Synthesis and Characterization of a stable Bismuth(III) A3-Corrole
Sprache des Titels:
Englisch
Original Kurzfassung:
An efficient metallation procedure for bismuth complexes with meso-substituted corrole ligands is presented. Reaction of 5,10,15-tris-pentafluorophenylcorrole H3(TpFPC) with Bi{N(SiMe3)3} converts the free ligand H3(TpFPC) to a neutral low-valent species Bi(TpFPC), which has been characterized by different spectroscopic techniques. (Spectro-) electrochemical studies were performed in order to describe the redox potentials of the Bi(TpFPC) complex and to ascribe the sites of electron transfer.
The first X-ray-crystal structure of a bismuth corrole is presented and compared to geometry optimized molecular structures obtained with density functional theory (DFT) calculations and the electronic structure of the novel bismuth corrole system is discussed in detail. Time-dependent DFT results support the proposed assignment of electronic transitions observed for the Bi(TpFPC) derivative. To account for the reactivity we investigated the photocatalytic properties of the Bi(TpFPC) complex and defined the global and the local reactivity descriptors from conceptual DFT calculations.