Department of General and Inorganic Chemistry

Donor-Acceptor Interactions Research Group

Study of structures and reactivity of donor-acceptor compounds in condensed, liquid and gaseous phases.

Group leader: Professor Alexey Y. Timoshkin, Ph.D. Acting head of the General and Inorganic Сhemistry department. E-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.

The author and supervisor of online courses:

“Inorganic chemistry: Introduction to chemistry of the elements” on Coursrera, on Stepik, on NPOO;
“Structure of matter: atoms, molecules, nanomaterials” on Coursrera.

Group Members

Group leader

Professor Alexey Yu. Timoshkin, Ph.D. Acting head of the Inorganic Сhemistry Department

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007-812-4284071
Audience 3154

Group members

	Davydova Elena I., Ph.D, Associate Professor Audience 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Pomogaeva Anna V., Ph.D, senior researcher Audience 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Lisovenko Anna S., Ph.D, senior researcher Audience 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Kondrat’ev Yurii V. Ph.D, Associate Professor Audience 113 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Kazakov Igor V., Ph.D, senior researcher Audience 113, 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Doinikov Dmitriy A., senior researcher Audience 113, 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.

Ph.D students

	Butlak Alina V., post-graduate student Audience 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Zavgorodnii Artem S., post-graduate student Audience 113, 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Chernysheva Anna M., post-graduate student Audience 113, 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.
	Gugin Nikita Yu., post-graduate student Audience 113, 3149, 3151, 3153, 3156 007-812-4284071 This email address is being protected from spambots. You need JavaScript enabled to view it.

Students

Parfenyuk Tatyana N., master student

Audience 3149, 3151, 3153, 3156

007-812-4284071

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Rastorguev Nikita S., bachelor student

Audience 3149, 3151, 3153, 3156

(812) 428 40 71

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Positions available

For participation in the post-position contest of St. Petersburg State University, contact the head of the research group A.Y. Timoshkin (E-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.).

Partners

Prof. M. Scheer (University of Regensburg),
Prof. J. Beckmann (University of Bremen),
Prof. F. Dielmann (University of Münster)
Prof. G. Frenking (Philipps-Universität Marburg),
Prof. J. Pinkas (University of Brno).

Current Research Topics

Synthesis and characterization of donor-acceptor compounds by X-ray structural analysis, IR and NMR spectroscopy; study of their thermal stability and vaporization by tensimetry and mass-spectrometry methods; reactivity studies of complexes in non-aqueous solutions and in the gas phase.
Quantum chemical computations of structural and thermodynamic characteristics of donor-acceptor complexes, studying of the reaction mechanisms.
Development of structural-thermodynamic approach in high temperature chemistry of coordination compounds.
Application of donor-acceptor compounds in catalysis, chemical vapor deposition and as precursors for the composite materials.
Donor-acceptor stabilization of reactive inorganic hydrides and study of their decomposition mechanisms.

Grants, Scholarships and Awards

Research grants for the past 5 years

Grant RSF-DFG 21-43-04404 "Mixed main group compounds of p block elements", 2021-2023.
RSF Grant 18-13-00196 "Acidity scales of Lewis acids and superacids", 2018-2020.
Grant SPSU-DFG "Donor-stabilized monomeric pnictidoalanes and gallanes", 2017-2019. (12.65.44.2017)
RSF Grant 14-13-00151 "Amidoboranes of main group metals: thermal stability and decomposition mechanisms", 2014-2016. (12.53.1173.2014)
SPSU Grant "Reactivity of group 13-15 inorganic heterocycles", 2014-2016. (12.38.255.2014)

Scholarships and Awards

Artem Zavgorodnii — SPSU-DAAD scholarship “Dmitrij Mendeleev” 2018
Anna Chernysheva — Scholarship from Saint Petersburg government 2018–2019
Anna Chernysheva — Won a competitive SPSU grant (28875246) for the internship in Germany. Project: “Synthesis and characterization of monomeric phosphanylalanes and phosphanylgallanes, stabilized by N-heterocyclic carbenes” 2018.
Anna Chernysheva — Won a competitive SPSU grant (12.42.719.2017) for the internship in Germany. Project: “Synthesis and characterization of donor-acceptor stabilized phosphanylalanes DH₂AlPR₂W(CO)₅ (D = NHC(IPr), R = H, CH₃)” 2017
Gugin Nikita — The winner of the XXVIII Mendeleev competition of students-chemists (13–18 may 2018, Novosibirsk)
Anna Chernysheva — The winner of the XVI Conference of Young Scientists “Actual problems of inorganic chemistry: from fundamental research to modern technology”, Moscow, Russia, 2017
Nadejda Scherbina — The winner of the nomination "Best Start" of the II School-Conference “Directed design of substances and materials with specified properties", Saint-Petersburg, 2017.

Publications

Representative publications

A. V. Butlak, I. V. Kazakov, A. Stauber, O. Hegen, M. Scheer, A. V. Pomogaeva, A. Y. Timoshkin Thermal decomposition of donor-stabilized phosphinoborane PH₂BH₂NMe₃: a tensimetry study Eur. J. Inorg. Chem. 2019, N. 35, P. 3885-3891. DOI: 10.1002/ejic.201900817

A.M. Chernysheva, M. Weinhart, M. Scheer, A. Y. Timoshkin Normal to abnormal I^tBu•AlH₃ isomerization in solution and in the solid state. Dalton Trans., 2020, Vol. 49, N. 15, P. 4665-4668. DOI: 10.1039/C9DT04698D

N. Y. Gugin, A. Virovets, E. Peresypkina, E. I. Davydova, A. Y. Timoshkin Structural Variety of Aluminium and Gallium Coordination Polymers Based on Bis-pyridylethylene: From Molecular Complexes to Ionic Networks. CrystEngComm, 2020, Vol. 22, N. 27, P. 4531–4543. DOI: 10.1039/D0CE00541J

EDGE ARTICLE : J. F. Kögel, A. Y. Timoshkin, A. Schröder, E. Lork, J. Beckmann, Al(OCAr^F₃)₃ — A Thermally Stable Lewis Superacid. // Chem . Sci ., 2018, 9, N. 43, 8178-8183. doi.org/10.1039/c8sc02981d

CENTENNIAL FEATURE ARTICLE: Timoshkin A.Y., Schaefer H.F. From Charge Transfer Complexes to Nanorods. // J. Phys. Chem . C . 2008, Vol. 112, N. 36, P. 13816 - 13836. doi.org/10.1021/jp801609z

REVIEW: Davydova E.I., Sevastianova T.N., Suvorov A.V., Timoshkin A.Y. Molecular complexes formed by halides of group 4,5,13-15 elements and the thermodynamic characteristics of their vaporization and dissociation found by the static tensimetric method. // Coord. Chem. Rev. 2010, Vol. 254, N. 17-18, P. 2031-2077. doi.org/10.1016/j.ccr.2010.04.001

REVIEW: Timoshkin A.Y. Group 13 imido metallanes and their heavier analogs [RMYR’]_n (M=Al,Ga,In; Y=N,P,As,Sb). // Coord. Chem. Rev. 2005, Vol. 249, N. 19-20, P.2094-2131. doi.org/10.1016/j.ccr.2005.03.016

REVIEW: Davydova E. I., Sevastianova T.N., Timoshkin A. Y. Molecular complexes of group 13 element trihalides, pentafluorophenyl derivatives and Lewis superacids. Coord. Chem. Rev., 2015, Vol. 297-298, P. 91-126. doi.org/10.1016/j.ccr.2015.02.019

Mück L.A., Timoshkin A.Y., von Hopffgarten M., Frenking G. Donor Acceptor Complexes of Noble Gases. // J. Am. Chem. Soc., 2009, Vol. 131, № 11, P. 3942–3949. dx.doi.org/10.1021/ja805990h

Timoshkin A.Y., Suvorov A.V., Bettinger H.F., Schaefer H.F. Role of the Terminal Atoms in the Donor-Acceptor Complexes MX₃-D (M=Al,Ga,In; X=F,Cl,Br,I; D=YH₃, YX₃, X^-; Y=N,P,As) // J. Am. Chem . Soc ., 1999, V. 121, N. 24, P. 5687-5699. doi.org/10.1021/ja983408t

Timoshkin A.Y., Bettinger H.F., Schaefer H.F. // The Chemical Vapor Deposition of Aluminum Nitride: Unusual Cluster Formation in the Gas Phase. J. Am. Chem. Soc., 1997, V. 119, N. 24, P. 5668-5678. doi.org/10.1021/ja964163s

Main publications of the group for the past 5 years

A. V. Butlak, I. V. Kazakov, A. Stauber, O. Hegen, M. Scheer, A. V. Pomogaeva, A. Y. Timoshkin Thermal decomposition of donor-stabilized phosphinoborane PH2BH2NMe3: a tensimetry study. Eur. J. Inorg. Chem. 2019, N. 35, P. 3885-3891. https://www.doi.org/10.1002/ejic.201900817
A.M. Chernysheva, M. Weinhart, M. Scheer, A. Y. Timoshkin Normal to abnormal ItBu•AlH3 isomerization in solution and in the solid state. Dalton Trans., 2020, Vol. 49, N. 15, P. 4665-4668. https://www.doi.org/10.1039/C9DT04698D
N. Y. Gugin, A. Virovets, E. Peresypkina, E. I. Davydova, A. Y. Timoshkin Structural Variety of Aluminium and Gallium Coordination Polymers Based on Bis-pyridylethylene: From Molecular Complexes to Ionic Networks. CrystEngComm, 2020, Vol. 22, N. 27, P. 4531–4543. https://www.doi.org/10.1039/D0CE00541J
O. Hegen, J. Braese, A. Y. Timoshkin, M. Scheer, Bidentate Phosphanyl- and Arsanylboranes. Chem. Eur. J., 2019, Vol. 25, N. 2. P. 485-489. https://doi.org/10.1002/chem.201804772
E. I. Davydova, A. Virovets, E. Peresypkina, A. V. Pomogaeva, A. Y. Timoshkin, Crystal Structures of Antimony(III) Chloride complexes with Pyridine. Polyhedron, 2019, Vol. 158, P. 97-101. https://doi.org/10.1016/j.poly.2018.10.056
A. V. Pomogaeva, A. Y. Timoshkin, M. Scheer, Why do B-P and Al-P polymers differ? Structures, stability and electronic properties of chain and ring [H2PEH2]n oligomers (E = B, Al; n = 1-15). Chem. Eur. J., 2018, V. 24, N. 64, P. 17046-17054. https://doi.org/10.1002/chem.201803008
O. Hegen, A. V. Virovets, A. Y. Timoshkin, M. Scheer, The Lewis base stabilized diphenylsubstituted Arsanylborane – A versatile building block for arsanylborane oligomers. Chem. Eur. J., 2018, V. 24, N. 62, P. 16521-16525. https://doi.org/10.1002/chem.201804341
J. F. Kögel, A. Y. Timoshkin, A. Schröder, E. Lork, J. Beckmann, Al(OCArF3)3 - A Thermally Stable Lewis Superacid. Chem. Sci., 2018, 9, N. 43, 8178-8183. https://doi.org/10.1039/c8sc02981d
J. Braese, A. Schinabeck, M. Bodensteiner, H. Yersin, A. Y. Timoshkin, M. Scheer, Gold(I) Complexes Containing Phosphanyl- and Arsanylborane Ligands. Chem. Eur. J., 2018, 24, 10073-10077. https://doi.org/10.1002/chem.201802682
Kondrat'ev, Yu. V., Butlak, A. V., Kazakov, I. V., Krasnova, I. S., Chislov, M. V., Timoshkin, A. Yu., Heat Effects of the Thermal Decomposition of Amidoboranes of Potassium, Calcium, and Strontium, Russ. J. Phys. Chem. A 2018, Vol. 92, № 4, pp 640–645. http://dx.doi.org/10.1134/S0036024418040143
S. Heinl, A. Y. Timoshkin, J. Müller, M. Scheer, Unexpected differences in the reactivity between the phosphorus and arsenic derivatives [(CpBIGFe)₂(µ,η4:4-E₄)] (E = P and As). Chem. Commun. 2018, Vol. 54, N. 18, P. 2244-2247. https://doi.org/10.1039/c7cc09730a
C. Marquardt, O. Hegen, A. Vogel, A. Stauber, M. Bodensteiner, A. Y. Timoshkin, M. Scheer, Depolymerization of Poly(phosphinoboranes): From Polymers to Lewis Base Stabilized Monomers. Chem. Eur. J. 2018, Vol. 24, N. 2, P. 360-363. https://doi.org/10.1002/chem.201705510
Doinikov, D. A., Kazakov, I. V., Krasnova, I. S., Timoshkin, A. Yu., An automatic digital tensimeter with a membrane zero-manometer. Russ. J. Phys. Chem. A 2017, 91, 1603–1608. https://doi.org/10.1134/S0036024417080088
Kazakov I.V., Butlak A.V., Shelyganov P.A., Suslonov V.V., Timoshkin A.Y. Reversible structural transformations of Rubidium and Cesium amidoboranes . Polyhedron, 2017, Vol. 127, P. 186-190. https://doi.org/10.1016/j.poly.2017.01.062
O. Hegen, C. Marquardt, A. Y. Timoshkin, M. Scheer. A convenient Route to mixed Pnictogenylboranes. Angew. Chem. Int. Ed., 2017, Vol. 56, N. 41, p. 12783–12787. https://doi.org/10.1002/anie.201707436
Pomogaeva A.V., Timoshkin A.Y. The effect of terminal substituents on the electronic properties of rod-shaped [HGaNH]n oligomers. Physical Chemistry Chemical Physics, 2016, Vol. 18, N. 29, P. 19859-19865. https://doi.org/10.1039/c6cp02576e
El Hamdi M., Solà M., Poater J., Timoshkin A. Y. Complexes of adamantane-based group 13 Lewis acids and superacids: bonding analysis and thermodynamics of hydrogen splitting. J. Comput. Chem. 2016, Vol. 37, N. 15., P. 1355-1362. https://doi.org/10.1002/jcc.24328
Pomogaeva A.V., Morokuma K, Timoshkin A.Y. Trimeric cluster of lithium amidoborane - the smallest unit for the modeling of hydrogen release mechanism. J. Comput. Chem., 2016, Vol. 37, N. 14, P. 1259-1264. https://doi.org/10.1002/jcc.24316
Doinikov D.A., Kollhammerova I., Löbl J., Necas M., Timoshkin A.Y , Pinkas J. Alumazene adducts with acetonitrile: structure and thermal stability. J. Organomet. Chem. 2016, Vol. 809, P. 38-44. https://doi.org/10.1016/j.jorganchem.2016.02.039
Kondrat’ev Yu.V, Butlak A.V., Kazakov I.V., Timoshkin A.Y. Sublimation and thermal decomposition of ammonia borane: competitive processes controlled by pressure. Therm. Acta, 2015, Vol. 622, P. 64-71. https://doi.org/10.1016/j.tca.2015.08.021

Equipment

Thermoscientific ISQ mass spectrometer with Direct Insertion Probe (DIP). The compact quadrupole mass spectrometer allows mass spectrometry studies of solid, liquid and gaseous samples. Transfer of solid and liquid samples into the gas phase is carried out using DIP with the implementation of programmable heating of the sample in the temperature range of 30–450 °C. Ionization is effected by electron impact with an electron energy of 70 eV. Data collection and analysis is carried out using the Thermo Scientific Xcalibur software package.

IR spectrometer Shimadzu IR Prestige-21. Allows measurement of the IR spectra of samples in the wavelength range of 250–7800 cm^-1 with a resolution of 0.5–1 cm^-1 and a signal-to-noise ratio of 40,000:1. IRsolution software is used to collect and analyze data.

Automatic static tensimeter isuniquely designed to enable continuous and long-term measurement of pressure and temperature in a closed glass system. Currently, measurements are possible in the temperature range from -196 °C to 400 °C and pressures of 1–760 torr. The collection and primary analysis of data is carried out on the basis of the software developed in the laboratory based on the LabView programming language. Analysis of the results of the conducted research allows us to draw conclusions about the thermal stability of compounds, the thermodynamic characteristics of the processes of dissociation, sublimation and evaporation, and the kinetics of the processes.

Differential automatic evaporation calorimeter DAK1-1a is used to directly determine the thermal effects of the processes of sublimation, evaporation and dissociation in the temperature range of 25–210 °C.

For work with compounds sensitive to moisture and oxygen, the laboratory is equipped with an InertLab 2GB glove box with an atmosphere of high-purity argon (residual moisture and oxygen content less than 0.1 ppm). The glove box is equipped with a freezer (up to -35 °C) and analytical balance, which allows for a full range of synthetic work and sample preparation for subsequent characterization. Schlenk lines are also used for work in an argon atmosphere.

The laboratory has a glass-blowing workshop for the performance of synthetic works in wholeglass vacuumed systems.

TimoshkinEquipm 7

Updated in 2020

Research group of professor Timoshkin A.