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

A Cu(II) complex, [Cu(HL)(NO)(CHOH)]·CHOH (1), was obtained by the reaction of Cu(NO)·3HO and H2L in methanol solvent (H2L is ()-4-amino-'-(2-hydroxy-3-methoxybenzylidene)benzohydrazide). H2L and compound 1 were characterized by various spectroscopic analyses and the molecular structure of [Cu(HL)(NO)(CHOH)]·CHOH was determined by single-crystal X-ray analysis. The results indicated the product is a mononuclear Cu(II) complex and contains a free NH functional group on the structure of the ligand. [Cu(HL)(NO)(CHOH)]·CHOH 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)(NO)(CHOH)]·CHOH 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 (CHO, 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.