International audienceThe synthesis of several new bismuth porphyrin complexes Bi(por)(X) containing the tpp or tpClpp (tpClpp = 5,10,15,20-tetra-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
A new coordination mode for the porphyrin ligand is found in [B O (BCl ) (tpClpp)] (tpClpp=dianion of 5,10,15,20-tetra-p-chlorophenylporphyrin; the p-chlorophenyl groups are omitted for clarity in the picture shown on the right). This complex contains a four-membered B O ring in the cavity of the ligand. The two boron atoms are coplanar with the porphyrin molecule, which undergoes an elongation along the B⋅⋅⋅B axis to accomodate the unusual guest.
Altes Porphyrin – neuer Inhalt: Zu den Nichtmetall‐haltigen Porphyrinen gehört ab jetzt auch der Porphyrinkomplex [B2O2(BCl3)2 (tpClpp)] (tpClpp = Dianion von Tetra‐para‐chlorphenylporphyrin; die Substituenten sind im Bild rechts der Übersichtlichkeit halber weggelassen), der einen B2O2‐Ring enthält. Die beiden Borzentren liegen in der Ebene des Porphyrinmoleküls, das entlang der B⋅⋅⋅B‐Achse gedehnt ist, damit der ungewöhnliche Gast hineinpaßt.
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