טכניון מכון טכנולוגי לישראל
הטכניון מכון טכנולוגי לישראל - בית הספר ללימודי מוסמכים  
M.Sc Thesis
M.Sc StudentInna Luobeznov
SubjectMono and Binuclear Corroles
DepartmentDepartment of Chemistry
Supervisor Full Professor Gross Zeev


Abstract

     As part of the interest of our research group in the preparation and utilization of corrole metal complexes, we decided to  investigate the copper and ruthenium complexes of 5,10,15-tris(pentafluorophenyl)corrole. We found that insertion of copper proceeded well, but the corresponding complex was not stable in solution and converted within a few hours into a mixture of binuclear corrole dimers. Accordingly, we have prepared the copper complex of 5,10,15-tris(2,6-dichlorophenyl)corrole, anticipating that dimerization of this sterically protected corrole will be a less severe problem. Indeed, the much larger stability of this mononuclear complex  allowed for its characterization by X-ray crystallography. A binuclear complex of this corrole was also prepared, by performing the metal insertion into it at high temperature. A detailed spectroscopic investigation of the four new complexes allowed for elucidation of their structural features and electronic states.

    Because of the importance of ruthenium in many catalytic processes and in porphyrin chemistry, we searched  for a suitable metal source and appropriate reaction conditions for the preparation of mononuclear ruthenium corroles. Adopting a recently published procedure, allowed for the preparation of a new binuclear derivative  with a triple bond between the metals. Mononuclear ruthenium corroles  were obtained when NO(g) was introduced during synthesis. A comparison between the novel ruthenium nitrosyl complex with an earlier reported iron analog  by X-ray crystallography, electrochemistry and spectroscopy revealed that all are quite ideal {MNO}6 complexes. They are diamagnetic, their metal-NO units are linear, and they display rich electrochemistry.

    Within this thesis, four mononuclear metallocorroles and two types of binuclear complexes (with metal-metal and carbon-carbon bonds between the subunits) were prepared. All these new complexes were fully characterized by a combination of spectroscopic methods, electrochemistry, and X-ray crystallography.