Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd2I2(µ-PPh2py)2 and a dimethylacetylenedicarboxylate A-frame complex Pd2Cl2(µ-Ppy3)2(µ-MeO2C•C=C•CO2Me); py = 2-pyridyl

Abstract

Dibromo- and diiodo[(2-pyridyl)phosphine]palladium(II) complexes are prepared by metathesis of cis-PdCl2(PPh3−npyn)2 species (n = 1–3) using the appropriate sodium halide; py = 2-pyridyl. NMR spectroscopy, particularly,13C{1H}, is used to distinguish cis and trans isomers. The dinuclear complexes Pd2X2(μ-PPh3−npyn)2, X = halide, are synthesized via a conproportionation reaction using PdX2(PPh3−npyn)2 and Pd2(dba)3; dba = dibenzylideneacetone. Both Pd2l2(μ-PPh2py)2 and a dimethylacetylenedicarboxylate A-frame complex Pd2Cl2(μ-Ppy3)2(μ-MeO2C•C=C•CO2Me) are characterized crystallographically as head-to-tail isomers. The former crystallizes in the monoclinic space group C2/c with a = 30.992(3), b = 18.764(1), c = 13.100(1) Å, β = 100.676(5)°, and Z = 8; the data were refined to R = 0.035 for 5874 reflections with I ≥ 3σ(I). The A-frame compound is triclinic of space group [Formula: see text] with a = 13.545(2), b = 15.064(2), c = 11.991(2) Å, α = 111.56(1), β = 95.36(1), γ = 97.63(1)°, and Z = 2; R = 0.033 from 7128 reflections with I ≥ 3σ(I). The Pd2X2(μ-PPhpy2)2 complexes exist as a mixture of diastereomers because of chirality induced at the phosphorus atoms. The Pd2X2(μ-Ppy3)2 complexes in water generate the [Pd2(H2O)2(μ-Ppy3)2]2+ dication, which is isolated as various salts. The mononuclear complexes in water generate aquo and hydroxo species. Keywords: dimethylacetylenedicarboxylate adducts, palladium complexes (dinuclear), pyridylphosphines.