Synthesis, structure, and catalytic activity of chiral Cu(II) and Ag(I) complexes with ( S, S)-1,2-diaminocyclohexane-based N 4-donor ligands

Abstract

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 NaBH 4 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 CuCl 2 · 2H 2O in methanol gives complexes [ N-(pyridin-2-ylmethylene)-( S, S)-1,2-cyclohexanediamine]CuCl 2 ( 3) and [Cu( S, S- 2)(H 2O)]Cl 2 · H 2O ( 4), respectively, in good yields. Complex 4 can further react with 1 equiv. of CuCl 2 · 2H 2O in methanol to give [Cu( S, S- 2)][CuCl 4] ( 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 AgNO 3 induces a polymer helicate {[Ag( S, S- 1)][NO 3]} n ( 6), while reaction of ligand 2 with AgPF 6 or AgNO 3 in methanol affords a mononuclear single helicate [Ag( S, S- 2)][PF 6] ( 7) or a dinuclear double helicate [Ag 2( S, S- 2) 2][NO 3] 2 · 2CH 3OH ( 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.