Steven J. Lange

Synthesis and coordination chemistry of unsymmetrical tetraazaporphyrins containing single oxathia- and thiacrown substituents

Abstract 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 .

Macrocyclic dithiomaleonitrile derivatives containing sulfur and nitrogen heteroatoms

Abstract A general synthetic method for incorporation of the dithiomaleonitrile unit into macrocycles containing sulfur, oxygen, and nitrogen heteroatoms is presented along with the single-crystal X-ray structures of the thiacrowns. In addition to being new ligands, these macrocycles are direct precursors to peripherally crown functionalized porphyrazines capable of coordinating multiple metal ions.

Unusual coordination of HgCl2 by a mixed oxathioether crown

The oxathioether crown 1,4,7,10-tetraoxa-13,16-dithiacyclooctadec-14-en-14,15-dicarbonitrile reacts with HgCl2 to give an endocyclic complex in which macrocylic coordination to HgII in the solid state is through only the O donor atoms.