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

Author:

Wei Gong‐Ping123,Liu Qing‐Yu13ORCID,Zhao Yan‐Xia13ORCID,He Sheng‐Gui123ORCID

Affiliation:

1. State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry Chinese Academy of Sciences Beijing 100190 P. R. China

2. University of Chinese Academy of Sciences Beijing 100049 P. R. China

3. Beijing National Laboratory for Molecular Sciences and CAS Research/Education Centre of Excellence in Molecular Sciences Beijing 100190 P. R. China

Abstract

AbstractLate 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.

Funder

National Natural Science Foundation of China

Youth Innovation Promotion Association of the Chinese Academy of Sciences

Publisher

Wiley

Subject

Physical and Theoretical Chemistry,Atomic and Molecular Physics, and Optics

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