Bismuth porphyrin complexes: syntheses and structural studies

Abstract

The synthesis of several new bismuth porphyrin complexes Bi(por)(X) containing the tpp or tpClpp (tpClpp = 5,10,15,20-tetra-p-chlorophenylporphyrin) porphyrin ligand and anions X = NO₃, Cl, Br, I are described. Molecular structures reported for Bi(tpClpp)(X) for X = Cl, Br show that the complexes crystallise as centrosymmetric dimers doubly bridged through Cl or Br. Bi(tpClpp)(NO₃) crystallises as a less symmetric dimer in which one NO₃ ligand bridges the two bismuth centres and the second NO₃ ligand interacts with only one bismuth atom. In all three structures the bismuth atoms are significantly displaced from the porphyrin N₄ planes and the Bi–halide or Bi–O distances are very long.