Laboratory of Coordination Chemistry

Institute of Chemistry, Academy of Sciences of Moldova,

Academiei str. 3, MD-2028 Chisinau, Moldova

Phone: + 373(22)739790; Fax: +373(22)739611;

e-mail:

Laboratory of Coordination Compounds was founded in 1959 as part of the Institute of Chemistry of the Moldovan branch of the Academy of Sciences of former USSR by the Academician Antonie Ablov, who guided it up to 1978. In the period of 1978-2006 the Laboratory of Coordination Compoundswas headed by Academician Nicolae Gerbeleu. In 2006 this laboratory was guided for a short period by Professor, Doctor Habilitate Mihail Revenco. Later in the same year, Doctor Habilitate Ion Bulhac was elected as a new head of the Laboratory of Coordination Chemistry.

Keywords: coordination chemistry; supramolecular chemistry; ligand design; transition metals; polynuclear complexes; coordination polymers

Research interests

The research interests cover all aspects of the preparation of mono-, polynuclear and supramolecular compounds based on transition metals and organic polyfunctional ligands and characterization of these complexes using a wide range of modern techniques. Current research activities are divided into two main areas:

Self-assembly and template design of the transition metal complexes with polydentate ligands. We are interested in development of

  • synthetic methods, especially template synthesis of the mono-, polynuclear and supramolecular compounds of the transition metals with organic polyfunctional ligands based on Shiff bases;
  • basic research in elucidating of the physical, chemical, magnetical, catalytical and structural properties of the synthesized compounds ;
  • applied research of the coordination compounds as stimulators of the vital activity of some microorganisms in the biosynthesis of enzymes, as well as stimulators for the increasing of productivity and drought resistance of cultivated plants.

Polynuclear carboxylate complexes and coordination polymers. Our efforts in this area are focused on the synthesis of different metal carboxylates both of the small clusters (mono-, bi-, trinuclear) and larger cages (from M4 to M16), as well as coordination polymers with the metals such as vanadium, chromium, manganese, iron, cobalt, nickel, copper, or zinc. Our group has pioneered high temperature routes to polynuclear carboxylate cages. This route has made cages containing between six and twelve metal centers, e.g. the first hexanuclear iron(III) carboxylates Fe6O2(OH)2(O2CCMe3)12 was obtained by heating [Fe3O(O2CCMe3)6(H2O)3].O2CCMe3 in tetradecane [ref. 10]. This work also led to the first high nuclearity chromium(III) cage in 1989 - a dodecanuclear Cr(III) cluster [Cr12O9(OH)3(O2CCMe3)15] [refs. 11,12] with an S = 6 ground state. The group has also pioneered the use of fluoride as a bridging ligand in polymetallic complexes - producing several fascinating metal-fluoride-carboxylate wheels [refs. 13-15]. One family of these - an octanuclear chromium wheel [Cr8F8(O2CCMe3)16] - has been widely studied as an archetypal anti-ferromagnetically coupled wheel. It is also the ancestor of a large family of AF heterometallic Cr7Mrings that has attracted considerable attention in the last five years [ref. 16]. We are also conducted research into coordination polymers that have a grate potential in catalysis, magnetic materials, etc. and using for their synthesis a variety of carboxylic acids or N-containing aromatic amines as bridging ligands. The properties of synthesized complexes are studied in collaboration with groups from Austria, Denmark, Germany, Italy, Switzerland, Russia, UK, Ukraine, and USA.

Selected publications

1. N.V. Gerbeleu. Reaction on matrix.Chisinau, Stiinta, 1980, (in Russian).

  1. N.V. Gerbeleu, C.М. Indricean. Mass- spectrometry of coordination compounds.Chisinau, Stiinta, 1984, (in Russian).
  2. N.V. Gerbeleu, V. Arion, J. Burgess. Template Synthesis of Macrocyclic compounds. Wiley-VCH. Weinheim. 1999.
  3. P. Bourosh, O. Bologa, Yu. Simonov, N. Gerbeleu, J. Lipkowski, M. Gdaniec. Synthesis and structure of products of interaction of H[AuCl4] with H2DMG and pyridine.Inorganica Chimica Acta 360 (2007) 3250.
  4. J. Gradinaru, A. Forni, V. Druta, F. Tessore, S. Zecchin, S. Quicci, N. Gerbeleu. Structural, spectral, EFISH and theoretical study of Ni(II), Cu(II), Zn(II) and VO(II) complexes with [N2O2] unsymmetrical Shiff bases of S-methylisothiosemicarbazide derivates. Inorganic Chemistry 46 (2007) 884.
  5. S.G. Baca, Yu. Sevryugina, R. Clerac, I. Malaestean, N. Gerbeleu, M. Petruckhina. Linear trinuclear manganese(II) complexes: crystal structures and magnetic properties. Inorganic Chemistry Communication 8 (2005) 474.
  6. D. Dragancea, V.B. Arion, S. Shova, E. Rentschler, N.V. Gerbeleu. Azine-bridged octanuclear copper(II) complexes assembled with a one-stranded ditopic thiocarbohydrazone ligand.Angewandte Chemie, International Edition 44 (2005) 7938
  7. N. Gerbeleu, Yu. Simonov, O. Bologa, P. Bourosh, E. Coropceanu. Transamination reaction of dimethylglyoxime cobalt(III) matrix. Russian Journal of Inorganic Chemistry. 51 (2006) 717.
  8. G. Aromi, A. S. Batsanov, P. Christian, M. Helliwell, A. Parkin, S. Parsons, A. A. Smith, G. A. Timco, R. E. P. Winpenny. Synthetic and structural studies of cobalt – pivalate complexes.Chemistry a European Journal 9 (2003) 5142.
  9. A.S. Batsanov, Yu.T. Struchkov, G.A. Timko. Crystal structure of hexanuclear iron(III) pivalate Fe6O2(OH)2(O2CCMe3)12.Russian Journal of Coordination Chemistry14 (1988) 266.
  10. N.V. Gerbeleu, G.A. Timko, Yu.T. Struchkov, K.M. Indrician, G.A. Popovich, Synthesis and structure of dodecanuclear chromium oxopivalate.Doklady Academii Nauk SSSR307 (1989) 118.
  11. D. Eric, J.L. McInnes, S. Piligkos , G.A. Timco, R.E.P. Winpenny, Studies of chromium cages and wheels. Coordination Chemistry Reviews 249, (2005), 2577–2590.
  12. N.V. Gerbeleu, A.S. Batsanov, G.A. Timko, Yu.T. Struchkov, K.M. Indrichan, G.A. Popovich, Hexadeca--2,2-dimethyl-propionato-(O,O')-octa--fluorocta chrome(III) bis(dimethylketone) and method of obtaining same.Patent SU No. 1299116, Priority date 1985-08-07.
  13. N.V. Gerbeleu, Yu.T. Struchkov, G.A Timko, A.S. Batsanov, K.M. Indrician, G.A. Popovich, “Octanuclear chromium(III) fluoride-trimethylacetate: a complex macrocycle” Doklady Academii Nauk SSSR313 (1990) 1459.
  14. N.V. Gerbeleu, Yu.T. Struchkov, G.A. Timko, O.S. Manole, A.S. BatsanovSynthesis and study of octanuclearfluorotrimethylacetate of iron(III).,Doklady Academii Nauk SSSR331 (1993) 184.
  15. M. Affronte, S. Carretta, G.A. Timco, R.E.P. Winpenny A ring cycle: studies of heterometallic wheels.Chemical Communications (2007) 1789 (Feature article).

Practical applications

  • Stimulation of plant and biomass growth

Dioxymates of cobalt(III) may be used as biostimulators and catalysts of different biotechnological and chemical processes. The biosynthetic processes of some fungi are also stimulated by complexes with tetradentate ligands based on alkylated thiosemicarbazide. Homo- and heteronuclear compounds of iron, cobalt and manganese show well-defined properties by growing stimulators that increase the productivity and drought resistance of corn, cucumbers, ground nuts and other crops.

Patents:

  1. N. Gerbeleu, Yu. Simonov, P. Bourosh, A. Deseatnic, O. Bologa, E. Coropceanu, V. Condruc, S. Clapco. Fluoride of hexafluorphosphate-bis(dithiocarbamide)bis(dimethylglyoximato)-cobalt(III) possessing properties of the microorganisms growth stimulator. Patent MD 2833 F1.
  2. A. Stefarta, V. Cernat, S. Buceaceaia, A. N. Aluchi, C, Turta, I. Bulgac, V. Sofransky, T. Jovmir. Hexa--acetato(O,O')-3-oxo-tris(N,N'-diethylnicotinamide)-diiron(III)cobalt(II) monohydrate having plants growing, vegetation and productivity regulation activity. Patent MD 955 G2.
  3. V. Piscorscaia, Gh. Siscanu, A. Stefirta, S. Toma, C. Turta, I. Bulgac, V. Sofransky, T. Jovmir. Process for increasing the soya resistively against low temperature. Patent MD 1015 G2.
  4. A. Stefirta, S. Toma, C. Turta, V. Vrabie, V. Cernat, I. Bulgac, V. Sofransky. Process for increasing the plants resistively in the conditions of humidity lowering. Patent MD 1131 G2.
  5. A. Stefirta, V. Vrabie, S. Toma, C. Turta, I. Bulgac. Process for cultivation of cucumber plants Cucumis sativus L. Patent MD 2044 G2.
  6. A. Stefirta, N. Aluchi, S. Buceaceaia, C. Turta, I. Bulgac, V. Celac. Hexa--acetato(O,O')-3-oxo-tris(N,N'-diethylnicotinamide)-differum(III) manganese(II) dihydrate - ground nut growth regulator and process for ground nut treatment. Patent MD 2361 G2.
  • New complexes as excellent colorants for polymers

We developed new thermostable metal-macrocyclic colorants for plastics with high temperature reprocessing. New metal complexes with azamacrocyclic ligands showing high stability against the action of temperature (290-300C), light and aggressive components can be used as colorants for plastics and artificial fibers.

Patents:

  1. N. Gerbeleu, L. Nemchinova, S. Baca. 2,2-Difluor-9-alkylthio-5,6-di(-furyl)-12-methyl-1,3-dioxa-4,7,8,10,11,14-hexaaza-2-boraciclotetradeca-4,6,8,11,13-pentaenato-N4,N7,N10,N14-nickel(II) as colorant for plastics//Patent MD1206 G2. (wide range of green colour shades)
  2. M. Cocu, S. Manole, N. Gerbeleu, J, Gradinaru, A. Forni. Triazamacrocyclic complex compound nickel(II) and their application as colorant for thermoplastic polymers. PatentMD 2881 G2 (wide range of violet colour).

-Catalysts. The [Cr8F8(O2CCMe3)16] complex shows catalytic properties in olefin polymerization. It is also a single molecule magnet, a precursor for porous materials, and complex that forms clathrates.

-

Patent:

  1. G.Timco, R. Winpenny, N. Gerbeleu, Iu. Malaestean, S. Grebenco, Ch. Muryn. Process for obtaining of hexadeca--trimethylacetato(O,O')-octa--fluorooctachrome (III), Patent MD 2832 F1. (Yield 80%).

-Inhibitors of corrosion. The invention relates to the field of metal protection from corrosion in water, particularly steel, and may be used for corrosion inhibition in the closed pipe manifolds. The result consists in decreasing at least 6-7 times the corrosion lost.

Patent:

1. V. Parsutin, N. Soltoian, S. Sidelnicova, O. Bologa, V. Safranschy. Inhibitor of steel corrosion in the water. Patent MD 3348 F1.

Short history of the Laboratory of Coordination Chemistry

1959 – Laboratory of Inorganic Chemistry

1975 – Laboratory of Chemistry of Coordination Compounds

2006 – Laboratory of Coordination Chemistry

Heads of the lab:

1959 – 1978 – Academician Antonie Ablov

1978 – 2006 – Academician Nicolae Gerbeleu

2006 –Dr. Hab., Prof. Mihai Revenco

2006 – present - Dr. Hab. Ion Bulhac

Group members

The Laboratory of Coordination Chemistry has 16 coworkers, including one university professor, 2 doctors habilitate and 8 doctors in chemistry.

Head of the Laboratory–Ion Bulhac, Doctor Habilitate of Chemistry, Professor Associate

  1. Mihail Revenco, Doctor Habilitate of chemistry, Senior Scientist,

University Professor

Phone: + 373(22)577494, e-mail:

  1. Grigore Timco, Doctor of Chemistry, Leading Senior Scientist, Associate Professor

Phone: + 373(22)739611, e-mail:

  1. Vasile Lozan, Doctor of Chemistry, Senior Scientist

Phone: + 373(22)739661, e-mail:

  1. Olga Bologa, Doctor of Chemistry, Senior Scientist

Phone: + 373(22)739661

  1. Julieta Gradinaru, Doctor of Chemistry, Senior Scientist

Phone: + 373(22)739611, e-mail:

  1. Svetlana Baca, Doctor of Chemistry, Senior Scientist, Associate Professor

Phone: + 373(22)739611, e-mail: ;

  1. Eduard Coropceanu, Doctor of Chemistry, Senior Scientist

Phone: + 373(22)739661, e-mail:

  1. Maria Cocu, Doctor of Chemistry, Senior Scientist

Phone: + 373(22)739963, e-mail:

  1. Yurie Malaestean, Doctor of Chemistry, Researcher

Phone: + 373(22)739611, e-mail:

  1. Anatolie Dobrov, Researcher

Phone: + 373(22)739661, e-mail:

  1. Diana Dragancea, Junior Scientist

Phone: + 373(22)739611, e-mail:

  1. Svetlana Grebenco, Junior Scientist

Phone: + 373(22)739611, e-mail:

  1. Andrei Rija, PhD.Student

Phone: + 373(22)739661, e-mail:

  1. Olga Ciobanica, PhD.Student

Phone: + 373(22)739661, e-mail:

  1. Panfile Tatiana, PhD. Student

Phone: + 373(22)739611

  1. Galina Dulicevskaya, undegraduate student

Phone: + 373(22)739661, e-mail: