Proiect PN-II-ID-PCE-2011-3-0933:   Project timespan   Project team   Abstract   Project objectives   Budget   Results   Scientific reports  

Title: New Organometallic Compounds of Heavy Group 15 Metals (Antimony, Bismuth) -- Potential Use in Catalysis

Funding authority: National Research Council of Romania
Contract number: 258 / 2011

Project manager: Prof. Dr. Cristian Silvestru

Project team:

Project timespan
2012 -- 2016

Abstract
The organometallic chemistry of antimony and bismuth raised considerably interest due to the important results obtained both in areas of fundamental and applied interest. The aim of the present proposal is to bring new dimensions to a topic (organometallic species stabilized through N→M intramolecular coordination) in which the research team involved in this project already has significant contributions, i.e. investigation of potential uses of such organometallic species. The proposed research activities will be focused on:
  • the design of hypervalent organometallic compounds of the type R2MOH, (R2M)2O, R2MOR', (RMO)n (M = Sb, Bi; R = one or two pendant arm ligand) and their reaction with CO2 (CO2 fixation);
  • study of the catalytic activity of such organometallic species for synthesis of polycarbonates and/or cyclic carbonates from CO2 and epoxides (CO2 activation);
  • study of the reaction of new hypervalent dibismuthanes R2Bi−BiR2 (R = one or two pendant arm ligand) with dioxygen - potential use in selective oxidation of organic substrates;
  • study of the catalytic activity and the stereoselectivity of new chiral hypervalent organometallic species, R2MOR and [R2M]+X- (M = Sb, Bi) for the Mannich reaction;
  • design of transition metal complexes of new chiral organoantimony species and study of the catalytic activity for metal-catalyzed cross-coupling reactions.

Project objectives

The specific objectives of the present project proposal are concerned to potential applications of organoSb / Bi compounds as an obvious continuation of the researches on topics previously developed by our group, i.e. hypervalent (hypercoorinated) organometallic species:
  • Design of hypervalent organometallic compounds of the type R2MOH, (R2M)2O, R2MOR', (RMO)n (R, R' = one or two pendant arm ligand) and their reaction with CO2 to form new examples of the types (R2M)2CO3, R2MOC(O)OR' and RMCO3 (M = Sb, Bi);
  • Study of the catalytic activity of compounds of the types R2MOH, (R2M)2O, R2MOR', (RMO)n (M = Sb, Bi; R, R' = one or two pendant arm ligand) for synthesis of polycarbonates and/or cyclic carbonates from CO2 and epoxides;
  • Study of the reaction of new hypervalent dibismuthanes R2Bi-BiR2 (R = one or two pendant arm ligand) with dioxygen - potential use in selective oxidation of organic substrates;
  • Study of the catalytic activity and the stereoselectivity of new chiral hypervalent organometallic compounds of the type R2MOR and [R2M]+X- (M = Sb, Bi; R = one or two pendant arm ligand) for the Mannich reaction;
  • Design of transition metal complexes of new chiral organoantimony species and study of the catalytic activity for metal-catalyzed cross-coupling reactions.

Budget
Budget chapter (expenses) 2012 (lei) 2013 (lei) 2014 (lei) 2015 (lei) 2016 (lei) Total
1 Salaries 220.000 170.338 140.000 114.116 164.774 809.228
2 Inventory 251.729,31 7.346,89 14.277,25 5.801,60 76.806,31 355.961,36
3 Mobility 23.270,69 654 722,75 0 10.163,20 34.810,64
4 Overhead 123.750 44.584,72 38.750 29.979,40 62.935,88 300.000
5 Total 618.750 222.923,61 193.750 149.897 314.679,39 1.500.000

Results 2012 - 2016

Articles
  1. Synthesis and characterization of organoantimony(III)-containing heteropolytungstates.
    M. Barsukova-Stuckart, L. F. Piedra-Garza, B. Gautam, G. Alfaro-Espinoza, N. V. Izarova, A. Banerjee, B. Bassil, M. Ullrich, H. J. Breunig, C. Silvestru and Ulrich Kortz, Inorg. Chem., 2012, 51, 12015-12022.
    DOI: 10.1021/ic301892s

  2. Organoantimony(III) compounds containing(imino)aryl ligands of the type 2-(RN=CH)C6H4 (R = 2',4',6'-Me3C6H2, 2',6'-iPr2C6H3): bromides and chalcogenides.
    A. M. Preda, C. I. Raţ, C. Silvestru, H. J. Breunig, H. Lang, T. Rüffer and M. Mehring, Dalton Trans., 2013, 42, 1144-1158.
    DOI: 10.1039/c2dt32494f
    Cover Picture: Dalton Trans. Issue 4 2013, DOI: 10.1039/C2DT90210A

  3. Hypervalent organoantimony and -bismuth compounds with pendant arm ligands.
    C. I. Raţ, C. Silvestru and H. J. Breunig, Coord. Chem. Rev., 2013, 42, 1144-1158.
    DOI: 10.1016/j.ccr.2012.07.026

  4. Organoselenium(II) halides containing the pincer 2,6-(Me2NCH2)2C6H3 ligand - an experimental and theoretical investigation.
    A. Pop, A. Silvestru, E. J. Juá rez-Pé rez, M. Arca, V. Lippolis and C. Silvestru, Dalton Trans., 2014, 43, 2221-2233.
    DOI: 10.1039/C3DT52886C

  5. Palladium(II) complexes with chiral organoantimony(III) ligands. Solution behavior and solid state structures.
    D. Copolovici, F. Isaia, H. J. Breunig, C. I. Raţ and C. Silvestru, RSC Advances, 2014, 4, 26569-26576.
    DOI: 10.1039/c4ra03482a

  6. Hypervalent monoorganopnicogen(III) (M = Sb, Bi) oxides, carbonate, alkoxides, aryloxides and oxalates with the pincer 2,6-[MeN(CH2CH2)2NCH2]2C6H3.
    G. Strîmb, A. Pöllnitz, C. I. Raţ and C. Silvestru, Dalton Trans., 2015, 4, 9927-9942.
    DOI: 10.1039/c5dt00603a

  7. Synthesis and structural characterization of substituted phenols with m-terphenyl backbone, 2,4,6-R3C6H2OH (R = 2,4,6-Me3C6H2, Me5C6).
    A. B. Şolea, M. Olaru, C. Silvestru and C. I. Raţ, Z. Naturforsch., 2015, 70, 77-81.
    DOI: 10.1515/znb-2014-0180

  8. Synthesis and characterization of 2-[Mes(Me)NCH2]C6H4Br and 2-[Mes{(O)CH}NCH2]C6H4Br - Precursors for novel one pendant arm ligands.
    G. Strîmb, C. I. Raţ and C. Silvestru, Rev. Roum. Chim., 2015, 60, 651-657.
    DOI: n.a.

  9. Homoleptic organometallic compounds of heavy pnicogens. Crystal and molecular structure of [2-(iPr2NCH2)C6H4]3M (M = Sb, Bi).
    I. Chirca, A. Soran, A. Silvestru and C. Silvestru, Rev. Roum. Chim., 2015, 60, 643-650.
    DOI: n.a.

  10. Organoantimony(III)-containing tungstoarsenates(III): from controlled assembly to biological activity.
    P. Yang, B. S. Bassil, Z. Lin, A. Haider, G. Alfaro-Espinoza, M. S. Ullrich, C. Silvestru and U. Kortz, Chem. Eur. J., 2015, 21, 15600-15606.
    DOI: 10.1002/chem.201502398

  11. Hypervalent diorganoantimony(III) fluorides via diorganoantimony(III) cations - a general method of synthesis.
    A. M. Preda, C. I. Raţ, C. Silvestru, H. Lang, T. Rüffer and M. Mehring, RSC Advances, 2015, 5, 99832-99840.
    DOI: 10.1039/c5ra21788a

  12. 19-Tungstodiarsenate(III) functionalized by organoantimony(III) groups: tuning the structurebioactivity relationship.
    P. Yang, Z. Lin, G. Alfaro-Espinoza, M. S. Ullrich, C. I. Raţ, C. Silvestru and U. Kortz, Inorg. Chem., 2016, 55, 251-258.
    DOI: 10.1021/acs.inorgchem.5b02189

  13. Ti2-containing 18-tungsto-2-arsenate(III) monolacunary host and the incorporation of a phenylantimony(III) guest.
    K.-Y Wang, Z. Lin, B. S. Bassil, X. Xing, A. Haider, B. Keita, G. Zhang, C. Silvestru and U. Kortz, Inorg. Chem., 2015, 54, 10530-10532.
    DOI: 10.1021/acs.inorgchem.5b01863

  14. Mixed triorganobismuthines RR'2Bi [R' = C6F5, 2,4,6-(C6F5)3C6H2] and hypervalent racemic Bi-chiral diorganobismuth bromides RR'BiBr (R' = C6F5, Mes, Ph) with the pendant arm ligand R = 2-(Me2NCH2)C6H4. Influences of the organic substituent.
    M. Olaru, M. Nema, A. Soran, H. J. Breunig and C. Silvestru, Dalton Trans., 2015, 45, 9419-9428.
    DOI: 10.1039/C5DT05074J

  15. Tetra-antimony(III)-bridged 18-tungsto-2-arsenates(V), [(LSbIII)4(A-α-AsVW9O34)2]10− (L = Ph, OH): turning bioactivity on and off by ligand substitution.
    P. Yang, Z. Lin, B. S. Bassil, G. Alfaro-Espinoza, M. S. Ullrich, M.-X. Li, C. Silvestru and U. Kortz, Inorg. Chem., 2016, 55, 3718-3720.
    DOI: 10.1021/acs.inorgchem.6b00107

Conferences attended in 2012-2016
  1. Chiral hypervalent organoantimony(III) cations.
    A. M. Preda, H. Lang, T. Rüffer, M. Mehring and C. Silvestru,
    at The XXV International Conference on Organometallic Chemistry (ICOMC), Lisbon (Portugal), September 2-7, 2012.

  2. Organometallic Compounds - Unusual Species Stabilized Through Intramolecular Coordination.
    C. Silvestru,
    plenary lecture at A 9-a Sesiune de Comunicări Ştiinţifice Studenţeşti, Universitatea Bucureşti, Bucureşti, May 17, 2013.

  3. The use of hypervalent organoantimony(III) cations as catalysts in the Mannich reactions.
    A. M. Preda, C. Silvestru,
    at International Symposium of The Romanian Catalysis Society, (RomCat2013), Cluj-Napoca (Romania), May 29-31, 2013.

  4. Organometallic Compounds - Unusual Species Stabilized Through Intramolecular Coordination.
    C. Silvestru,
    invited conference at The 13th Edition of Timişoara's Academic Days, Timişoara, June 13, 2013.

  5. Main Group Organometallics - From Molecular Species to Inorganic Polymers.
    C. Silvestru,
    invited conference at Zilele Academice Ieşene - A XXIV-a Sesiune de Comunicări Ştiinţifice a Institutului de Chimie Macromoleculară "Petru Poni" Iaşi, October 3-5, 2013.

  6. Chelated antimony(III) and bismuth(III) alkoxides.
    A. Pöllnitz, G. Strîmb, C. Silvestru,
    at The 5th EuCheMS Chemistry Congres, Istanbul (Turkey), August 31 - September 4, 2014.

  7. New hypervalent organoantimony(III) and -bismuth(III) compounds.
    I. Chirca, A. M. Preda, C. Silvestru,
    at A XXXIII-a Conferinţă Naţională de Chimie, Căciulata, October 1-3, 2014.

  8. Syntheses and structural characterization of organoantimony(III) compounds with 2-(Ph2NCH2)C6H4 and 2-[Mes(Me)NCH2]C6H4 substituents.
    G. Strîmb, C. I. Raţ, C. Silvestru,
    at A XXXIII-a Conferinţă Naţională de Chimie, Căciulata, October 1-3, 2014.

  9. Palladium Coordination Compounds with Bulky Isocyanide Ligands.
    K. T. Kegyes, M. Olaru, C. Silvestru, C. I. Raţ,
    at Zilele Academice Ieșene - A XXV-a Sesiune de Comunicări Științifice a Institutului de Chimie Macromoleculară "Petru Poni", Iași, September 24-26, 2015.

  10. Evaluation of the Potential as Catalyst for Mannich Reactions of Selected Ionic Diorganoantimony(III) Compounds.
    A. Biro, C. I. Raţ, C. Silvestru,
    at A XXXIV-a Conferinţă Naţională de Chimie, Căciulata, October 4-7, 2016.

Contributions to BSc Theses
  1. Ana-Maria Lavinia Rahovan, Reacţii ale [2-(Me2NCH2)C6H4SbO)3 cu PhP(O)(OH)2, Me5C6B(OH)2 şi CF3COOH.
    BSc Thesis, July 2013.

  2. Atena B. Şolea, Synthesis and structural characterization of bulky phenols with m-tephenyl backbone.
    BSc Thesis, June 2014.

  3. Crina Marina Moga, Tehnologie pentru fabricarea produsului Na2S·9H2O. Aplicaţii în sinteza compuşilor Bi(III)-organici.
    BSc Thesis, June 2014.

  4. Gabriel I. Dunes, Complecși ai metalelor din grupa a 10-a cu liganzi stiban.
    BSc Thesis, July 2016.

Reports
  • The yearly scientific reports containing experimental details of unpublished compounds data can be provided for project evaluation purposes only. To obtain copies of these reports please contact Prof. Dr. Cristian Silvestru by e-mail at cristian.silvestru (at) ubbcluj.ro .

Scientific reports

Scientific report for 2012-2014 time span is available here here.
Scientific report for 2015 time span is available here here.
Scientific report for 2012-2016 time span is available here here.