ic700516p_si_008.cif (11.5 kB)

Binuclear Palladium(I) and Palladium(II) Complexes of ortho-Functionalized 1,3-Bis(aryl)triazenido Ligands

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posted on 23.07.2007, 00:00 by Juan José Nuricumbo-Escobar, Carlos Campos-Alvarado, Gustavo Ríos-Moreno, David Morales-Morales, Patrick J. Walsh, Miguel Parra-Hake
Three new bis(aryl)triazene ligands, Ar-NNNH-Ar‘ [Ar = o-C6H4-CO2Me, Ar‘ = p-C6H4-CH3 (2); Ar = Ar‘ = o-C6H4-CO2Me (3); Ar = o-C6H4-SMe, Ar‘ = p-C6H4-CH3) (4)], have been synthesized. The reaction of 14 with PdCl2(NCCH3)2 in the presence of a base afforded a series of binuclear diamagnetic palladium complexes. In these reactions, ligands 13 afforded the palladium(I) complexes [PdI(o-MeO2C-C6H4-NNN-o-C6H4-CO2Me)]2 (5, monoclinic, space group P21/c, a = 8.6070(10) Å, b = 14.3220(10) Å, c = 12.7310(10) Å, β = 100.2950(10)°, Z = 2), [PdI(o-MeO-C6H4-NNN-o-C6H4-OMe)]2 (6, triclinic, space group P1̄, a = 6.6288(5) Å, b = 10.2631(10) Å, c = 11.0246(11) Å, α = 85.579(6)°, β = 80.885(6)°, γ = 74.607(6)°, Z = 1), and [PdI(o-MeO2C-C6H4-NNN-p-C6H4-CH3)]2 (7, tetragonal, space group I41/a, a = 20.866(3) Å, b = 20.866(3) Å, c = 13.156(2) Å, Z = 8). In contrast, the reaction of ligand 4 with PdCl2(NCCH3)2 resulted in the formation of a palladium(II) dimer, [PdII(o-MeS-C6H4-NNN-p-C6H4-CH3)Cl]2 (8, orthorhombic, space group P21212, a = 10.4058(5) Å, b = 16.2488(8) Å, c = 9.9500(5) Å, Z = 2).

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