Kinetic study of the oxygen-transfer reactions from the oxo diperoxo complexes of molybdenum(VI) and tungsten(VI) to (thiolato)- and (sulfenato)cobalt(III) complexes

Journal Article · Wed Dec 28 00:00:00 EST 1988 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00299a017· OSTI ID:5242128

Ghiron, A F; Thompson, R C ^[1]

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1. Univ. of Missouri, Columbia (USA)

The (thiolato)cobalt(III) complex (en){sub 2}Co(SCH{sub 2}CH{sub 2}NH{sub 2}){sup 2+} is oxidized first to (en){sub 2}Co(S(O)CH{sub 2}CH{sub 2}NH{sub 2}){sup 2+} and then much more slowly to (en){sub 2}Co(S(O){sub 2}CH{sub 2}CH{sub 2}NH{sub 2}){sup 2+} by the oxo diperoxo complexes of Mo(VI) and W(VI). Nearly quantitative oxygen atom transfer from peroxide to the coordinated sulfur acceptor accompanies these reactions. The reactions are strictly catalytic with respect to the d{sup o} metal ions, provided sufficient hydrogen peroxide is present to maintain them as oxo diperoxox complexes. The activation of the coordinated peroxo group is impressive; the relative reactivities for each substrate stand in the order WO(O{sub 2}){sub 2} > WO(OH)(O{sub 2}){sub 2}{sup {minus}} > MoO(O{sub 2}){sub 2} > MoO(OH)(O{sub 2}){sub 2}{sup {minus}} {much gt} H{sub 2}O{sub 2}. Second-order rate constants and, with the exception of those for WO(O{sub 2}){sub 2}, activation parameters for all these reactions were determined. The data are insufficient to distinguish whether nucleophilic attack by coordinated sulfur occurs directly at the peroxo ligand or after prior coordination at Mo(VI) or W(VI).

• OSTI ID: 5242128
• Journal Information: Inorganic Chemistry; (USA), Vol. 27:26; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COBALT COMPLEXES
BINDING ENERGY
REACTION KINETICS
REDOX REACTIONS
OXYGEN COMPLEXES
ACTIVATION ENERGY
ELECTRONS
HYDROGEN PEROXIDE
LIGANDS
MOLYBDENUM IONS
OXIDATION
SULFUR COMPOUNDS
TUNGSTEN IONS
VALENCE
CHARGED PARTICLES
CHEMICAL REACTIONS
COMPLEXES
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HYDROGEN COMPOUNDS
IONS
KINETICS
LEPTONS
OXYGEN COMPOUNDS
PEROXIDES
TRANSITION ELEMENT COMPLEXES
400200* - Inorganic
Organic
& Physical Chemistry