ChemInform Abstract: Thianthrene 5-Oxide as a Mechanistic Probe in Oxygen Transfer Reactions: Complexation of the Substrate in Oxidations with Transition Metal Peroxides.

1986 ◽  
Vol 17 (22) ◽  
Author(s):  
W. ADAM ◽  
B. B. LOHRAY
Keyword(s):  
Transition Metal ◽  
Oxygen Transfer ◽  
Transfer Reactions ◽  
Mechanistic Probe

Oxygen transfer reactions. 3. The oxidation of sulfides by sodium perruthenate

1995 ◽  
Vol 73 (1) ◽  
pp. 49-55 ◽  
Author(s):  
Donald G. Lee ◽  
Huifa Gai
Keyword(s):  
Reaction Mechanism ◽  
Transition Metal ◽  
Transition State ◽  
Oxygen Transfer ◽  
Coordination Shell ◽  
Transfer Reactions ◽  
Hydroxide Ion ◽  
First Order ◽  
Order Dependence ◽  
Substituent Constants

The transfer of oxygen from transition metal oxidants to sulfur (MO4− + R2S → MO3− + R2SO) has been studied using the oxidation of alkylthio or arylthioacetic acids (RSCH2CO2H) by perruthenate as models. These reactions exhibit a first-order dependence on the concentrations of both the oxidant and the reductant, and are directly proportional to the basicity of the medium. The Hammet ρ value is negative (ρ = −0.66), a better correlation being obtained when σ, rather than σ+, substituent constants are used. The entropies of activation for the reactions are large and negative, indicating that the transition state is highly structured. A reaction mechanism involving an activating expansion of the ruthenium coordination shell through incorporation of a hydroxide ion is proposed. Oxygen transfer is then initiated by reaction of a nonbonding pair of sulfur electrons with either a vacant ruthenium d-orbital or a Ru=O π*-orbital. Keywords: perruthenate, sulfides, oxygen transfer, oxidation.

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