Green carbon–carbon homocoupling of terminal alkynes by a silica supported Cu(ii)-hydrazone coordination compound

Abstract

A Cu(II) complex, [Cu(HL)(NO₃)(CH₃OH)]·CH₃OH (1), was obtained by the reaction of Cu(NO₃)₂·3H₂O and H₂L in methanol solvent (H₂L is (E)-4-amino-N′-(2-hydroxy-3-methoxybenzylidene)benzohydrazide). H₂L and compound 1 were characterized by various spectroscopic analyses and the molecular structure of [Cu(HL)(NO₃)(CH₃OH)]·CH₃OH was determined by single-crystal X-ray analysis. The results indicated the product is a mononuclear Cu(II) complex and contains a free NH₂ functional group on the structure of the ligand. [Cu(HL)(NO₃)(CH₃OH)]·CH₃OH was used for the preparation of a heterogeneous catalyst by supporting it on functionalized silica gel. The heterogeneous catalyst (Si-Cu) was prepared by an amidification reaction of [Cu(HL)(NO₃)(CH₃OH)]·CH₃OH with functionalized silica gel. The resulting silica-supported catalyst (Si-Cu) was characterized by TGA, FT-IR, EPR, DRS, EDS, XRD, SEM and XPS analyses. Si-Cu was employed in a carbon–carbon coupling reaction and the effects of the amount of Si-Cu and temperature were investigated in the catalytic coupling. The structure of one of the products of the catalytic reactions (C₁₆H₂₂O₂, CP1) was determined by single-crystal X-ray analysis, which proved the formation of a C–C bond and the production of di-acetylene by homocoupling of terminal alkyne. This catalytic system is stable and it can be reused for a coupling reaction without a significant change in its catalytic activity.