Oxidation and Reduction of Cerium(IV) Sandwich Complexes with Porphyrin Ligands Linked by Aliphatic Diether Bridges of Variable Chain Length

✍ Scribed by Johann W. Buchler; Torsten Dippell

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 408 KB
• Volume: 1998
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199804)1998:4<445::aid-ejic445>3.0.co;2-d

✦ Synopsis

IV) bisporphyrinates / Sandwich complexes / Diporphyrins / π Radical-cations and dications / Cerium(III) bisporphyrinate anions Starting from 5-(4-hydroxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin (2a), the new bis(porphyrinyloxy)alkanes 4a and 4d were synthesized by ether formation with the α,ωdibromoalkanes Br(CH 2 ) n Br (n = 8, 11; 3a, 3d). 4a was obtained by a two-step reaction with the 5-[4-(8-bromooctyloxy)phenyl]-10,15,20-tris(4-methylphenyl)porphyrin (2b) as an intermediate. The diporphyrins 4a and 4d were metalated with cerium(III) acetylacetonate to yield the new (porphyrin)cerium sandwich complexes 1a and 1d which were characterized by UV/Vis, IR, 1 H-NMR, 13 C-NMR spectroscopy and