Work

Tandem Deacetalization–Knoevenagel Condensation Reactions for the Synthesis of Benzylidene Malononitrile Using Ruthenium(II) Cymene Complexes

Year: 2024

Type: article

Abstract: In this study, we report the synthesis and full characterization of five novel ruthenium(II) cymene complexes with the general formula [Ru(cym)(L’)Cl], featuring N,O- and N,N-coordinating pyrazolone-based hydrazone ligands. We have characterized these complexes using single X-ray crystallography, Fourier-transform infrared spectroscopy (FT-IR), Nuclear magnetic resonance (NMR), elemental analysis, and Electrospray Ionization Mass Spectroscopy (ESI-MS). Crystallographic analysis confirmed that all of the complexes have a similar type of half-sandwich, pseudo-octahedral “three-legged piano-stool” geometry where the cymene moiety displays the typical η 6 -coordination mode and the hydrazone ligands coordinate to the Ru(II) center in a bidentate fashion. These complexes, with multiple catalytic sites, demonstrated high efficiency in catalyzing one-pot cascade deacetalization–Knoevenagel condensation reactions under mild conditions, achieving up to 92% of final product yield at 75 °C after 4 h of reaction time under solvent-free condition. Additionally, DFT calculations provided insight into the catalytic mechanism, suggesting a pathway driven by metal–ligand cooperation, assisted by the basic oxygen site of the pyrazolone ring and by the weakly acidic character of the NNH proton of the hydrazone group.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.4c03109