Tetratellura[36]octaphyrin(1.1.1.1.1.1.1.1) Metalation: From Dynamic Behavior to Rigid Chiral Figure-of-Eight Molecule; Activation of the C–Te Bond by Ruthenium

Abstract

The large expanded telluraporphyrin, tetratellura [36]octaphyrin(1.1.1.1.1.1.1.1), was synthesized in 7% yield by acid-catalyzed condensation of pyrrole with 2,5bis(phenylhydroxymethyl)tellurophene and subsequent oxidation. The macrocycle acquires the chiral figure-eight conformation with two alternative spatial arrangements of the heterocyclic rings. The molecule exhibits dynamic behavior in solution, which was studied by means of 1 H NMR spectroscopy. The reaction with chlorine led to a reversible oxidative addition at two distant tellurium atoms, which altered the preferred conformations. Metalation of the tetratellura [36]octaphyrin with triruthenium dodecacarbonyl selectively activated two of the eight Te−C bonds, resulting in the formation of an organometallic diruthenium compound. During the reaction, two tellurophene rings were converted to 1-ruthena-2-telluracyclohexadiene units containing octahedral ruthenium(II) centers. The rigid structure of this chiral complex allowed the separation of enantiomers.