1. A molecule mechanical force field with precise reproducing capability was created based on the crystal structure database of [(alkoxycarbonyl)methyl]cobalt tricarbonyl tertphosphine compounds.
1.1. By statistically analyzing inner coordinates of numerous, 25 molecule structures, the initial parameter set of molecule mechanic force field was produced. High values were chosen for initial force constants, which were decreased to achieve the maximal elasticity of the parameter set.
1.2. Optimizing parameters was carried out in 31 steps, in the end the average error between calculated and X-ray structures were below 0.01 Å and below 1º for bind distance and angle, respectively.
1.3. After optimizing the modified MM2, force field was improved by 22 new parameters:
2 atom type, 4 bind distance-, 10 bind angle- and 6 torsion parameters.
1.4. The initial molecules were optimized geometrically with the improved force field. It was stated the average errors of calculations and the values of standard deviations were negligible. The force field reproduces precisely the complexes that have to be studied.
2. The clockwork mechanism taking place during the transformation of enantiomer pairs into each other, developed by myself, was modelled using improved MM2 parameter set and was confirmed, and it was improved by the 2:1 type mechanism of tertphosphane ligand inversion.
2.1. Two-dimensional, net method conformation analysis was made through the example of ethylester derivative. The controlled torsion angles were rotated by each 1 º among the values found in the equilibrium geometry of enantiomers. Thus, in the investigation 14414 structures were obtained, and their energies were represented in an energy surface diagram.
2.2. The route of transformation between enantiomers was determined. Structures in the trajectory were analyzed, and the clockwork mechanism taking place during the transformation of enantiomer pairs into each other was confirmed.
2.3. It was certified that reP → siP és a reP → reM epimerization was impeded by the substantial energy barrier originated from the encounter of phenyl rings.
2.4. It was determined during the transformation of complexes, inversion of triphenylphosphane occurred in a ratio of 2:1 similar to the free triphenylphosphane.
3. It was identified a well determined part of known compounds did not follow the clockwork mechanism, but they inverted according to the ordinary gear attached rotation mechanism.
3.1. It was established that the studied complexes can be easily divided into two main groups [(reP, siM) or (siP, reM)] due to their crystal-phase configuration.
3.2. It was observed groups (ester group, CO and triphenylphosphane ligand), building complexes with siP és reM configurations in the crystal cell, always rotate in opposite direction similar to the ordinary gear.
4. The only compound of the existing X-ray structures was investigated in which all of the four possible chiral conformers (reP, reM, siP, siM) can be equally found, and the potential reason for the existence of structures was verified by molecule mechanic calculations
4.1. Two-dimensional conformation analysis was used to establish stereoselectivity could not be shown in benzylester derivative.
4.2. It was stated that at complex formation only one of the enantiomer pairs (reP és siM vagy reM és siP) forms, but the conformers transform easily into each other (reP↔reM és siM↔siP) because of the low energy barrier of ‘phenyl inversion’.
Thermodynamical control prevails.
5. The possibility of selective formation of [(alkoxycarbonyl)methyl]cobalt tricarbonyl triphenylphosphane type complexes was explained through the example of ethylester by calculating chemistry.
5.1. Calculating the reaction route geometrical and energy data were received about intermediers not isolated so far in laboratory (cis-acyl and cis-alkyl complexes, C and F complex), which data could make the preparative work of researchers easier.
5.2. It was also established that two complexes formed at the end of the reaction instead of statistically possible four ones. These complexes are images of each other. The two complexes formed are reP és a siM, these configurations can be found in the crystal cell of investigated complex.
8 Köszönetnyilvánítás
Mindenekelőtt hálás köszönettel tartozom témavezetőmnek Dr. Bencze Lajosnak, aki az elmúlt évek alatt mindvégig támogatott, segített és értékes szakmai tanácsokkal látott el.
Örülök, hogy megismerhettem feleségét Judith nénit, akinek itt is köszönöm azt a rengeteg gyümölcsöt, süteményt, amiket nagy örömmel fogyasztottunk el férjével együtt az estébe nyúló szakmai és baráti beszélgetések alkalmával.
Köszönettel tartozom a Pannon Egyetem Szerves Kémia Intézeti Tanszéken dolgozó összes kollégának, hogy minden segítséget megadtak a dolgozatom elkészítéséhez. A teljesség igénye nélkül köszönöm tehát: Dr. Bakos József, Dr. Tőrös Szilárd, Dr. Ungváry Ferenc, Dr.
Kégl Tamás, Tóth Gergely, Horváth Anita, Kuik Árpád és Balogh János szakmai és emberi segítségét.
Természetesen hálás köszönettel tartozom szüleimnek, akikre mindenben számíthattam.
Köszönöm, hogy ragaszkodtattok ahhoz, hogy mindig felszálljak a buszra …
Utoljára, de nem utolsó sorban feleségemnek, Nórának és kislányomnak, Pannának adnék hálát, hogy a megerőltető munka után, otthon mindig szeretet, türelem és béke várt.
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