Degradation of ionized OV(OCH3)3 in the gas phase.: From the neutral compound all the way down to the quasi-terminal fragments VO+ and VOH+

The consecutive fragmentation of ionized trimethyl vanadate( V), OV( OCH3)(3) ( 1), is examined by experiment and theory. After an elimination of formaldehyde from the molecular ion 1(+), subsequent dissociations proceed via losses of first H-2 and then two molecules of formaldehyde to finally yield the VOH+ cation; these redox reactions involve the V-II/V-IV manifold. At elevated energies, expulsion of CH3O center dot from 1(+) can efficiently compete to afford OV( OCH3)(2)(+), a formal V-V compound, from which subsequent losses of H-2 and two units of CH2O lead to bare VO+, thereby exploring 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 computational studies provide deep insight into the ion structures and the relative energetics of these dissociation reactions. In particular, a quantitative energetic scheme is obtained that ranges from neutral OV( OCH3) 3 all the way down to the quasi-terminal fragment ions VOH+ and VO+, respectively.