title: Is it true dioxygenase or classic autoxidation catalysis? Re-investigation of a claimed dioxygenase catalyst based on a Ru(2)-incorporated, polyoxometalate precatalyst.
abstract: A 1997 Nature paper reported that a novel Ru(2)-incorporated sandwich-type polyoxometalate, {[WZnRu(III)(2)(OH)(H(2)O)](ZnW(9)O(34))(2)}(11)(-), is an all-inorganic dioxygenase catalyst for the hydroxylation of adamantane and the epoxidation of alkenes using molecular oxygen. Specifically, it was reported that the above Ru(2)-containing polyoxometalate catalyzes the following reaction by a non-radical-chain, dioxygenase mechanism: 2RH + O(2) --> 2ROH (R = adamantane). A re-investigation of the above claim has been performed, resulting in the following findings: (1) iodometric analysis detects trace peroxides (0.5% relative to adamantane), the products of free-radical-chain autoxidation, at the end of the adamantane hydroxylation reaction; (2) a non-dioxygenase product, H(2)(18)O, is observed at the end of an adamantane hydroxylation reaction performed using (18)O(2); (3) kinetic studies reveal a fractional rate law consistent with a classic radical-chain reaction; (4) a non-dioxygenase approximately 1:1 adamantane products/O(2) stoichiometry is observed in our hands (instead of the claimed 2:1 adamantane/O(2) dioxygenase stoichiometry); (5) adamantane hydroxylation is initiated by the free radical initiator, AIBN (2,2'-azobisisobutyronitrile), or the organic hydroperoxide, t-BuOOH; (6) four radical scavengers completely inhibit the reaction; and (7) {[WZnRu(III)(2)(OH)(H(2)O)](ZnW(9)O(34))(2)}(11)(-) is found to be an effective catalyst for cyclohexene free-radical-chain autoxidation. The above results are consistent with and strongly supportive of a free-radical-chain mechanism, not the previously claimed dioxygenase pathway.
authors.affiliation: Department of Chemistry, Colorado State University, Ft. Collins, Colorado 80523, USA.
authors.forename: Cindy-Xing
authors.initials: CX
authors.lastname: Yin
authors.forename: Richard G
authors.initials: RG
authors.lastname: Finke
mesh_terms: D002384:Catalysis; D049308:Dioxygenases / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D012428:Ruthenium; D049308:Dioxygenases; D010100:Oxygen