Reactivity control of nitrate-incorporating octadecavanadates by changing the oxidation state and metal substitution.

Clarification and control of the active sites at the atomic/molecular level are important to develop nanocatalysts. The catalytic performance of two oxidation states of nitrate-incorporating octadecavanadates, [V18O46(NO3)]5- (V18) and [V18O46(NO3)]4- (V18ox), and a copper-substituted one, [Cu2V16O44(NO3)]5- (Cu2V16), in selective oxidation was investigated. Both V18 and V18ox possessed the same double-helical structures and one of two tetravalent vanadium sites of V18 was oxidized in V18ox. The comparison of the mobility of the incorporated nitrate reveals that tetravalent vanadium centres show stronger interaction with the incorporated anions than pentavalent ones. The oxidation reaction with V18ox proceeded more smoothly with tert-BuOOH as an oxidant than that with V18. The reactivity and selectivity of the oxidation of 2-cyclohexen-1-ol were different among the derivatives. V18ox showed the higher reactivity with 72% selectivity to epoxide. With V18, reactivity was lower but higher selectivity to epoxide was achieved. In the presence of Cu2V16, 2-cyclohexen-1-one was selectively obtained with 81% selectivity. The order of the reactivity for cyclooctene was V18ox, V18 and Cu2V16. These results shows that the cap part of the double-helix acts as the active site. Even though the vanadium-oxygen species exhibit the same structures, the catalytic properties can be controlled by changing the valence of vanadium and metal substitution.