Mono-and dinuclear complexes of a new binucleating porphyrin, α,α-5, 15-bis(o-(nicotinoylamino)phenyl)-2, 8, 12, 18-tetraethyl-3, 7, 13, 17-tetramethylporphyrin. Crystal structures of a mononuclear nickel(II) complex and a binuclear copper-platinum complex

Abstract

The synthesis and characterization of a new binucleating porphyrin ligand, α,α-5, 15-bis(o-(nicotinoylamido)phenyl)-2, 8, 12, 18-tetraethyl-3, 7, 13, 17-tetramethylporphyrin, [H2(DPE)]-(py)2 is reported. Treatment of [H2(DPE)]-(py)2 with methanol solutions of Ni(II) or Cu(II) leads to the formation of mononuclear metal complexes, [M(DPE)]-(py)2, in which the metal has inserted into the porphyrin core, leaving the pyridine binding site free. Addition of a second metal to form a binuclear complex, [M(DPE)]-(py)2MʹCl2, can be accomplished using the reagent Mʹ(DMSO)2Cl2, Mʹ= Pd, Pt, and Zn. [Ni(DPE)]-(py)2 and [Cu(DPE)]-(py)2PtCl2 have been characterized by single-crystal X-ray analysis. Crystal data for [Ni(DPE)]-(py)2: NiO2Ns- C56H52-2CHC13, triclinic, P1, a = 14.306 (4) Å,b = 14.719 (5) Å,c= 14.296 (5) Å, α = 94.86 (3)°, β = 96.38 (3)°, γ = 63.45 (2)°, Z-2, R = 0.049, and Rv = 0.064. Crystal data for [Cu(DPE)]-(py)2PtCl2: CuPt02N8C56H52, triclinic, P1, a = 19.333 (1) Å, b = 23.74 (1) Å, c = 12.984 (5) Å,α= 103.28 (4)°, β = 108.29 (3)°, γ = 76.47 (3)°, Z = 4, R = 0.073, and Rw = 0.085. Pt-Pt distances between the two molecules in the asymmetric unit are 3.766 (3) Å. © 1992, American Chemical Society. All rights reserved.