Synthesis and Coordination Chemistry of Unsymmetrical Tetraazaporphyrins Containing Single Oxathia- and Thiacrown Substituents

• Published in: Tetrahedron Vol. 56; no. 38; pp. 7371 - 7377
• Main Authors: Lange, Steven J., Sibert, John W., Barrett, Anthony G.M., Hoffman, Brian M.
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 15.09.2000; Elsevier
• Subjects: Chemistry; Chemistry, Organic; maleonitrile; oxathia ether; Physical Sciences; porphyrazine; Science & Technology; tetraazaporphyrin; thiacrown ether; porphyrazine; oxathia ether; maleonitrile; tetraazaporphyrin; thiacrown ether; THIOETHER CHEMISTRY; CRYSTAL-STRUCTURE; SPECTROSCOPIC PROPERTIES; TETRAAZA MACROCYCLES; X-RAY STRUCTURES; PHTHALOCYANINE ANALOGS; SOLITAIRE-PORPHYRAZINES; COPPER PHTHALOCYANINE; CROWN-ETHER VOIDS; METAL-COMPLEXES
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/S0040-4020(00)00615-3

Singly crowned porphyrazines containing oxathia- and thiacrown ethers were prepared from a mixed condensation of 1,2-dicyanobenzene or its 3,4-dibutyl analog and the appropriate crowned maleonitrile precursor. Peripheral metal-binding to each porphyrazine was examined spectrophotometrically. The oxathiaether-crowned porphyrazines were found to coordinate Ag(I) and HgCl 2, though all complexes suffered from poor solubility and complexes with the latter were unstable in polar media. With an interest in the formation of comparatively more stable and soluble heavy and transition metal complexes, two new sets of thiaether-crowned porphyrazines were examined. In these cases, coordination of Hg(II), Ag(I), Cu(I) and Cu(II) was observed with no evidence for complexation of Tl(I), Pb(II) or CdCl 2.