Synthesis and Characterization of V v(3.6-DBSQ)(3.6-DBCat) 2. a d o Metal Complex with Dioxygenase Catalytic Activity

Inorganic Chemistry

Volumn 48, Issue 8, 2009, Pages 3496-3498

  Morris, Aimee M ^a,b   Pierpont, Cortlandt G ^a,b   Finke, Richard G ^a,b  

^a Veterinary Dentistry and Oral Surgery   (United States)

^b UNIVERSITY OF COLORADO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

3,6 DI TERT BUTYLCATECHOLATE; 3,6 DI TERT BUTYLSEMIQUINONE; 3,6-DI-TERT-BUTYLCATECHOLATE; 3,6-DI-TERT-BUTYLSEMIQUINONE; CATECHOL DERIVATIVE; DIOXYGENASE; ORGANOMETALLIC COMPOUND; QUINONE DERIVATIVE; VANADIUM;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; METABOLISM; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

CATALYSIS; CATECHOLS; CRYSTALLOGRAPHY, X-RAY; DIOXYGENASES; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; QUINONES; VANADIUM;

EID: 65349176575     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic802122q     Document Type: Article

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17. (b) It therefore seems reasonable that the initial activating Cat f O2 electron-transfer step should take place with the formation of a quasiouter- sphere intermediate that leads to one of the reduced oxygen species shown in eqs 1-3.
18. In an earlier publication, we cited 28 literature 3,5-DBCat oxidation precatalyst systems based on vanadium(Yin, C.-X.; Finke, R. G. J. Am. Chem. Soc. 2005, 127, 9003-9013). By monitoring the O2 uptake, we were able to establish that these precatalysts proceed with the initial formation of H2O2 and 3,5-di-tert-butyl-1,2-benzoquinone (3,5-DBBQ) in the presence of excess H2(3,5-DBCat). The catalyst resting state, [VO(3,5-DBSQ)(3,5-DBCat)]2, is formed in an autocatalytic step and then breaks in half to a monomeric dioxygenase catalyst according to the observed kinetics.12
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28. Morris, A. M.; Pierpont, C. G.; Finke, R. G. Manuscript in preparation.
29. w) ) 0.0540 (0.0840), GOF ) 1.071.
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32. The large intensity of the band at 670 nm leads one to wonder if this band is a LLIT band. However, this band is higher in energy than expected and, to our knowledge, is unprecedented for LLIT systems.
33. TTOs were calculated by the formula ∑[oxygenated products (mmol)]/ [V(3,6-DBSQ)(3,6-DBCat)2 (mmol)].