"Estonian Science Foundation Research Grant" project ETF7374
ETF7374 "Superacidity and Superbasicity Scales in different Media (1.01.2008−31.12.2011)", Ivo Leito, University of Tartu, Faculty of Physics and Chemistry, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, University of Tartu, Faculty of Science and Technology (old).
ETF7374
Superhappelisuse ja superaluselisuse skaalad erinevates keskkondades
Superacidity and Superbasicity Scales in different Media
1.01.2008
31.12.2011
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
InstitutionRolePeriod
University of Tartu, Faculty of Physics and Chemistrycoordinaator01.01.2008−31.12.2011
University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu Universitycoordinaator01.01.2008−31.12.2011
University of Tartu, Faculty of Science and Technology (old)coordinaator01.01.2008−31.12.2011
PeriodSum
01.01.2008−31.12.2008260 400,00 EEK (16 642,59 EUR)
01.01.2009−31.12.2009249 984,00 EEK (15 976,89 EUR)
01.01.2010−31.12.2010227 112,00 EEK (14 515,10 EUR)
01.01.2011−31.12.201114 515,20 EUR
61 649,78 EUR
87948,82

Ülitugevad happed ja alused – superhapped ja superalused – ning nende derivaadid pälvivad üha kasvavat tähelepanu nii praktilisest kui ka teoreetilisest vaatepunktist. Superhapete ja superaluste uurimise eluliselt oluline osa on nende tugevuse mõõtmine. Käesoleva projekti raames luuakse selliste mõõtmiste jaoks usaldusväärsed tööriistad - superhappelisuse ja superaluselisuse skaalad erinevates keskkondades. Superhapped: superhappelisuse skaala ulatusega ca 10 suurusjärku luuakse 1,2-dikloroetaani keskkonnas. Loodav skaala seotakse meie poolt varem loodud keskmise tugevusega happelisuse skaalaga atsetonitriili keskkonnas, kasutades happeid, mille pKa väärtused on samaaegselt mõlemal skaalal. Sellisel moel on võimalik saada pKa väärtuste hinnangud atsetonitriilis hapetele, mis on liiga tugevad selleks, et neid vahetult atsetonitriilis mõõta, ja on võimalik olemasolevat atsetonitriili happelisuse skaalat pikendada superhappelisse piirkonda. Olemasolev gaasifaasiline happelisuse skaala saab tugevate hapete piirkonnas (alla 300 kcal/mol) verifitseeritud ja pikendatud superhappelisse piirkonda. Plaanis on luua ka täiesti uus keskkond superhapete uurimiseks, millel on kõrge polaarsus, kuid samal ajal väga madal aluselisus. Selle solvendi molekuli ehitus hakkab baseeruma sulfolaani skeletil, mille polaarsust tõstetakse ja aluselisust alandatakse) fluoro- ja CF3 rühmadega. Superalused: Tetrahüdrofuraani aluselisuse skaalat laiendadatakse lisades uusi aluseid erinevatest perekondadest. Sellisel moel saadud superaluselisuse andmetest tetrahüdrofuraani keskkonnas ennustatakse vastavate aluste aluselisused atsetonitriili keskkonnas neile alustele, mis on liiga tugevad, et neid atsetonitriilis vahetult mõõta. Gaasifaasilist aluselisuse skaalat laiendatakse kuni P4 fosfaseenide aluselisuse tasemeni (280-300 kcal/mol). Happelisuse ja aluselisuse andmed (pKa väärtused lahustes ja DeltaGacid ning GB väärtused gaasifaasis) mõõdetakse võimalikult paljudele erinevate superhapete ja superaluste perekondade esindajatele.
Acids and bases of very high strength – superacids and superbases – and their derivatives are receiving increasing attention from both practical and theoretical points of view. Measurements of acidity and basicity are a vital part of studies of superacids and superbases. Reliable tools – scales of superacidity and superbasicity in different media – will be created. Superacids: superacidity scale in 1,2-dichloroethane (DCE) spanning for ca ten orders of magnitude will be set up. The DCE acidity scale will be linked to our existing MeCN acidity scale via acids that are present on both scales. This way estimates of MeCN pKa values of the superacids, which cannot be directly measured in MeCN, can be obtained and the current MeCN acidity scale can be extended into the superacidic region. The gas-phase superacidity scale will be verified and extended in the region of superacidity (region below 300 kcal/mol). New solvent will be designed for studies of superstrong acids, based on sulfolane skeleton with inclusion of several –F and/or –CF3 substituents. Superbases: superbasicity scale in THF will be extended adding bases from different families of superbases. Based on the THF superbasicity scale pKa values of superbases that cannot be directly measured in acetonitrile will be calculated. The current gas-phase superbasicity scale will be extended up to the basicity level of P4 phosphazenes (280-300 kcal/mol). Acidity-basicity data (pKa values in solvents and DeltaGacid as well as GB values in the gas phase) will be measured for as many as possible representatives of different families of strong and superstrong acids and bases.

Principal investigator (1)

PersonDegreeInstitution and occupationCVPeriod
Ivo LeitoDoctor's DegreeUniversity of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University, Professor of Analytical Chemistry (1,00)EST / ENG01.01.2008−31.12.2010

Senior research staff (22)

PersonDegreeInstitution and occupationCVPeriod
Anna-Maria AasEST / ENG01.01.2011−31.12.2011
Tõiv HaljasorgEST / ENG01.09.2010−31.12.2011
Lauri JalukseDoctor's DegreeEST / ENG01.01.2008−31.12.2010
Sandip Ashokrao KadamDoctor's DegreeDoktorantEST / ENG01.09.2011−31.12.2011
Karl KaupmeesDoctor's DegreeEST / ENG07.09.2008−31.12.2011
Karin KipperDoctor's DegreekeemikEST / ENG14.03.2008−31.12.2009
Kristo KleemannMaster's DiplomaEST / ENG01.09.2011−31.12.2011
Ivar KoppelDoctor's DegreeErakorraline vanemteadurEST / ENG01.01.2008−31.12.2011
Anneli Kruve-ViilDoctor's DegreeEST / ENG01.01.2008−28.04.2008
Agnes KüttDoctor's DegreeEST / ENG01.01.2008−31.12.2009
Asko LaanisteDoctor's DegreeüliõpilaneEST / ENG01.01.2011−31.12.2011
Kerli LaukEST / ENG01.01.2009−31.12.2010
Lauri LippingDoctor's DegreeEST / ENG01.01.2008−31.12.2011
Meelis MetusMagistrantEST / ENG01.01.2009−31.12.2010
Merit OssMaster's DiplomadoktorantEST / ENG01.01.2008−31.12.2011
Gea OvsjannikovMagistrantEST / ENG01.01.2008−31.12.2010
Viljar PihlDoctor's DegreeEST / ENG01.01.2008−31.12.2010
Elin RaamatMaster's DiplomaDoktorantEST / ENG01.01.2008−31.12.2010
Jaan SaameMaster's DiplomaMagistrantEST / ENG01.01.2009−31.12.2011
Gert SuurkuuskMaster's DiplomaEST / ENG01.09.2009−31.12.2010
Anu TeearuDoctor's DegreeMagistrantEST / ENG01.01.2008−30.06.2009
Signe VahurDoctor's Degreekeemik EST / ENG01.01.2009−31.12.2009
Publications
Publications
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.
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.
Himmel, D.; Goll, S. K.; Leito, I.; Krossing, I. (2011). Anchor Points for the Unified Bronsted Acidity Scale: The rCCC Model for the Calculation of Standard Gibbs Energies of Proton Solvation in Eleven Representative Liquid Media. Chemistry - A European Journal, 17 (21), 5808−5826.10.1002/chem.201003164.
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.
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.
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.
Himmel, D.; Goll, S. K.; Leito, I.; Krossing, I. (2010). A unified pH scale for all phases. Angewandte Chemie-International Edition, 49, 6885−6888.
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.
Kaupmees, K.; Kaljurand, I.; Leito, I. (2010). Influence of water content on the acidities in acetonitrile. Quantifying charge delocalization in anions. Journal of Physical Chemistry A, 11788−11793.10.1021/jp105670t.
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, 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.
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.
Eckert, F.; Leito, I.; Kaljurand, I.; Kütt, A.; Klamt, A.; Diedenhofen, M. (2009). Prediction of acidity in acetonitrile solution with COSMO-RS. Journal of Computational Chemistry, 30 (5), 799−810.dx.doi.org/10.1002/jcc.21103.
Leito, Ivo; Raamat, Elin; Kütt, Agnes; Saame, Jaan; Kipper, Karin; Koppel, Ilmar A.; Koppel, Ivar; Zhang, Min; Mishima, Masaaki; Yagupolskii, Lev M.; Garlyauskayte, Romute Yu.; Filatov, Andrey A. (2009). Revision of the Gas-Phase Acidity Scale below 300 kcal mol-1. Journal of Physical Chemistry A, 113 (29), 8421−8424.10.1021/jp903780k.
Coles, M. P.; Aragón-Sáez, P. J.; Oakley, S. H.; Hitchcock, P. B.; Davidson, M. G.; Maksić, Z. B.; Vianello, R.; Leito, I.; Kaljurand, I.; Apperley, D. C. (2009). Superbasicity of a Bis-guanidino compound with a flexible linker: A theoretical and experimental study. Journal of the American Chemical Society, 131 (46), 16858−16868.10.1021/ja906618g.
Kütt, A.;Rodima, T.;Leito, I.;Koppel, I.A. (2009). Acidities of Superacids in 1,2-Dichloroethane. Book of Abstracts: 19th International Symposium on Fluorine Chemistry; Jackson Hole, Wyoming, USA; August 23-28, 2009.
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.
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.
Haav, Kristjan; Saame, Jaan; Kütt, Agnes; Leito, Ivo (2012). Basicity of Phosphanes and Diphosphanes in Acetonitrile. European Journal of Organic Chemistry, 000−000.10.1002/ejoc.201200009.
Strukil, Vjekoslav; Dilovic, Ivika; Matkovic-Calogovic, Dubravka; Saame, Jaan; Leito, Ivo; Sket, Primoz; Pavlec, Janez; Eckert-Maksic, Mirjana (2012). Molecular structure and acid/base properties of 1,2-dihydro-1,3,5-triazine derivatives. New Journal of Chemistry, 36 (1), 86−96.10.1039/c1nj20595a.
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.
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.
Elin Raamat, Master's Degree, 2009, (sup) Ivo Leito; Agnes Kütt, Aromatic sulfonimides - a forgotten family of compounds, University of Tartu, Faculty of Science and Technology (old), Institute of Chemistry, Tartu University.
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.