Wydział Chemii

Anna Skarżyńska

Miłosz Siczek

Piotr Durlak

2026

ChemCatChem

1-14

10.1002/cctc.202500483

Naukowa

Angielski

Artykuł

A group of ruthenium(II) complexes stabilized by the tautomeric forms of H-spirophosphorane ligands HP(OCH₂CMe₂NH)₂ L1 and HP(OCMe₂CMe₂O)(OCH₂CMe₂NH) L2 was prepared from various precursors. Starting with [RuCl₂(DMSO-S)₃(DMSO-O)], two complexes, [RuCl₂{P(OCH₂CMe₂NH)(OCH₂CMe₂NH₂)}(DMSO)₂] [Ru1L1] and [RuCl₂{P(OCMe₂CMe₂O)(OCH₂CMe₂NH₂)}(DMSO)₂] [Ru2L2], were obtained. The treatment of [RuCl₂(PPh₃)₃] with phosphorane ligands in acetonitrile produces [RuCl₂{P(OCH₂CMe₂NH)(OCH₂CMe₂NH₂)}(MeCN)(PPh₃)] [Ru3L1] and [RuCl₂{P(OCMe₂CMe₂O)(OCH₂CMe₂NH₂)}(MeCN)(PPh₃)] [Ru4L2]. However, when the reaction was conducted in dichloromethane with excess ligands L1 or L2, diastereomers of [RuCl₂{P(OCH₂CMe₂NH)(OCH₂CMe₂NH₂)}₂] [Ru5L1] and [RuCl₂{P(OCMe₂CMe₂O) (OCH₂CMe₂NH₂)}₂] [Ru6L2] were obtained. Two additional diastereomers of the latter complexes were prepared starting with [Ru(p-cymene)Cl₂]₂. Finally, the equimolar reaction of [RuCl₂(PPh₃)₃] and L1 in dichloromethane resulted in the formation of the dimer [Ru(μ-Cl)Cl{P(OCH₂CMe₂NH)(OCH₂CMe₂NH₂)}(PPh₃)]₂ [Ru7L1]. The resulting complexes were analyzed using a variety of analytical techniques, including multinuclear nuclear magnetic resonance, infrared spectroscopy, single-crystal X-ray diffraction, and elemental analysis. Density functional theory (DFT) calculations were employed to evaluate the stability of the complexes. Subsequently, well-defined catalyst precursors were assessed in the hydrogen transfer reaction. The catalyst [Ru1L1] demonstrated excellent activity toward the formation of aromatic alcohols in the hydrogen transfer reaction from 2-propanol to aromatic ketones.

Density functional theory (DFT) calculations, Phosphorus ligands, Ruthenium complexes, Hydrogen transfer reaction, X-ray structure

http://dx.doi.org/10.1002/cctc.202500483

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