Synthesis, structure, and catalytic activity of chiral Cu(II) and Ag(I) complexes with (S,S)-1,2-diaminocyclohexane-based N4-donor ligands

Condensation of (S,S)-1,2-cyclohexanediamine with 2 equiv. of 2-pyridine carboxaldehyde in toluene in the presence of molecular sieves at 70 °C gives N,N′-bis(pyridin-2-ylmethylene)-(S,S)-1,2-cyclohexanediamine (S,S-1) in 95% yield. Reduction of 1 with an excess of NaBH4 in MeOH at 50 °C gives N,N′-bis(pyridin-2-ylmethyl)-(S,S)-1,2-cyclohexanediamine (S,S-2) in 90% yield. Reaction of 1 or 2 with 1 equiv. of CuCl2 · 2H2O in methanol gives complexes [N-(pyridin-2-ylmethylene)-(S,S)-1,2-cyclohexanediamine]CuCl2 (3) and [Cu(S,S-2)(H2O)]Cl2 · H2O (4), respectively, in good yields. Complex 4 can further react with 1 equiv. of CuCl2 · 2H2O in methanol to give [Cu(S,S-2)][CuCl4] (5) in 75% yield. The rigidity of the ligand coupled with the steric effect of the free anion plays an important role in the formation of the helicates. Treatment of ligand S,S-1 with AgNO3 induces a polymer helicate {[Ag(S,S-1)][NO3]}n (6), while reaction of ligand 2 with AgPF6 or AgNO3 in methanol affords a mononuclear single helicate [Ag(S,S-2)][PF6] (7) or a dinuclear double helicate [Ag2(S,S-2)2][NO3]2 · 2CH3OH (8) in good yields, respectively. All compounds have been characterized by various spectroscopic data and elemental analyses. Compounds 1, 3–5, 7 and 8 have been further subjected to single-crystal X-ray diffraction analyses. The Cu(II) complexes do not show catalytic activity for allylation reaction, in contrast to Ag(I) complexes, but they do show catalytic activity for Henry reaction (nitroaldol reaction) that Ag(I) complexes do not.

Graphical abstractA series of chiral Cu(II) and Ag(I) complexes have been prepared. The Cu(II) complexes do not show catalytic activity for allylation reaction, in contrast to Ag(I) complexes, but they do show catalytic activity for Henry reaction (nitroaldol reaction) that Ag(I) complexes do not.Figure optionsDownload full-size imageDownload as PowerPoint slide