Metal nitrosyl chemistry: Interesting oxidation and nitrosylation of a metal-bound ligand framework in a diamido-bis(phosphine) ruthenium(II) complex

• A Trost diamidato-bis(phosphine)-based ligand Ru(II)Cl2 compound was prepared.
• A ligand-oxidized-nitrosylated Ru(II)Cl2 complex was made on reaction with NO+.
• Solid state (X-ray) and solution (NMR) structures of the complexes are reported.

The complex Ru((R,R)-DACH-Naph)Cl2 ((R,R)-2), a neutral Ru(II) complex of the Trost diamido-bis(phosphine) ligand ((R,R)-DACH-Naph (H21)) was synthesized in 86% yield via the direct stoichiometric reaction of H21 and RuCl2(DMSO)4 in refluxing toluene. Complex (R,R)-2 was further reacted with excess [NO][BF4] producing Ru((HON)2-DICH-Naph)Cl2 (4) in 48% yield; a Ru(II) complex where the Trost ligand has been oxidized to a diimine and nitrosylated, on the backbone cyclohexyl ring, to a dioxime. The structures of (R,R)-2 and 4 were revealed in the solid state by single-crystal X-ray analysis and in the solution state via 1H NMR spectroscopy.

Synthesis of a neutral Trost-based diamidato-bis(phosphine) ligand Ru(II)Cl2 complex and its subsequent reaction with excess [NO][BF4] yielding a ligand-oxidized and -nitrosylated Ru(II)Cl2 complex.Figure optionsDownload as PowerPoint slide