Preparation of Neutral [Ru(OCR)P(NN)], Cationic [Ru(OCR)P(NN)](OCR) and Pincer [Ru(OCR)(CNN)P] (P = PPh, P = diphosphine) Carboxylate Complexes and their Application in the Catalytic Carbonyl Compounds Reduction.

The diacetate complexes -[Ru(κ-OAc)(PPh)(NN)] (NN = ethylenediamine (en) (), 2-(aminomethyl)pyridine (ampy) (), 2-(aminomethyl)pyrimidine (ampyrim) ()) have been isolated in 76-88% yield by reaction of [Ru(κ-OAc)(PPh)] with the corresponding nitrogen ligands. The ampy-type derivatives and undergo isomerization to the thermodynamically most stable cationic complexes [Ru(κ-OAc)(PPh)(NN)]OAc ( and ) and -[Ru(κ-OAc)(PPh)(NN)] ( and ) in methanol at RT. The -[Ru(κ-OAc)(P)] (P = dppm (), dppe ()) compounds have been synthesized from [Ru(κ-OAc)(PPh)] by reaction with the suitable diphosphine in toluene at 95 °C.

Mild N-Alkylation of Amines with Alcohols Catalyzed by the Acetate Ru(OAc) (CO)(DiPPF) Complex.

The acetate complex Ru(OAc) (DiPPF) (2) obtained from Ru(OAc) (PPh )  (1) and 1,1'-bis(diisopropylphosphino)ferrocene (DiPPF) reacts cleanly with formaldehyde affording Ru(OAc) (CO)(DiPPF) (3) in high yield. The monocarbonyl complex 3 (0.4-2 mol %) efficiently catalyzes the N-alkylation of primary and secondary alkyl and aromatic amines using primary alcohols ROH (R=Et, nPr, nBu, PhCH ) under mild reaction conditions (30-100 °C) with an alcohol/amine molar ratio of 10-100.

The Development of Phosphine-Free "Tethered" Ruthenium(II) Catalysts for the Asymmetric Reduction of Ketones and Imines.

In this account, we describe the design, synthesis and applications of tethered versions of the Ru(II)/N-tosyl-1,2-diphenylethylene-1,2-diamine (TsDPEN) class of catalyst that are commonly used for asymmetric transfer hydrogenation and asymmetric hydrogenation of ketones and imines. The review covers key aspects of the reaction mechanisms and examples of applications, including industrial applications to pharmaceutically important target molecules. In addition, closely related catalysts based on Rh(III) and Ir(III) are also described.