"Estonian Science Foundation Research Grant" project ETF8162
ETF8162 "The study of the design,synthesis,and basicity and acidity of strong and superstrong Bronsted bases and acids. (1.01.2010−31.12.2013)", Ilmar Koppel, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University.
ETF8162
Tugevate ja ülitugevate Brönstedi aluste ja hapete disain,süntees ning aluselisuse ja happelisuse uurimine
The study of the design,synthesis,and basicity and acidity of strong and superstrong Bronsted bases and acids.
1.01.2010
31.12.2013
Estonian Science Foundation Research Grant
Field of researchSubfieldCERCS specialtyFrascati Manual specialtyPercent
4. Natural Sciences and Engineering4.11. Chemistry and Chemical TechnologyP400 Physical chemistry 1.3. Chemical sciences (chemistry, other allied subjects)100,0
PeriodSum
01.01.2010−31.12.2010234 000,00 EEK (14 955,33 EUR)
01.01.2011−31.12.201114 955,60 EUR
01.01.2012−31.12.201214 955,60 EUR
01.01.2013−31.12.201314 955,60 EUR
59 822,13 EUR
89476,31

Uurimisprojekti eesmärgiks on tugevate ja ülitugevate Brönstedi aluste ja hapete disaini printsiipide üldistamine ja edasiarendamine ning nende elektronstruktuuri ja termodünaamiliste ja katalüütiliste omaduste ainete struktuurist ja keskkonna/ solvendi omadustest sõltuvuse eksperimentaal-teoreetiline uurimine ja uudsete superaluste ja superhapete happelis-aluseliste omaduste nn."kasvupiiride" väljaselgitamine.Disainitakse suur grupp materjale-ülitugevaid happeid ja aluseid ja nende derivaate,mis omavad potentsiaalselt olulist tähtsust ja tehnoloogilisi rakendusi modernsete jõuallikate (kütuseelemendid,Li-ioonpatareid)ja energiasalvestite(superkondensaatorid) disainis,stereoselektiivsete,regenereeritavate(ka "veesõbralike")katalüsaatoritena orgaanilises sünteesis ja naftakeemiatööstu- ses.Solvendiefektide mõju uurimiseks püstitatakse ja laiendatakse tugevate aluste ja hapete tugevuse skaalasid gaasifaasis, mittevesilahustes(DMSO,THF,MeCN,heptaan,diklooretaan jne) ja ioonsetes vedelikes.Uute superhapete ja -aluste happelis- aluseliste omaduste mittevesilahustes mõõtmise meetodid on kasutatavad ravimite,kahjulike kemikaalide ja bioloogiliselt aktiivsete ainete analüüsis.
The major goals of the present research proposal are the the generalization and development of the principles of the design of strong and superstrong Brönsted bases and acids,the experimental and theoretical study of their electronic structure,and thermodynamic and catalytic properties on their structure and solvent effects as well as the study of the "limits of growth" of the acid-base properties of the newly designed/created superacidic and superbasic materials.The large group of materials- superstrong acids and bases and their derivatives which are expected to have important technological implications for creation of modern,higly effective and environmentally friendly power sources(fuel cells,Li-ion batteries),energy storage devices(electrochemical supercondensators),in the synthesis of stereoselective,recoverable ,and "water-friendly" catalysts for organic synthesis and petrochemical industry,will be designed.For the study of the solvent effects on the acid-base properties of strong and superstrongBrönsted bases and acids the scales of acidity and basity will be significantly expanded or created in the gas pgase,aprotic non-aqueous solvents(DMSO,MeCN,THF,1,1-dichloroethane,heptane,etc.)and in ionic liquids.The lätter information is of great importane for the analysis of drugs,,hazzardous chemicals,and biologically active compounds.

Principal investigator (1)

PersonDegreeInstitution and occupationCVPeriod
Ilmar KoppelDoctor's DegreeEST / ENG01.01.2010−31.12.2012

Senior research staff (13)

PersonDegreeInstitution and occupationCVPeriod
Agnes HeeringMaster's DiplomaEST / ENG01.01.2012−31.12.2012
Ivari KaljurandDoctor's DegreeEST / ENG01.01.2010−31.12.2012
Gerli KarinaUniversity of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Other staff (1,00)EST / ENG01.01.2012−31.12.2012
Karl KaupmeesDoctor's DegreeEST / ENG01.11.2012−31.12.2012
Ivar KoppelDoctor's DegreeEST / ENG01.01.2010−31.12.2012
Agnes KüttDoctor's DegreeEST / ENG01.01.2010−31.12.2012
Lauri LippingDoctor's DegreeEST / ENG01.01.2010−31.08.2011
Märt LõkovMaster's DiplomaWorkplace missingEST / ENG01.01.2013−31.12.2012
Vilve NummertDoctor's DegreeEST / ENG01.01.2010−31.12.2012
Lilli PaamaDoctor's DegreeUniversity of Tartu, Faculty of Science and Technology (old), Dean's Office, Project Manager (1,00)EST / ENG01.01.2010−31.12.2012
Mare PiirsaluDoctor's DegreeEST / ENG01.01.2010−31.12.2012
Toomas RodimaDoctor's DegreeEST / ENG01.01.2010−31.12.2012
Anu TeearuDoctor's DegreeUniversity of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Chemist (0,25)EST / ENG01.01.2012−31.12.2012
Publications
Publications
Kütt, A.; Werner, F. ; Koppel, I.A. (2012). Pentakis(trifluoromethyl)benzenediazonium Cation,a Useful BuildingBblock. Book of abstracts: 20th International Symposium on Fluorine Chemistry; Kyoto,Japan; July 22-27,2012. Kyoto, 1A-12−1A-12.
Kütt, A.; Koppel, I.A. (2012). Pentakis-and Tetrakis(trifluoromethyl)cyclopentadiene andits Derivatives. Book of Abstracts: 20th International Symposium on Flluorine Chemistry 2012; Kyoto; July 22-27. 2012. Kyoto, P-71−P-71.
Kaljurand, Ivari; Leito, Ivo; Koppel, Ilmar A. (2012). Suitability of dual solid probe FT-ICR-MS system for gas-phase acidity and basicity measurements of low volatile compounds. 19th International Mass Spectrometry Conference Programme: 19th International Mass Spectrometry Conference; Kyoto; 15.09.-21.09.2012. 70.
Nummert, V.; Mäemets, V.; Piirsalu, M.; Koppel, I.A. (2012). 17O NMR studies of ortho-substituents in substituted phenyl tosylates. MAGNETIC RESONANCE IN CHEMISTRY, 50 (10), 696−704.DOI10.1002/mrc.3864.
Kunetskiy, R.A.;Polyakova, S.M.;Vavrik, J.;Cisarova, I.;Saame, J.;Nerut, E.R.;Koppel, I.;Koppel, I.A.;Kütt, A.;Leito, I.;Lyapkalo, I.M. (2012). A New Class of Organosuperbases,N-Alkyl-and N-Aryl-1,3-dialkyl-,4,5-dimethylimidazol-2-ylidene Amines:Synthesis,Structure,pKBH+ Measurements,and Properties. Chemistry - A European Journal, 18 (12), 3621−3630.10.1002/chem.201102249.
Kütt, Agnes; Werner, Franz; Kaljurand, Ivari; Leito, Ivo; Koppel, Ilmar (2013). Pentakis(trifluoromethyl)benzenediazonium Cation: A Useful Building Block for the Syntheis of Trifluoromethyl-Substituted Derivatives. ChemPlusChem, 78 (9), 932−936.10.1002/cplu.201300160.
Kaljurand, Ivari; Rodima, Toomas; Koppel, Ivar; Koppel, Ilmar A.; Saame, Jaan; Leito, Ivo; Kögel, Julius; Sundermeyer, Jörg (2013). Choosing superbases for extending the experimental gas-phase basicity scale. Book of Abstracts: 14th European Symposium on Organic Reactivity, Prague, Czech Republic, September 1-6, 2013. Praha, 37.
Raamat, E.; Kaupmees, K.; Ovsjannikov, G.; Trummal, A.; Kütt, A.; Saame, J.; Koppel, I.; Kaljurand, I.; Lipping, L. Rodima, T.; Pihl, V.; Koppel, I. A.; Leito, I. (2013). Acidities of strong neutral Brønsted acids in different media. Journal of Physical Organic Chemistry, 26 (2), 162−170.10.1002/poc.2946.
Abboud, J-L.; Koppel, I.A.; Koppel, I. (2013). Additivity of substituent effects on the acidity of alcohols. Journal of Physical Organic Chemistry, 26 (6), 467−472.10.1002/poc.3110.
Toomsalu, E; Koppel, I. A.; Burk, P. (2013). Critical Test of Some Computational Chemistry Methods for Prediction of Gas-Phase Acidities and Basicities. Journal of Chemical Theory and Computation, 9 (9), 3947−3958.dx.doi.org/10.1021/ct4003916.
Zhang, M.;Badal, M.;Koppel, I.A.;Mishima, M. (2013). Gas-Phase Acidities of alpha-and alpha,alpha-SO2CF3-Substituted Toluenes. Varying Resonance Demand in the Electron-Rich System. Bulletin of the Chemical Society of Japan, 86 (7), 813−820.10.1246/bcsj.20130052.
Nummert, V.; Piirsalu, M.; Koppel, I.A. (2013). Prediction of ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous acetonitrile. Central European Journal of Chemistry, 11 (12), 1964−1975.10.2478/s11532-013-0321-5.
Nummert, V.; Piirsalu, M.; Koppel, I.A. (2013). Prediction of ortho substituent effect in alkaline hydrolysis of substituted phenyl benzoates in aqueous acetonitrile. Journal of Physical Organic Chemistry, 26 (4), 352−359.10.1002/poc.3096.
Koppel, I.A.; Burk, P.; Kasemets, K.; Koppel, I. (2013). Relativistic Effects on Acidities and Basicities of Brönsted Acids and Bases Containing Gold. Physical Chemistry Chemical Physics, 15 (41), 17971−17975.10.1039/C3CP52435C.
Kaljurand, Ivari; Lilleorg, Roman; Murumaa, Algis; Mishima, Masaaki; Burk, Peeter; Koppel, Ivar; Koppel, Ilmar A.; Leito, Ivo (2013). The basicity of substituted N,N-dimethylanilines in solution and in the gas phase. Journal of Physical Organic Chemistry, 26 (2), 171−181.10.1002/poc.2956.
Kütt, A.;Koppel, I.A. (2013). Bis(pentakis(trifluoromethyl)phenyl)amine and its derivatives. P1.17−P1.17.
Nummert, V.; Mäemets, V.; Piirsalu, M.; Vahur, S.; Koppel, I.A. (2011). 17O NMR study of ortho and alkyl substituent effects in substituted phenyl and alkyl esters of benzoic acids. Collection of Czechoslovak Chemical Communications, 12 (76), 1737−1763.10.1135/cccc2011100.
Lipping, L.; Kütt, A.; Kaupmees, K.; Koppel, I.; Burk, P.; Leito, I.; Koppel, I. A. (2011). Acidity of Anilines: Calculations vs Experiment. Journal of Physical Chemistry A, 115, 10335−10344.10.1021/jp204064q.
Trummal, A.; Rummel, A.; Lippmaa, E.; Koppel, I.; Koppel, I.A. (2011). Calculations of pKa of Superacids in 1,2-Dichloroethane. Journal of Physical Chemistry A, 115, 6641−6645.
Kütt, A.; Rodima, T.; Saame, J.;Raamat, E.; Mäemets, V.; Kaljurand, I.; Koppel, I.A.; Garlyauskayte, R.Y.; Yagupolskii, Y.L.; Yagupolskii, L.M.; Bernhardt, E.; Willner, H.; Leito, I. (2011). Equilibrium acidities of superacids. Journal of Organic Chemistry, 76 (2), 391−395.10.1021/jo101409p.
Nummert, V.;Maemets, V.;Piirsalu, M.;Koppel, I.A. (2011). Influence of ortho substituentson 17O NMR chemical shifts in phenyl esters of substituted benzoic acids. Journal of Physical Organic Chemistry, 24 (7), 539−552.10.1002/poc.1784.
Karelson, M.;Koppel, I.A.;Leito, I.;Kaljurand, M.;Samel, N.;Lopp, M.;Pehk, T. (2011). Chemistry in Estonia-Review and Outlook. In: Engelbrecht, J. (Ed.). Research in Estonia. Present and Future (319−345).. Tallinn: Estonian Academy of Sciences.
Kütt, A.; Rodima, T.; Trummal, A.; Saame, J.; Kaljurand, I.; Koppel, I.A.; Yagupolskii, Y.I.; Leito, I. (2011). Acidities of Superacids in 1,2-Dichloroethane. Book of Abstracts ESOR XIII: The 13th European Symposium on Organic Reactivity,Tartu,Estonia,11-16 September,2011. Toim. Burk, Peeter. Tartu , P18−P18.
Lipping, L.; Kütt, A.; Kaupmees, K.; Koppel, I.; Koppel, I.A.; Leito, I. (2011). Aniliinide happelisused:Arvutused vs.Eksperiment. XXXII Eesti Keemiapäevad Teaduskonverentsi Teesid: XXXII Eesti Keemiapäevad Tartu 14-16 Aprill, 2011. Tartu: Tartu Ülikooli Kirjastus, 56−56.
Trummal, A.; Rummel, A.; Lippmaa, E.; Koppel, I.; Koppel, I.A. (2011). Calculation of pKa of Superacids in 1,2-Dichloroethane. Abstracts of Papers: Ninth triennial congress of the World Association of Theoretical and Computational Chemists(WATOC),Santiago de Compostela,Spain;July 17-22,2011. Spain,Santiago de Compostela, 094−094.
Leito, I.; Kütt, A.; Rodima, T.; Lipping, L.; Kaljurand, I.; Saame, J.; Koppel, I.; Koppel, I.A. (2011). Design and Acidity Measurements of Superacidic Molecules. Book of Abstracts ESOR XIII: The 13th European Symposium on Organic Reactivity,Tartu,Estonia,11-16 September,2011;invited lecture. IL3−IL3.
Nummert, V.; Piirsalu, M.; Mäemets, V.; Koppel, I.A. (2011). Orto-substituentide mõju asendatud fenüülbensoaatide 17O TMR keemilistele nihetele. XXXII Eesti Keemiapäevad Teaduskonverentsi Teesid: XXXII Eesti Keemiapäevad;Tartu; 14-16 Aprill,2011. Tartu: Tartu Ülikooli Kirjastus, 65−65.
Koppel, I.A.; Kütt, A.; Leito, I.; Koppel, I.; Rodima, T.; Kaljurand, I; Saame, J; Kolomeitsev, A.A. (2011). Superbasicity of Neutral Molecules-Quo Vadis Plenary lecture. Book of Abstracts ESOR: The 13th European Symposium on Organic Reactivity Tartu,Estonia,11-16 September 2011. Tartu, O19−O19.
Leito, I.; Kütt, A.; Rodima, T.; Lipping, L.; Kaljurand, I.; Saame, J.; Koppel, I.; Koppel, I.A. (2011). Superhappeliste Molekulide Disain ja Happelisuse Mõõtmine. XXXII Eesti Keemiapäevad Teaduskonverentsi Teesid: XXXII Eesti Keemiapäevad Tartu, 14-16 Aprill, 2011. Tartu : Tartu Ülikooli Kirjastus, 54−54.
Leito, I.; Koppel, I. A.; Burk, P.; Tamp, S.; Kutsar, M.; Mishima, M.; Abboud, J.-L. M.; Davalos, J. Z.; Herrero, R.; Notario, R. (2010). Gas-Phase Basicities Around and Below Water Revisited. Journal of Physical Chemistry A, 114 (39), 10694−10699.10.1021/jp104917a.
Nummert, V.; Piirsalu, M.; Koppel, I.A. (2010). Influence of solvent on the ortho substituent effect in the alkaline hydrolysis of phenyl esters of substituted benzoic acids. Journal of Physical Organic Chemistry, 23 (6), 497−504.10.1002/poc.1628.
Lipping, L.; Koppel, I.; Koppel, I. A.; Kolomeitsev, A.; Röschenthaler, G.-V.; Leito, I. (2010). Polytrifluoromethylation versus Polyfluorination of the Isomers of Kekule Benzene and Phenol: A Theoretical Study. Journal of Organic Chemistry, 75 (19), 6436−6444.10.1021/jo101061u.
Kütt, Agnes; Koppel, Ilmar. (2014). Pentakis(trifluoromethyl)phenol from Nitrobenzene. RSC Advances, 4, 41895−41901.dx.doi.org/10.1039/c4ra04540h.
Zhang, M.;Badal, M.;Koppel, I.A.;Mishima, M. (2013). Gas-Phase Acidities of alpha-and alpha,alpha-SO2CF3-Substituted Toluenes. Varying Resonance Demand in the Electron-Rich System. Bulletin of the Chemical Society of Japan, 86 (7), 813−820.
Toomsalu, E; Koppel, I. A.; Burk, P. (2013). Critical Test of Some Computational Chemistry Methods for Prediction of Gas-Phase Acidities and Basicities. Journal of Chemical Theory and Computation, 9 (9), 3947−3958.dx.doi.org/10.1021/ct4003916.
Trapp, N.; Scherer, H.; Hayes, S.A.; Berger, R.J. F.; Kütt, A.; Mitzel, N.W.; Saame, J.; Krossing, I. (2011). The perfluorinated alcohols (F5C6)(F3C)(2)COH and (F5C6)(F10C5)COH: synthesis, theoretical and acidity studies, spectroscopy and structures in the solid state and the gas phase. Physical Chemistry Chemical Physics, 13 (13), 6184−6191.10.1039/C0CP02596H.
Koppel, I.A. (2014). Limits of Growth in Chemistry of Superacids and Superbases. Conference of Centre of Excellence of High Technological Materials for Sustainable Development,Tartu,Feb.7,2014. Tartu,.
Kaljurand, I. (2014). Experimental FT-ICR Study of Gas-Phase Superbasicity. Conference of Centre of Excellence of High Technological Materials for Sustainable Development,Tartu,Feb.7,2014. Tartu,.
Supervision
Supervision
Lauri Lipping, Doctor's Degree, 2011, (sup) Ilmar Koppel; Ivar Koppel; Ivo Leito, The acidity of strong and superstrong Brönsted acids,an outreach for the "limits of growth":a quantum chemical study, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University.
Jaan Saame, Master's Degree, 2012, (sup) Ivo Leito; Agnes Kütt, Superaluselisuse skaalade laiendamine, kasutades uudseid orgaanilisi superaluseid (Expanding of Superbasicity Scales Using Novel Organic Superbases), University of Tartu.
Karl Kaupmees, Master's Degree, 2010, (sup) Ivari Kaljurand; Ivo Leito, Veesisalduse mõju happelisuse skaalale atsetonitriilis, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Chair of Analytical Chemistry.