Synthesis, Electrochemical Behavior, and Catalytic Activity of Cobalt Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids.

A one-pot synthesis of cobalt(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrins (CoTADAPs) from the corresponding 5-aryl-1-arylamino-9-chlorodipyrrins and cobalt(II) acetate is reported. The CoTADAPs exhibited characteristic electrochemical behavior and catalyzed the intramolecular cyclization of N-benzyl-N-Boc-3-diazopropan-1-amines, probably via σ-CoIII-alkyl radical intermediates.

Synthesis, Optical Properties, and Electrochemical Behavior of 5,10,15,20-Tetraaryl-5,15-diazaporphyrin-Amine Hybrids.

This work reports a series of covalently linked hybrids comprising 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (M-TADAP; M = Ni, Zn, Cu) and amines. M-TADAP-amine hybrids were prepared via the metal-templated cyclization of the corresponding metal(II)-dipyrrin complexes and redox reactions on the DAP unit. In the UV/vis/near-IR absorption spectra of the hybrids containing an 18π-electron DAP ring, broad charge-transfer bands were observed, reflecting the electron-donating property of the para-aminophenyl groups and the electron-accepting property of the 18π TADAP dication. The electrochemical behavior of the M-TADAP-amine hybrids was strongly dependent on the structure of the peripheral amine units. Further electrochemical oxidation of the hybrids bearing N-Ph groups conceivably generated amine-centered radicals, which sequentially underwent irreversible coupling to form benzidine-linked M-TADAP polymer films. The Ni-TADAP-benzidine polymer exhibited the electric conductivity of 1×10-3  S m-1 .