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Reactivity Control of CH Bond Activation over Vanadium–Silver Bimetallic Oxide Cluster Cations
Author(s) -
Li XiaoNa,
Wu XiaoNan,
Ding XunLei,
Xu Bo,
He ShengGui
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201467
Subject(s) - bimetallic strip , reactivity (psychology) , vanadium oxide , chemistry , vanadium , oxide , crystallography , cluster (spacecraft) , inorganic chemistry , ion , valence (chemistry) , metal , medicine , alternative medicine , organic chemistry , pathology , computer science , programming language
Vanadium–silver bimetallic oxide cluster ions (V x Ag y O z + ; x =1–4, y =1–4, z =3–11) are produced by laser ablation and reacted with ethane in a fast‐flow reactor. A reflectron time of flight (Re‐TOF) mass spectrometer is used to detect the cluster distribution before and after the reactions. Hydrogen atom abstraction (HAA) reactions are identified over VAgO 3 + , V 2 Ag 2 O 6 + , V 2 Ag 4 O 7 + , V 3 AgO 8 + , V 3 Ag 3 O 9 + , and V 4 Ag 2 O 11 + ions, in which the oxygen‐centered radicals terminally bonded on V atoms are active sites for the facile HAA reactions. DFT calculations are performed to study the structures, bonding, and reactivity. The reaction mechanisms of V 2 Ag 2 O 6 + +C 2 H 6 are also given. The doped Ag atoms with a valence state of +1 are highly dispersed at the periphery of the V x Ag y O z + cluster ions. The reactivity can be well‐tuned gradually by controlling the number of Ag atoms. The steric protection due to the peripherally bonded Ag atoms greatly enhances the selectivity of the V–Ag bimetallic oxide clusters with respect to the corresponding pure vanadium oxide systems.