title: Synthesis and characterization of a stable bismuth(III) A3-corrole.
abstract: An efficient metalation procedure for bismuth complexes with meso-substituted corrole ligands is presented. Reaction of 5,10,15-tris-pentafluorophenylcorrole H(3)(TpFPC) with Bi{N(SiMe(3))(3)} converts the free ligand H(3)(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 crystal structure of a bismuth corrole is presented and compared to the geometry-optimized molecular structure obtained with density functional theory (DFT) calculations. We show an example of a 4-coordinate metallocorrole with a very large out-of-plane displacement and significant doming. 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.
authors.affiliation: Institute of Inorganic Chemistry, Johannes Kepler University Linz (JKU), Altenberger Strasse 69, A-4040 Linz, Austria.
authors.forename: Lorenz Michael
authors.initials: LM
authors.lastname: Reith
authors.forename: Martin
authors.initials: M
authors.lastname: Stiftinger
authors.forename: Uwe
authors.initials: U
authors.lastname: Monkowius
authors.forename: Günther
authors.initials: G
authors.lastname: Knör
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Schoefberger
mesh_terms: D001729:Bismuth / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D011166:Porphyrins; C431863:corrole; D001729:Bismuth