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Synthesis, characterization and electrochemistry of bismuth porphyrins. X-ray crystal structure of (OEP)Bi(SO3CF3)

✍ Scribed by Lydie Michaudet; Dominique Fasseur; Roger Guilard; Zhongping Ou; Karl M. Kadish; Slimane Dahaoui; Claude Lecomte

Publisher: John Wiley and Sons
Year: 2000
Tongue: English
Weight: 122 KB
Volume: 04
Category: Article
ISSN: 1088-4246
DOI: 10.1002/(sici)1099-1409(200004/05)4:3<261::aid-jpp203>3.0.co;2-b

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✦ Synopsis

The metalation of several free base porphyrins by the bismuth salts Bi(NO~3~)~3~ and Bi(SO~3~CF~3~)~3~ in DMF or pyridine is described. The resulting stable Bi(III) porphyrin complexes are characterized by electrochemistry, ^1^H NMR and UV-vis spectroscopy. The structure of ( OEP ) Bi ( SO ~3~ CF ~3~) was also determined by single-crystal X-ray diffraction and shows that ( OEP ) Bi ( SO ~3~ CF ~3~) exists as a dimer which is stabilized by electrostatic interactions in which the two [(OEP)Bi]^+^ cations are linked via oxygen atoms of two symmetrically related [Formula: see text] anions, leading to a heptacoordinated bismuth center. Electrochemical oxidation of ( OEP ) Bi ( SO ~3~ CF ~3~) and ( T p TP ) Bi ( SO~3~CF~3~ ) shows that only the porphyrin macrocycles are oxidized.

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