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C−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV3O10− and FeV5O15−: A Comparison with Scandium‐Vanadium Oxide Clusters

Von Wiley-VCH zur Verfügung gestellt

Hydrogen atom abstraction from C2−C4 alkanes at 298 K by iron-vanadium bimetallic oxide cluster anions FeV3O10 and FeV5O15 featuring iron-bonded O⋅ radicals (Fe−O⋅) is characterized experimentally, which offers a new regulation rule to tune the activity of M−O⋅ radicals.


Late transition metal-bonded atomic oxygen radicals (LTM−O⋅) have been frequently proposed as important active sites to selectively activate and transform inert alkane molecules. However, it is extremely challenging to characterize the LTM−O⋅-mediated elementary reactions for clarifying the underlying mechanisms limited by the low activity of LTM−O⋅ radicals that is inaccessible by the traditional experimental methods. Herein, benefiting from our newly-designed ship-lock type reactor, the reactivity of iron-vanadium bimetallic oxide cluster anions FeV3O10 and FeV5O15 featuring with Fe−O⋅ radicals to abstract a hydrogen atom from C2−C4 alkanes has been experimentally characterized at 298 K, and the rate constants are determined in the orders of magnitude of 10−14 to 10−16 cm3 molecule−1 s−1, which are four orders of magnitude slower than the values of counterpart ScV3O10 and ScV5O15 clusters bearing Sc−O⋅ radicals. Theoretical results reveal that the rearrangements of the electronic and geometric structures during the reaction process function to modulate the activity of Fe−O⋅. This study not only quantitatively characterizes the elementary reactions of LTM−O⋅ radicals with alkanes, but also provides new insights into structure-activity relationship of M−O⋅ radicals.

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