Binuclear Palladium(I) and Palladium(II) Complexes of ortho-Functionalized 13-Bis(aryl)triazenido Ligands

摘要

Three new bis(aryl)triazene ligands, Ar-NNNH-Ar′ [Ar=Ar′=o-C6H4-CO2Me (>2); Ar=o-C6H4-CO2Me, Ar′=p-C6H4-CH3 (>3); Ar=o-C6H4-SMe, Ar′=p-C6H4-CH3) (>4)], have been synthesized. Reaction of >1–4 with PdCl2(NCCH3)₂ in the presence of a base afforded a series of binuclear diamagnetic palladium complexes. In these reactions, ligands >1–3 afforded the palladium(I) complexes [Pd^I(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), [Pd^I(o-MeO-C₆H₄-NNN-o-C₆H₄-OMe)]₂ (>6, triclinic, space group P$\bar{1}$. 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 [Pd^I(o-MeO₂C-C₆H₄-NNN-p-C₆H₄-CH₃)]₂ (>7, tetragonal, space group I 41/a, a=20.866(3) Å, b=20.866(3) Å, c=13.156(2) Å, Z=8). In contrast, reaction of ligand >4 with PdCl₂(NCCH₃)₂ resulted in the formation of a palladium(II) dimer, [Pd^II(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).