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+
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- 作者：Detlef Schrö ; der ; Marianne Engeser ; Helmut Schwarz ; Esther C. E. Rosenthal ; Jens Dö ; bler ; Joachim Sauer
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：August 7, 2006
- 年：2006
- 卷：45
- 期：16
- 页码：6235 - 6245
- 全文大小：238K
- 年卷期：v.45,no.16(August 7, 2006)
- ISSN：1520-510X
文摘
The consecutive fragmentation of ionized trimethyl vanadate(V), OV(OCH3)3 (1), is examined by experiment andtheory. After an elimination of formaldehyde from the molecular ion 1+, subsequent dissociations proceed via lossesof first H2 and then two molecules of formaldehyde to finally yield the VOH+ cation; these redox reactions involvethe VII/VIV manifold. At elevated energies, expulsion of CH3O
from 1+ can efficiently compete to afford OV(OCH3)2+,a formal VV compound, from which subsequent losses of H2 and two units of CH2O lead to bare VO+, therebyexploring the VIII/VV 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(OCH3)3 all the way down to thequasi-terminal fragment ions VOH+ and VO+, respectively.
from 1+ can efficiently compete to afford OV(OCH3)2+,a formal VV compound, from which subsequent losses of H2 and two units of CH2O lead to bare VO+, therebyexploring the VIII/VV 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(OCH3)3 all the way down to thequasi-terminal fragment ions VOH+ and VO+, respectively.