"Estonian Science Foundation Research Grant" project ETF6701
ETF6701 "The design and Study of Acidity and Basicity of Novel Neutral Superacids and Superbases (1.01.2006−31.12.2009)", Ilmar Koppel, University of Tartu, University of Tartu, Faculty of Physics and Chemistry, University of Tartu, Faculty of Science and Technology (old).
ETF6701
Uute neutraalsete superhapete ja superaluste disain ja happelisuse ning aluselisuse uurimine
The design and Study of Acidity and Basicity of Novel Neutral Superacids and Superbases
1.01.2006
31.12.2009
Estonian Science Foundation Research Grant
Field of researchSubfieldCERCS specialtyFrascati Manual specialtyPercent
4. Natural Sciences and Engineering4.11. Chemistry and Chemical Technology 1.3. Chemical sciences (chemistry, other allied subjects)100,0
InstitutionRolePeriod
University of Tartucoordinaator01.01.2006−31.12.2007
University of Tartu, Faculty of Physics and Chemistrycoordinaator01.01.2006−31.12.2007
University of Tartu, Faculty of Science and Technology (old)coordinaator01.01.2008−31.12.2009
PeriodSum
01.01.2006−31.12.2006252 000,00 EEK (16 105,74 EUR)
01.01.2007−31.12.2007252 000,00 EEK (16 105,74 EUR)
01.01.2008−31.12.2008252 000,00 EEK (16 105,74 EUR)
01.01.2009−31.12.2009241 920,00 EEK (15 461,51 EUR)
63 778,73 EUR
0,00

Käesoleva grandiprojekti peaülesanneteks on tugevate ja ülitugevate hapete ja aluste komputeriseeritud disaini printsiipide üldistamine ja edasiarendamine ning nende elektronstruktuuri ja termodünaamiliste ning katalüütiliste omaduste solvendi iseloomust ning omadustest sõltuvuse eksperimentaal-teoreetiline uurimine.Uusi ülitugevaid substituente sisaldavate superhapete arvutuslik gaasifaasiline happelisus peaks ületama tunduvalt traditsiooniliste mineraalhapete vastava näitaja.Samas võib oodata,et mõnede karboraanide derivaatide konjugeeritud hapete absoluutne happelisus võib ületada H2SO4 vastava näitaja kuni 80 suurusjärgu võrra. Samal ajal võib prognoosida,et fosfaseenidel,fosfori üliididel,karbeenidel,jne.baseeruvate superaluste aluselisus on võrreldav tugevaimate anorgaaniliste aluste omaga.Eeltoodust tulenevalt uuritakse ka spontaanse gaasifaasilise prootoni üleminekureaktsiooni võimalikkust ülitugeva happe ja aluse interaktsioonis. Solvendiefektide mõju uurimiseks püstitatakse ja laiendatakse tugevate hapete ja aluste tugevuse skaalasid gaasifaasis,CH3CN,THF,heptaanis ja ioonsetes vedelikes.Saadud tulemusi modelleeritakse lähtudes teoreetilistest mudelitest. Uued ülitugevad happed ja alused ja nende derivaadid võivad omada potentsiaalselt olulisi tehnoloogilisi rakendusi modernsete jõuallikate disainis,stereoselektiivsete katalüsaatoritena orgaanilises sünteesis ja naftakeemiatööstuses.
The major goals of the present proposal are the generalization and development of the principles of the design of superstrong Brönsted acids and bases and the study of their electronic structure,thermodynamic and catalytic properties and dependence on the nature of the solvents.The predicted intrinsic acidity of superacids containing new superstrong electron-acceptor substituents is expected to exceed by far the same quantity for the traditional mineral acids.Some conjugate acids of derivatives of carboranes are predicted to exceed the intrinsic acidity of H2SO4 by ca 80 powers of ten.At the same time,the expected basicity of several organic superbases(phosphazenes,phosphorus ylides,carbenes,etc.)should be comparable to that of strongest inorganic bases. The feasibility of the spontaneous proton transfer between neutral superbase and -acid in the gas phase is expected to be the case.For the study of the solvent effects the acidity and basicity scales of strong bases and acids in the gas phase,THF,MeCN,heptane, and some ionic liquids will be established.Their theoretical modelling will be undertaken.The new superstrong acids and bases and their derivatives areexpected to have important technological implications(materials for power sources,catalysts,etc.)

Principal investigator (1)

PersonDegreeInstitution and occupationCVPeriod
Ilmar KoppelDoctor's DegreeEST / ENG01.01.2006−31.12.2009

Senior research staff (11)

PersonDegreeInstitution and occupationCVPeriod
Koit HerodesDoctor's Degreeanalüütilise keemia dotsentEST / ENG01.01.2006−31.12.2006
Ivar KoppelDoctor's DegreeEST / ENG01.01.2006−31.12.2009
Agnes KüttDoctor's DegreeEST / ENG01.01.2006−31.12.2009
Lauri LippingDoctor's DegreeEST / ENG01.01.2007−31.12.2009
Vilve NummertDoctor's DegreeUniversity of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Research Fellow extraordinarius (1,00)EST / ENG01.01.2007−31.12.2009
Gea OvsjannikovUniversity of Tartu, Faculty of Science and Technology (old), Other staff (1,00)EST / ENG01.01.2009−31.12.2009
Lilli PaamaDoctor's DegreeprojektijuhtEST / ENG01.01.2006−31.12.2009
Viljar PihlDoctor's DegreeEST / ENG01.01.2006−31.12.2009
Mare PiirsaluDoctor's DegreeUniversity of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Research Fellow (1,00)EST / ENG01.01.2006−31.12.2009
Toomas RodimaDoctor's DegreeUniversity of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Research Fellow (1,00)EST / ENG01.01.2006−31.12.2009
Lilli SooväliDoctor's DegreeUniversity of Tartu, Faculty of Physics and Chemistry, Institute of Chemical Physics, Chair of Analytical Chemistry, erakorraline teadur (1,00)EST / ENG01.01.2006−31.12.2006
Publications
Publications
Kütt, A.; Koppel, I.; Koppel, I. A.; Leito, I. (2009). Boratabenzene Anions C5B(CN)6- and C5B(CF3)6- and the Superacidic Properties of their Conjugate Acids. ChemPhysChem, 10 (3), 499−502.10.1002/cphc.200800305.
Nummert, V.; Piirsalu, M.; Mäemets, V.; Vahur, S.; Koppel, I. (2009). Effect of ortho substituents on carbonyl carbon C-13 NMR chemical shifts in substituted phenyl benzoates. Journal of Physical Organic Chemistry, 22 (12), 1155−1165.10.1002/poc.1569.
Lipping, L.; Leito, I.; Koppel, I.; Koppel, I.A. (2009). Gas-Phase Brønsted Superacidity of Some Derivatives of Monocarba-closo-Borates: a Computational Study. Journal of Physical Chemistry A, 113 (46), 12972−12978.10.1021/jp905449k.
Guerrero, A.; Herrero, R.; Davalos, J.Z.; Koppel, I.; Abboud, J.-L.M.; Chana, A.; Koppel, I.A. (2009). Hydrogen-Bonding Interactions of (CF3)3CH and (CF3)3C-in the Gas Phase. An experimental (FT-ICR) and Computational Study. Journal of Physical Chemistry A, 113 (23), 6422−6429.
Trummal, A.; Rummel, A.; Lippmaa, E.; Burk, P.; Koppel, I.A. (2009). IEF-PCM Calculations of Absolute pKa for Substituted Phenols in Dimethyl Sulfoxide and Acetonitrile Solution. Journal of Physical Chemistry A, 113 (21), 6206−6212.
Nummert, V.; Piirsalu, M.; Vahur, S.; Travnikova, O.; Koppel, I. A. (2009). Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr. Collection of Czechoslovak Chemical Communications, 74 (1), 29−42.10.1135/cccc2008019.
Leito, I.; Raamat, E.; Kütt, A.; Saame, J.; Kipper, K.; Koppel, I.A.; Koppel, I.; Zhang, M.; Mishima, M.; Yagupolskii, L.M.; Garlyauskayte, R.Y.; Filatov, A.A. (2009). Revision of Gas-Phase Acidity Scale below 300 kcal/mol. Journal of Physical Chemistry A, 113 (29), 8421−8424.
Burk, P.; Leito, I.; Koppel, I.A.; Mishima, M.; Abboud, J.-L. (2009). Gas-phase basicities around and below water -Revisited. Book of Abstracts, 2009: 12th Kyushu International Symposium on Physical Organic Chemistry; Fukuoka, Japan; 15.-18.12.2009. Fukuoka, L08−L08.
Abboud, J.-L.; Fukaya, H.; Koppel, I.A.; Mishima, M.; Ono, T.; Pasikowska, M.; Siehl, H.-U.; Sonoda, T.; Zhang, M. (2009). On the gas-phase and solution acidity of oxygen and carbon-acids with perfluorinated tertiary-carbon units. Book of Abstracts: 12th Kyushu International Symposium on Physical Organic Chemistry; Fukuoka, Japan; 15.-18.12.2009. Fukuoka, P49−P49.
Burk, P.; Koppel, I.A. (2009). Relativistic Effects on Intrinsic Acidities and Basicities of some Neutral Brönsted Acids and Bases. Book of Abstracts: 13th International Conference of Quantum Chemistry; Helsinki; June 23-27, 2009. Helsinki, 362.
Leito, I.;Raamat, E.;Kütt, A.;Saame, J.;Kipper, K.;Koppel, I.A.;Koppel, I.;Zhang, M.;Mishima, M. (2009). Revision of the Gas-Phase Acidity of Strong Acids. Book of Abstracts: 19th International Symposium on Fluorine Chemistry,Jackson Hole,Wyoming,USA,August 23-28,2009.
Lipping, L.;Leito, I.;Koppel, I.;Koppel, I.A. (2009). The gas-phase Superacidity of Derivatives of MonocarbaCloco-Borates:a Computational Study. Book of Abstracts: 19th International Symposium on Fluorine Chemistry,Jackson Hole,Wyoming,USA,August 23-28,2009.
Lipping, L.; Leito, I.; Koppel, I.; Koppel, I.A. (2009). The Quest for the Strongest Neutral Brönsted Acid:a DFT and G3(MP2) Study. Book of Abstracts: The 12th KISPOC Symposium; Fukuoka, Japan; December 15-18 2009. Fukuoka,Japan, 29−29.
Eckert-Maksić, M.; Glasovac, Z.; Trošelj, P.; Kütt, A.; Rodima, T.; Koppel, I.; Koppel, I. A. (2008). Basicity of Guanidines with Heteroalkyl Side Chains in Acetonitrile. European Journal of Organic Chemistry, 30, 5176−5184.10.1002/ejoc.200800673.
Burk, P.; Koppel, I.; Trummal, A.; Koppel, I.A. (2008). Feasibility of Spontaneous Gas-phase Proton Transfer Between Neutral Brönsted Acida and Bases. Journal of Physical Organic Chemistry, 21, 571−574.10.1002/poc.1322.
Kütt, A.; Movchun, V.; Rodima, T.; Dansauer, T.; Rusanov, E.B.; Leito, I.; Kaljurand, I.; Koppel, J.; Pihl, V.; Koppel, I; Ovsjannikov, G.; Toom, L.; Mishima, M.; Medebielle, M.; Lork, E.; Röschenthaler, G.-V.; Koppel, I.A.; Kolomeitsev, A.A. (2008). Pentakis(trifluoromethyl)phenyl, a Sterically Crowded and Electron-withdrawing Group: Synthesis and Acidity of Pentakis(trifluoromethyl)benzene, -toluene, -phenol, and aniline. Journal of Organic Chemistry, 73 (7), 2607−2620.
Leito, I.; Kütt, A.; Rõõm, E.-I.; Koppel, I. (2007). Anions N[C(CN)2]3– and P[C(CN)2]3– and the Superacidic Properties of their Conjugate Acids. Journal of Molecular Structure: THEOCHEM, 815, 41−43.10.1016/j.theochem.2007.03.017.
Rõõm, E.-I.; Kütt, A.; Kaljurand, I.; Koppel, I.; Leito, I.; Koppel, I.A.; Mishima, M.; Goto, K.; Miyahara, Y. (2007). Bronsted Basicities of Diamines in the Gas Phase,Acetonitrile,and Tetrahydrofuran. Chemistry - A European Journal, 13 (27), 7631−7643.10.1002/chem.200700097.
Kaljurand, I.; Koppel, I.A.; Kütt, A.; Rõõm, E.-I.; Rodima, T.; Koppel, I.; Mishima, M.; Leito, I. (2007). Experimental Gas-Phase Basicity scale of Superbasic Phosphazenes. Journal of Physical Chemistry A, 111 (7), 1245−1250.
Herrero, R.; Davalos, J.Z.; Abboud, J.-L.M., Alkorta, I.; Koppel, I.; Koppel, I.A.; Sonoda, T.; Mishima, M. (2007). The intrinsic(gas-phase)acidities of bridgehead alcohols.An experimental(FT-ICR) and computational study. International Journal of Mass Spectrometry, 267, 302−307.
Nummert, V.;Piirsalu, M.;Koppel, I.A. (2007). Variation of the temperature-depenent substituent effects with solvent in alkaline hydrolysis of substituted phenyl and alkyl benzoates and phenyl tosylates. Journal of Physical Organic Chemistry, 20, 778−790.
Leito, I.; Kütt, A.; Kaljurand, I.; Rõõm, E.-I.; Rodima, T.; Koppel, I.A. (2007). Brönsted Acidity of Neutral and Cationic Acids in Nonaqueous Solvents:Recent Developments. Abstracts of Papers: The 233rd American Chemical Society Nartional Meeting; Chicago, IL; USA; March 25-29, 2007. Chicago,IL, INOR1036−INOR1036.
Burk, P.; Koppel, I.A.; Koppel, I.; Trummal, A. (2007). Feasibility of the Spontaneous Gas-Phase Proton Transfer equilibria Between Neutral Brönsted Acids and Bases. Abstracts of Papers: The 233rd American Chemical Society National Meeting; Chicago, IL, USA: March 25-29, 2007. INOR1037−INOR1037.
Koppel, I.A.; Leito, I.; Koppel, I.; Lipping, L.; Trummal, A.; Burk, P. (2007). Superacidity and Superbasicity of Neutral Brönsted Acids and Bases: The Limits of Growth. Abstracts of Papers: 233rd American Chemical Society National Meeting; Chicago, IL, USA; March 25-29, 2007. INOR571−INOR571.
Burk, P.;Koppel, I.;Trummal, A.;Koppel, I.A. (2007). Feasibility of the spontaneous proton transfer equilibria between neutral Brönsted acids and bases. Abstracts of Scientific Conference: 30th Estonian Chemistry Days,Tartu,November 16-17,2007. Ed. Rinken, A. Tartu: Tartu Ülikooli Kirjastus, 18−19.
Koppel, I.A.;Leito, I.;Koppel, I.;Lipping, L.;Trummal, A.;Burk, P. (2007). Superacidity and superbasicity of neutral Brönsted acids and bases:the principles of design and the limits of growth. Abstracts of Scientific Conference: 30th Estonian Chemistry Days,Tartu,November 16-17,2007. Ed. A.Rinken. Tartu Ülikooli Kirjastus, 56−57.
Burk, P.; Koppel, I.A.;Leito, I.;Tämm, K. (2007). The limits of growth for superacidity and superbasicity of neutral Bronsted acids and bases. Book of Abstracts ESOR XI: XI European Symposium on Organic Reactivity,Faro,Portugal,July 1st-6th,2007. 109.
Kütt, A.; Leito, I.; Kaljurand, I.; Sooväli, L.; Vlasov, V.M.; Yagupolskii, L.M.; Koppel, I.A. (2006). A Comprehensive Self-Consistent Spectrophotometric Acidity Scale of Neutral Bronsted Acids in Acetonitrile. Journal of Organic Chemistry, 71 (7), 2829−2838.
Sooväli, L.; Rodima, T.; Kaljurand, I.; Kütt, A.; Koppel, I.A.; Leito, I. (2006). Basicity of some P1 phosphazenes in water and in aqueous surfactant solution. Organic and Biomolecular Chemistry, 4 (11), 2100−2105.
Nummert, V.; Travnikova, O.; Vahur, S.; Leito, I.; Piirsalu, M.; Mäemets, V.; Koppel, I.; Koppel, I.A. (2006). Influence of Substituents on the Infrared Stretching Frequencies of Carbonyl Group in Esters of Benzoic Acid. Journal of Physical Organic Chemistry, 19 (10), 654−663.10.1002/poc.1112.
Nummert, V.; Piirsalu, M.; Maemets, V.; Koppel, I. (2006). Kinetic study of hydrolysis of benzoates. Part XXV. Ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in water. Collection of Czechoslovak Chemical Communications, 71 (1), 107−128.
Nummert , V.; Piirsalu , M.; Koppel , I.A. (2006). Kinetic study of hydrolysis of benzoates. Part XXVI. Variation of the substituent effect with solvent in alkaline hydrolysis of substituted alkyl benzoates. Collection of Czechoslovak Chemical Communications, 71, 1557−1570.
Lipping, Lauri; Koppel, Ilmar; Koppel, Ivar; Leito, Ivo (2006). Some weakly coordinating anions based on carboranes. Proceedings of the Estonian Academy of Sciences. Chemistry, 55 (3), 145−154.
Burk, P.; Koppel, I.; Leito, I. (2006). Hape-alus reaktsioonide uurimine Tartu Ülikoolis. Koppel, I.; Saari, P. (Toim.). Teadusmõte Eestis. Täppisteadused (159−168).. Tallinn: Estonian Academy of Sciences.
Tulp, I.; Tämm, K.; Burk, P.; Trummal, A.; Koppel, I.A.; Karelson, M.; Maran, U. (2006). The quantum chemical modeling of solvent effect in the QSPR analysis of pKa of phenols in the H2O and DMSO. The 12th International Workshop on Quantitative Structure-Activity Relationships in Environmental Toxicology; 2006; France.
Kütt, Agnes (2009). Studies of Acid-Base Equilibria in non-Aqueous Media: The Complete Study. VDM Verlag Dr. Müller Aktiengesellschaft & Co. KG.
Supervision
Supervision
Lauri Lipping, Master's Degree, 2006, (sup) Ilmar Koppel; Ivo Leito; Ivar Koppel, Karboraanidel baseeruvad superhapped ja nõrgalt koordineeruvad anioonid (Some superacids and weakly coordinating anions based on carboranes), Tartu Ülikool, Füüsika-keemiateaduskond.
Lilli Sooväli, Doctor's Degree, 2006, (sup) Ilmar Koppel; Ivo Leito, Spectrophotometric measurements and their uncertainty in chemical analysis and dissociation constant measurements (Spectrophotometric measurements and their uncertainty in chemical analysis and dissociation constant measurements), University of Tartu, Faculty of Physics and Chemistry.
Eva-Ingrid Rõõm, Doctor's Degree, 2007, (sup) Ilmar Koppel; Ivo Leito; Ivari Kaljurand, Acid-Base Equilibria in Nonpolar Media, University of Tartu, Faculty of Physics and Chemistry.
Agnes Kütt, Doctor's Degree, 2008, (sup) Ivo Leito; Ilmar Koppel; Ivari Kaljurand, Studies of Acid-Base Equilibria in non-Aqueous Media, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University.
Aleksander Trummal, Doctor's Degree, 2009, (sup) Ilmar Koppel; Peeter Burk; Endel Lippmaa, Computational Study of Structural and Solvent Effects on Acidities of Some Brönsted Acids, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University.