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

A Cu(II) complex, [Cu(HL)(NO3)(CH3OH)]middotCH(3)OH (1), was obtained by the reaction of Cu(NO3)2middot3H2O 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)]middotCH(3)OH 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)]middotCH3OH 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 amidifi-cation reaction of [Cu(HL)(NO3)(CH3OH)]middotCH(3)OH with functionalized silica gel. The resulting silica-sup-ported 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 cata-lytic reactions (C16H22O2, CP1) was determined by single-crystal X-ray analysis, which proved the for-mation 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.

Automated summary

A Cu(II) complex [Cu(HL)(NO3)(CH3OH)]middotCH(3)OH (1) was synthesized by reacting Cu(NO3)2middot3H2O with H2L in methanol solvent. The structure of [Cu(HL)(NO3)(CH3OH)]middotCH(3)OH was determined by single-crystal X-ray analysis, showing that it is a mononuclear Cu(II) complex with a free NH2 functional group. The complex was supported on functionalized silica gel to prepare a heterogeneous catalyst (Si-Cu) which was characterized by various analytical techniques. Si-Cu exhibited good catalytic activity in carbon-carbon coupling reactions and showed stability for reuse.