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Gas‐Phase Chemistry of Vanadium Oxide Cluster Cations V m O n + ( m = 1–4; n = 1–10) with Water and Molecular Oxygen
Author(s) -
Feyel Sandra,
Schröder Detlef,
Schwarz Helmut
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800685
Subject(s) - chemistry , vanadium , vanadium oxide , oxygen , inorganic chemistry , valence (chemistry) , cluster (spacecraft) , oxide , oxidation state , crystallography , metal , organic chemistry , computer science , programming language
Bare vanadium oxide cluster cations V m O n + ( m = 1–4; n =1–10) generated by electrospray ionization are investigated with respect to their reactivity toward water and molecular oxygen by using mass spectrometric techniques. Besides ion hydration, the ion/molecule reactions of V m O n + with oxygen‐labeled water (H 2 18 O) also lead to 16 O/ 18 O exchange reactions of the vanadium oxide clusters cations. Although the probability of degenerate 16 O/ 18 O exchange between V m O n + and water is fairly high for the cluster cations with a medium valence state of vanadium, oxygen‐atom exchange reactions between V m O n + and 18 O 2 can only be accomplished by VO + , V 3 O 6 + , and V 4 O 8 + . Particularly interesting is the fact that not only oxygen atoms from vanadyl units are exchanged in the cluster cations, but bridging oxygen atoms are also most likely involved in the processes. Other reaction channels for the interaction of V m O n + cluster cations with molecular oxygen are reported as well, such as oxidative degradation of the low‐valent cluster cations upon collision with O 2 and formation of association complexes for the high‐valent cluster cations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)