Oxidations of ER[sub 3] (E = P, As, or Sb) by hydrogen peroxide: Methylrhenium trioxide as catalyst

Journal Article · Tue Jan 10 23:00:00 EST 1995 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00106a030· OSTI ID:6582633

Abu-Omar, M M; Espenson, J H ^[1]

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1. Iowa State Univ., Ames, IA (United States)

Catalytic and noncatalytic conversions of tertiary phosphines to their oxides by hydrogen peroxide have been investigated. The catalyst is methylrhenium trioxide, CH[sub 3]ReO[sub 3]. The kinetics were investigated in acetonitrile-water (1:1 by volume) at 25[degree]C. Stepwise interactions between CH[sub 3]ReO[sub 3] and H[sub 2]O[sub 2] form CH[sub 3]Re([eta][sup 2]-O[sub 2])(O)[sub 2](OI[sub 2]). A, and CH[sub 3]Re([eta][sup 2]-O[sub 2])[sub 2](O)(OH[sub 2]), B. In CH[sub 3]CN-H[sub 2]O (1:1 v/v) the equilibrium constants are K[sub 1] = 13 [+-] 2 L mol[sup [minus]1] and K[sub 2] = 136 [+-] 28 L mol[sup [minus]1] at pH 1.0 and 25[degree]C. The forward and reverse rate constants for the formation of A in this medium are k[sub 1] = 32.5 [+-] 0.3 L mol[sup [minus]1] s[sup [minus]1] and k[sub [minus]1] - 3.0 [+-] 0.2 s[sup [minus]1]. Systematic changes in the substituents on phosphorus were made to vary the nucleophilicity of the phosphine and its cone angles; the kinetic effects are discernible, although they lie in a narrow range. Triphenylarsine and triphenylstibine were also studied, and their rates are within a factor of 2 of that for PPh[sub 3]. The rhenium peroxides A and B show a small difference in reactivity. The bimolecular reactions between A and most of the phosphines have rate constants of the order 10[sup 5] L mol[sup [minus]1] s[sup [minus]1]. The kinetic data support a mechanism that allows nucleophilic attack of the substrate at the rhenium peroxides. 38 refs., 12 figs., 3 tabs.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6582633
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 117:1; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
665100 -- Nuclear Techniques in Condensed Matter Physics -- (1992-)
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ANTIMONY COMPOUNDS
ARSENIC COMPOUNDS
CATALYSTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
INFORMATION
KINETICS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PEROXIDES
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
RESONANCE
RHENIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS