The consecutive fragmentation of ionized trimethyl vanadate(V), OV(OCH
3)
3 (
1), is examined by experiment andtheory. After an elimination of formaldehyde from the molecular ion
1+, subsequent dissociations proceed via lossesof first H
2 and then two molecules of formaldehyde to finally yield the VOH
+ cation; these redox reactions involvethe V
II/V
IV manifold. At elevated energies, expulsion of CH
3O
![](/images/entities/bull.gif)
from
1+ can efficiently compete to afford OV(OCH
3)
2+,a formal V
V compound, from which subsequent losses of H
2 and two units of CH
2O lead to bare VO
+, therebyexploring the V
III/V
V redox manifold. Experiments using complementary mass spectrometric techniques, i.e.,neutralization-reionization experiments and ion/molecule reactions, in conjunction with extensive computationalstudies provide deep insight into the ion structures and the relative energetics of these dissociation reactions. Inparticular, a quantitative energetic scheme is obtained that ranges from neutral OV(OCH
3)
3 all the way down to thequasi-terminal fragment ions VOH
+ and VO
+, respectively.