Nitrous Oxide Mediated Oxygen Atom Insertion into a Ruthenium−Hydride Bond. Synthesis and Reactivity of the Monomeric Hydroxoruthenium Complex (DMPE)₂Ru(H)(OH)

Abstract

of protic reagents to 1 results in the replacement of the OH group with several other ligands, including aryloxo, thiolato, siloxo, C-bound enolate, acetylide, and triphenylstannyl; more deep-seated changes take place when 1 reacts with p-tolualdehyde and hexafluoroacetone.We wish to report the first observation of oxygen atom transfer from N 2 O into a late transition metalhydrogen bond and the chemistry of the hydroxohydridoruthenium complex produced in this reaction.Many catalytic processes involve intermediates that are proposed to contain late transition metal-heteroatom (N, O, S) bonds. 1-3 Recent work has been directed toward the synthesis of these potentially reactive species, but there remain few examples of monomeric late metal hydroxide complexes, 3-18 species which are thought to be important in the hydration of olefins to alcohols, the hydration of nitriles to carboxamides, and the Wacker process. 3,[19][20][21][22] We recently reported the preparation and characterization of the monomeric hydroxoruthenium complex

Metal Insertion into C−C Bonds in Solution

“…Thus, the reaction mechanism is similar to that of the Baeyer ± Villiger reduction of ketones. [26c] Bergman et al demonstrated that ruthenium complexes capable of producing unsaturated species cleave the C À C bond in acetone [27] and hexafluoroacetone [28] (Scheme 8). Cleavage of the CÀC bond in cyclic aliphatic ketones with [Rh(PPh 3 ) 3 Cl] has been reported by Murakami, Ito et al Exclusive activation of the less substituted C À C bond a to a carbonyl group has been observed.…”

Theoretical Investigation of the Controlled Metathesis Reactions of Methylruthenium(II) Complexes with Terminal Acetylenes

“…As shown in Figure 5 (1) Methane has been formed with a H 2 C-H···Ru interaction. After dissociation of the resulting methane molecule, the methoxyl ligand smoothly binds to the metal center to form a Ru-OMe σ bond, thus giving methoxide intermediate IM1, [38,39] which is calculated to be 15.6 kcal mol -1 more stable in free energy than mono-acetylido complex B. (2) The Ru···O(Me) distance was computed to be as long as 4.135 Å, which results in the unstable intermediate.…”

Nitrogen Monoxide and Nitrous Oxide Binding and Reduction

“…Bergman and coworkers [195,196] demonstrated that N 2 O is capable of mediating O-atom insertion into a late metal-hydrogen bond, in this case to afford a hydroxy-Ru complex (Scheme 2.10).…”