Synthesis and Electrochemistry of Aluminum Porphycenes. Crystal and Molecular Structure of Methyl-σ-Bonded Aluminum Etioporphycene

✍ Scribed by Roger Guilard; Virginie Pichon-Pesme; Hassane Lachekar; Claude Lecomte; Ally M. Aukauloo; Pierre L. Boulas; Karl M. Kadish

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 229 KB
• Volume: 01
• Category: Article
• ISSN: 1088-4246
• DOI: 10.1002/(sici)1099-1409(199704)1:2<109::aid-jpp13>3.0.co;2-4

✦ Synopsis

The synthesis and characterization of three monomeric aluminum porphycenes with anionic or σ-bonded axial ligands is reported. The investigated compounds are represented as (EtioPc)Al(CH 3 ) and (EtioPc)AlX where EtioPc represents the dianion of etioporphycene and X = Cl -or OH -. Each synthesized complex was characterized by mass spectrometry, 1 H NMR, IR and UV-visible spectroscopies as well as by electrochemistry. Comparisons are made between the properties of complexes in the aluminum etioporphycene series and related chloro-or methyl σ-bonded Al(III) porphyrins containing octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP) macrocycles. Comparisons are also made between the currently investigated compounds and a previously reported Al(III) µ-oxo dimer, [(EtioPc)Al] 2 O. In addition, the crystal and molecular structure of (EtioPc)Al(CH 3 ) was determined by X-ray diffraction. The molecular structure of this methyl-σ-bonded aluminum etioporphycene provides the first structural data for an aluminum porphycene compound. The aluminum(III) atom in (EtioPc)Al(CH 3 ) is pentacoordinated and is located 0.54 Å from the plane of the four N-nitrogens.