Arylhydrazone ligands as Cu-protectors and -catalysis promoters in the azide–alkyne cycloaddition reaction

Abstract

A series of water soluble copper(II) complexes, [Cu(κO¹O²N-H₂L¹)(H₂O)₂]·2H₂O (2), [Cu(κO-H₃L¹)₂(H₂O)₄] (3), [Cu(κO-H₄L²)₂(H₂O)₄] (5) and [Cu(H₂O)₆]·2H₂L³·2(CH₃)₂NCHO (7), were prepared by the reaction of Cu(NO₃)₂·3H₂O with sodium (Z)-2-(2-(1-amino-1,3-dioxobutan-2-ylidene)hydrazineyl)benzenesulfonate, [Na(μ₄-1:2κO¹,2κO²,3κO³,4κO⁴-H₃L¹)]_n (1; for 2 and 3), sodium (Z)-3-(2-(1-amino-1,3-dioxobutan-2-ylidene)hydrazineyl)-4-hydroxybenzene-sulfonate, [Na(μ-1κO¹,2κO²-H₄L²)]₂ (4; for 5) or sodium (Z)-2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazineyl)naphthalene-1-sulfonate, [Na(μ-1κO¹O²,2κO³-H₂L³)(CH₃OH)₂]₂ (6; for 7). Compounds 1–7 were fully characterized, also by single-crystal X-ray diffraction analysis, and applied as homogeneous catalysts for the azide–alkyne cycloaddition (AAC) reaction to afford 1,4-disubstituted 1,2,3-triazoles. A structure–catalytic activity relationship has been recognized for the first time on the basis of the occurrence of resonance- and charge-assisted hydrogen bond interactions (RAHB and CAHB), in charge and ligand binding modes, enabling the catalytic activity of the compounds to be ordered as follows: Cu(NO₃)₂ ≪ 7 (complex salt with RAHB and CAHB) < 3 (with RAHB and CAHB) < 5 (with RAHB) < 2 (neither RAHB nor CAHB). Complex 2, without such non-covalent interactions, was found to be the most efficient catalyst for the AAC reaction, affording up to 98% product yield after being placed for 15 min, at 125 °C, in a water/acetonitrile mixture under low power (10 W) MW irradiation.