. Phys. Chem., 2013, 227, 69–88First Example of Hydrogen Bonding to Platinum Hydride
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Ligand–Metal Cooperating PC(sp3)P Pincer Complexes as Catalysts in Olefin Hydroformylation
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Hydrogen bonding and proton transfer to ruthenium hydride complex CpRuH(dppe): metal and hydride dichotomy.
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Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study
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Russ. Chem. Bull., 2013, 62, 751-757Iridium and rhodium complexes with the planar chiral thioether ligands in asymmetric hydrogenation of ketones and imines
2012
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Spectrosc. Prop. Inorg. Organomet. Compd., 2012, 43, 1–28 (book chapter)IR spectroscopy of hydrides and its application to hydrogen bonding and proton transfer studies
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ChemPhysChem, 2012, 13, 2677Directionality of Dihydrogen Bonds: The Role of Transition Metal Atoms
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Comput Theor Chem, 2012, 998, 129-140Hydrogen–deuterium exchange in hydride chemistry: Dihydrogen bonded complexes as key intermediates
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Inorg. Chem., 2012, 51, 6486-6497Dimerization Mechanism of Bis(triphenylphosphine)copper(I) Tetrahydroborate: Proton Transfer via a Dihydrogen Bond
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Dalton Trans., 2012, 41, 11849-11859Coordination chemistry of diphenylphosphinoferrocenylthioethers on cyclooctadiene and norbornadiene rhodium(I) platforms
2011
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J. Organomet. Chem., 2011, 696, 1174-1183Modeling the platinum-catalyzed intermolecular hydroamination of ethylene: the nucleophilic addition of HNEt2 to coordinated ethylene in trans-PtBr2(C2H4)(HNEt2)
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Angew. Chem. Int. Ed., 2011, 50, 1367–1370Acid-base interaction between transition metal hydrides results in dihydrogen bonding and assists H2 evolution
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Inorg. Chem., 2011, 50, 12539-52Coordination and Organometallic Chemistry of Relevance to the Rhodium-Based Catalyst for Ethylene Hydroamination