Mõnede lämmastiku, fosfori ja süsiniku aluste aluselisus atsetonitriili keskkonnas

Väitekirja elektrooniline versioon ei sisalda publikatsiooneHappelisus ja aluselisus on keemiliste ühendite ühed olulisemad omadused. Hape-alus tasakaalud toimuvad suuremal või vähemal määral peaaegu kõigis keemilistes protsessides ja tihti mõjutavad nende käike oluliselt. Happelisuse ja aluselisuse uuringuid vesikeskkonnas on läbiviidud juba pikka aega ja hapete ning aluste käitumine selles on hästi teada. Paljud protsessid, kus ained käituvad hapete või alustena toimuvad mittevesikeskkondades. Sellistes keskkondades avaldub ainete happelisus või aluselisus oluliselt erinevalt. Mittevesikeskondade eeliseks on see, et neis saab läbi viia väga tugevate või nõrkade hapete ning aluste pKa uuringuid. Käesoleva doktoritöö eesmärgiks oli erinevate aineperekondade esindajate aluselisuse väärtused atsetonitriili keskkonnas. Nendeks aineperekondadeks olid triarüülfosfaanid, arüülhüdrasoonid, pentafulveenid ja lämmastikheterotsüklid. Atsetonitriil on solvent, mida kasutakse laialdaselt erinevates keemia valdkondades. Uuritud ainetest on lämmastikheterotsüklid, mis on kõige levinumad. Neid esineb looduses, ravimites, pestitsiidies ja nad leiavad rakendust ka paljudes muudes vadkondades. Kui võrrelda doktortöö raames määratud heterotsüklite pKa väärtusi atsetonitriili keskkonnas arvutatud gaasifaasi aluselisuse väärtustega ja kirjandusest leitud pKa väärtustega vees on võimalik teha järeldusi erinevate struktuuriefektide kohta, mis mõjutavad lämmastikeheterotsüklite aluselisust. Nendeks struktuurseteks tunnusteks on peri vesiniku olemasolu, sisemolekulaarne vesinikside, täiendavalt liidetud aromaatne tuum, lämmastike suhteline asukoht tsüklis ja tsükli suurus. Selle tulemusena leiti, et need efektid toimivad kõigis kolmes keskkonnas, aga erineval määral. Leiti, et pKa väärtused vees ja atsetonitriilis korrelleeruvad hästi lämmastikheterotsüklite puhul. Näidati, et arüülhüdrasoonide ja pentafulveenide pKa väärtused korrelleeruvad hästi Hammetti substituendi konstantidega. Töös esitatud korrelatsioonid ja struktuuri mõjutuste uuringut aluselisusele saab edaspidi kasutada sarnaste ühendite pKa väärtuste ennustamiseks.The acidity and basicity are among the most important properties of chemical compounds. The acid-base equilibria take place at least to some extent in almost all chemical processes and often decisively influences the course of these processes. Acidity and basicity studies in water has a long history and the behaviour of acids and bases in this medium is well known. Many processes where compounds behave as acids or bases take place in non-aqueous media. In non-aqueous media molecules display acidity and basicity often quite differently. The benefit of non-aqueous solvents in the acid-base equilibria studies is that very strong or weak acids and bases and water sensitive compounds can be studied. The aim of this thesis was to determine the basicities of members of different compound families – triarylphosphanes, arylhydrazones, pentafulvenes and nitrogen heterocycles - in acetonitrile. A solvent that is widely used in many different fields of chemistry. Of the studied compounds nitrogen heterocycles are the most widespread figuring in nature, medicine, pesticides and finding use in many other fields. The determined pKa values in acetonitrile combined with computed gas phase basicities and pKa values in water from literature made it possible to rationalize structure effects influencing the basicity of these compounds. These structural features were the presence of the peri hydrogen, intramolecular hydrogen bond, fusion of additional benzene ring, relative position of nitrogen atoms in the ring and the ring size. It was found that these effects are present in all studied media but to a different extent. It was shown that the pKa values of nitrogen heterocycles correlate well in water and acetonitrile. The pKa values of substituted penatafulvenes and arylhydrazones correlate well with the Hammett substituent parameters. The obtained correlations, as well as rationalization of structure-basicity relationships can be used for pKa estimations of similar compounds

Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds

Hypervalent bromine(III) reagents possess a higher electrophilicity and a stronger oxidizing power compared to their iodine(III) counterparts. Despite the superior reactivity, bromine(III) reagents have a reputation of hard‐to‐control and difficult‐to‐synthesize compounds. This is partly due to their low stability, and partly because their synthesis typically relies on the use of the toxic and highly reactive BrF3 as a precursor. Recently, we proposed chelation‐stabilized hypervalent bromine(III) compounds as a possible solution to both problems. First, they can be conveniently prepared by electro‐oxidation of the corresponding bromoarenes. Second, the chelation endows bromine(III) species with increased stability while retaining sufficient reactivity, comparable to that of iodine(III) counterparts. Finally, their intrinsic reactivity can be unlocked in the presence of acids. Herein, an in‐depth mechanistic study of both the electrochemical generation and the reactivity of the bromine(III) compounds is disclosed, with implications for known applications and future developments in the field.Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659European Regional Development Fund http://dx.doi.org/10.13039/501100008530HORIZON EUROPE European Research Council http://dx.doi.org/10.13039/100019180Estonian Research Competency Council http://dx.doi.org/10.13039/501100005189Peer Reviewe

Tris(benzophenoneimino)phosphane and related compounds

The dataset includes files supporting the article named "Tris(benzophenoneimino)phosphane and related compounds". Monocrystal XRD data, calculated .cosmo files, calculated pKaH values for related and correlation compounds, gas-phase geometry optimization and frequency calculation files, and NMR files are given

Accurate Method To Quantify Binding in Supramolecular Chemistry

An approach for accurate and comparable measurement of host–guest binding affinities is introduced whereby differences in binding strength (?logKass values) are measured between two host molecules toward a particular guest under identical solvent conditions. Measuring differences instead of absolute values enables obtaining highly accurate results, because many of the uncertainty sources (the solvation/association state of the guest in solution, deviations in solvent composition, etc.) cancel out. As a proof of concept, this method was applied to the measurement of the binding strength of 28 synthetic anion receptors toward acetate in acetonitrile containing 0.5% water. The receptors included differently substituted indolocarbazoles, ureas, thioureas, and some others. Possible deprotonation of more acidic receptors of each compound class by acetate was checked by measuring their acidities (?pKa values) relative to acetic acid in the same solvent. A self-consistent (consistency standard deviation 0.04 log units) binding affinity scale ranging for around 2.7 log units was constructed from the results. Absolute logKass values were found by anchoring the scale to the absolute logKass values of two receptor molecules, determined independently by direct measurements. This new approach is expected to find use in accurate quantification of a wide range of binding processes relevant to supramolecular chemistry

Acid-base and anion binding properties of tetrafluorinated 1,3-benzodiazole, 1,2,3-benzotriazole and 2,1,3-benzoselenadiazole

The influence of fluorination on the acid-base properties and the capacity of structurally related 6-5 bicyclic compounds – 1,3-benzodiazole 1, 1,2,3-benzotriazole 2 and 2,1,3-benzoselenadiazole 3 to σ-hole interactions, i.e. hydrogen (1 and 2) and chalcogen (3) bondings, is studied experimentally and computationally. The tetrafluorination increases Brønsted acidity of diazole and triazole scaffolds and Lewis acidity of selenadiazole scaffold and decreases basicity. Increased Brønsted acidity facilitates anion binding via the formation of hydrogen bonds; particularly, tetrafluorinated derivative of 1 (compound 4) binds Cl–. Increased Lewis acidity of tetrafluorinated derivative of 3 (compound 10), however, is not enough for binding with Cl– and F– via the formation of chalcogen bonds in contrast to previously studied Te analog of 10. It is suggested that the maximum positive values of molecular electrostatic potential at the σ-holes, VS,max, can be reasonable metrics in the further design and synthesis of new anion receptors, with selenadiazole–diazole / triazole hybrids as a special target. Related chlorinated compounds are also discussed. Introduction Design and synthesis of new anion receptors functioning via various σ-hole interactions,[1] e.g. hydrogen and chalcogen bondings (Brønsted and Lewis acidity, respectively), attract much current attention, particularly due to potential biomedical, technological and environmental applications.[2-4] Effective tool in the field is polyfluorination, for (hetero) aromatics affecting many properties significant for chemistry, materials science and biomedicine, including a capacity to σ-hole interactions.[1,5-9] Structurally-related, 1,2-diaminobenzene-derived, 1,3- benzodiazole (benzimidazole) 1, 1,2,3-benzotriazole 2, and 2,1,3-benzoselenadiazole 3, already having numerous applications in current chemistry, materials science and biomedicine,[7,10] are appropriate targets for studying effects of polyfluorination on Brønsted (1 and 2) and Lewis (3) acidity and anion-binding properties (Scheme 1)