Ruthenium(II) Phosphine/Picolylamine Dichloride Complexes Hydrogenation and DFT Calculations

Treating [Ru(PPh3)(3)Cl-2] with the amine 2-picolylamine (Picam) ligand in a 1:1 molar ratio, the Ru(II) complex trans-Ru(PPh3)(2)(Picam)Cl-2 (1) is obtained in methylene chloride and can be isolated as a pure solid compound. The single-crystal structure of 1 was determined by X-ray crystallography. The geometry at the Ru metal center is a distorted octahedral environment with a trans arrangement of the two chlorides. A trans effect of the bond lengths was observed within the structure. Similarly, treating [Ru(PPh3)(3)Cl-2] with 1:1:1 molar ratios of 2-picolylamine (Picam) and 1,1 '-bis(diphenylphosphine)ferrocene (DPPF) ligands yielded the Ru(II) complex trans-Ru(DPPF)(Picam)Cl-2 (2). In identical conditions, the homogeneous hydrogen transfer catalytic reactivity of complexes 1 and 2 has been tested in a basic 2-propanol solution and they indicate different catalytic activity. It was discovered that monodentate and bidentate phosphine ligands of Ru(II) complexes, as well as cis- and trans-chloro configuration display different catalytic properties from our experimental data, in agreement with literature data. Based on DFT calculations, the relative molecular catalytic reactivity of all available experimental data is understood from the relative calculated molecular energy.

Automated summary

This study investigates the crystal structure and catalytic activity of Ru metal complexes. The experimental results demonstrate that different ligands and coordination configurations have influences on the catalytic performance, which are in agreement with the literature data. The effects of molecular energy on catalytic activity can be understood through DFT calculations.