טכניון מכון טכנולוגי לישראל
הטכניון מכון טכנולוגי לישראל - בית הספר ללימודי מוסמכים  
Ph.D Thesis
Ph.D StudentSimkhovich Liliya
SubjectSynthesis, Characterization, and Catalytic Applications
of Novel Porphyrins and Corroles and Their Metal
Complexes
DepartmentDepartment of Chemistry
Supervisor Professor Zeev Gross


Abstract

          The research of core-modified porphyrins is receiving increased attention in recent years. Among the derivatives that form complexes with transition metals, corroles are the most interesting. Corroles act as aromatic (18 p-electron system) tetradentate trianionic ligands toward metal ions, and stabilize peculiarly high oxidation states. Despite the fact that corroles share many common properties with porphyrins, corrole’s research is much less developed because of problems in their synthesis. Most probably, that is the only reason that the potential of corroles in catalysis or any other application was never explored.

          We have explored a new facile synthesis of corrole from commercially available precursors, pyrrole and aldehyde.  These expectations were fulfilled with electron-poor aldehydes. Thus, we succeeded in preparation and full characterization of the following novel corroles: 5,10,15-tris(pentafluorophenyl)corrole - H3(tpfc); 5,10,15-tris(2,6-dichlorophenyl) corrole - H3(tdclc); and 5,10,15-tris(heptafluoropropyl)corrole - H3(thfpc) - the first meso-alkylated corrole.

          We have developed different methodologies for metal insertion into corroles and interconversion of the various complexes, and have fully characterized many new metallocorroles (spectroscopy and X-ray crystallography).

          The first utilization of corrole metal complexes in catalysis - hydroxylation of alkanes, epoxidation, cyclopropanation, and aziridination of olefins - was demonstrated in our work. In addition, we have designed and succeeded in preparation of a new type of chiral ligands with potential in asymmetric catalysis  - N-alkylated corroles.