ja991503b_si_003.pdf (504.19 kB)
An All-Inorganic, Polyoxometalate-Based Catechol Dioxygenase That Exhibits >100 000 Catalytic Turnovers
journal contribution
posted on 1999-10-07, 00:00 authored by Heiko Weiner, Richard G. FinkeFollowing a critical analysis of the dioxygenase literature and injection of the insights therein into
the development of new dioxygenase catalysts, two new, of four total exemplary, polyoxoanion precatalysts
have been synthesized, characterized, and then discovered to exhibit record catalytic lifetime 3,5-di-tert-butylcatechol (DTBC; 1) dioxygenase activity using molecular oxygen as the terminal oxidant. A total of 24
additional polyoxoanion and other precatalysts have also been surveyed for their DTBC dioxygenase activity.
The four exemplary precatalyst complexes are the trivanadium(V)-containing, orange-red parent polyoxoanions
(n-Bu4N)7[SiW9V3O40], I, and (n-Bu4N)9[P2W15V3O62], II, and their previously unknown polyoxoanion-supported, dark green iron complexes (n-Bu4N)5[(CH3CN)xFe·SiW9V3O40], III, and (n-Bu4N)5[(CH3CN)xFe·P2W15V3O62], IV. Careful, high (95 ± 5%) mass balance studies are reported, studies rare in the dioxygenase
literature, but studies made possible in the case of I−IV by their high activity and long lifetimes which yielded
sizable amounts of isolable, and thus unequivocally characterizable, products (the characterization of products
2, 3, 4, and 6 includes single-crystal X-ray crystallography structures): 3,5-di-tert-butyl-1-oxacyclohepta-3,5-diene-2,7-dione (muconic acid anhydride), 2; 4,6-di-tert-butyl-2H-pyran-2-one, 3; a new, previously unidentified
product (once misidentified in the literature), spiro[1,4-benzodioxin-2(3H), 2‘-[2H]pyran]-3-one, 4‘,6,6‘,8-tetrakis(1,1-dimethylethyl), 4; 3,5-di-tert-butyl-5-(carboxymethyl)-2-furanone, 5; and the autoxidation product,
3,5-di-tert-butyl-1,2-benzoquinone, 6. Quantitative yields for each of the above products are also reported.
Solvent effects on the dioxygenase reaction are evaluated by survey studies in 5 solvents; the highest yields
are observed in non-coordinating solvents such as 1,2-dichloroethane. Oxygen uptake studies are reported; the
results confirm the 1 O2:1 DTBC stoichiometry which defines a catechol dioxygenase and address, for the
first time, the details of how this ∼1:1 stoichiometry actually arises from the linear combination of the individual
stoichiometries of the five, formally parallel, major reactions yielding the five major products. Initial kinetic
studies are also reported; the O2 uptake kinetics reveal a novel product and catalyst evolution mechanism
consisting of an A → B induction period, followed by an A + B → 2 B autocatalytic step for complexes I and
III, where A = O2 and B is a product of the DTBC plus O2 reaction. Catalyst lifetime experiments with
(n-Bu4N)5[(CH3CN)xFe·SiW9V3O40], III, as a prototype precatalyst reveal a DTBC dioxygenase catalytic lifetime
of >100 000 total catalytic turnovers (TTOs), a record compared to any reported dioxygenase, man-made or
enzymic. A Summary and Conclusions section is presented, as is a list of the needed additional, in-progress,
kinetic, mechanistic, and catalyst isolation and characterization studies. The long-term goal of such studies is
the development of even longer-lived, more selective dioxygenase catalysts able to oxygenate the full range
of interesting substrates of enzymic dioxygenases, as well as abiological substrates such as propene.