(oxo)(phosphine)ruthenium(IV) complexes: oxygen atom transfer in the oxidation of olefins, sulfides, sulfoxides, and free phosphines

Journal Article · Thu Dec 01 04:00:00 EST 1988 · J. Coord. Chem.; (United States)

DOI:https://doi.org/10.1080/00958972.1988.9728139· OSTI ID:5830811

Marmion, M E; Leising, R A; Takeuchi, K J

Kinetic and mechanistic studies of the oxidation of olefins, sulfides, and sulfoxides by (Ru/sup IV/(bpy)/sub 2/(O)(PR/sub 3/))(ClO/sub 4/)/sub 2/ (bpy = 2,2'-bipyridine; R = ethyl or phenyl) complexes have been conducted in both methylene chloride and acetonitrile. In all cases, the rate law shows a first-order dependence on both the concentration of (oxo)ruthenium(IV) species and the target substrate. In addition, product distributions of substrate oxidation exhibit a strong dependence on both the particular phosphine ligand and the solvent utilized in the experiment. On the basis of labelling experiments and kinetic evidence, a mechanism is proposed involving a two-electron, oxygen atom insertion into the target substrate. Notably, an (oxidized substrate)ruthenium(II) complex has been isolated and characterized for the oxidation of styrene by the (oxo)(triethylphosphine)ruthenium(IV) complex, where a cyclic voltammogram of this complex displays one quasi-reversible Ru(III)/Ru(II) couple with an E/sub 1/2/ = 1.24 V vs SSCE. Kinetic analysis of styrene oxidation indicates that the formation of benzaldehyde from styrene does not occur simply by two sequential two-electron steps. In this regard, alternative mechanisms are discussed.

• Research Organization: SUNY, Buffalo (USA)
• OSTI ID: 5830811
• Journal Information: J. Coord. Chem.; (United States), Journal Name: J. Coord. Chem.; (United States) Vol. 19:1-3; ISSN JCCMB
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
AZINES
BIPYRIDINES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
KINETICS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
OXYGEN
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PYRIDINES
REACTION KINETICS
REDOX REACTIONS
RUTHENIUM COMPLEXES
SOLVENTS
SULFIDES
SULFOXIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES