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The isomers of ionized dimethyl sulfoxide (C 2 H 6 OS +· ) and their CH 3 OS + fragments. An ab initio and multiple‐stage mass spectrometric (MS n ) study
Author(s) -
Gozzo Fábio Cesar,
Eberlin Marcos N.
Publication year - 1995
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1190301106
Subject(s) - chemistry , isomerization , dissociation (chemistry) , ab initio , metastability , ion , transition state , mass spectrometry , excited state , ab initio quantum chemistry methods , computational chemistry , photochemistry , molecule , organic chemistry , atomic physics , catalysis , chromatography , physics
The relative stabilities, isomerizations and dissociations of ionized dimethyl sulfoxide (DMSO), its three C 2 H 6 OS +· isomers and of all their 14 conceivable CH 3 OS + fragments (1–14), have been investigated by ab initio calculations at the MP2/6–31G(d,p)//6–31G(d,p) + ZPE and G2 levels of theory, and by multiple‐stage two‐ and three‐dimensional mass spectrometry performed in a pentaquadrupole instrument. The ab initio relative energies of the isomers, their connecting transition states, and their dissociation thresholds were used to elaborate potential energy surface diagrams that precisely corroborate and unify several previously divergent experimental observations on these systems. The most kinetically favorable isomerization of (CH 3 ) 2 SO +· (I) to its aci ‐form CH 2 S(OH)CH 3 +·(II) displays a transition state considerably lower in energy than the threshold for its direct dissociation by CH 3 ⋅ loss. Therefore, low‐energy, long‐lived metastable ions I are predicted to isomerize to II, and to dissociate in turn to CH 2 S + OH (2) upon CH 3 ⋅ loss. Ions I excited a few electronvolts above the threshold are, on the other hand, predicted to dissociate directly to CH 3 S + O (1). Isomerization of I to the most stable C 2 H 6 OS +· ion, that is CH 3 SOCH 3 +·(III), displays the most energetic transition state and should be negligible, whereas III is predicted to dissociate by CH 3 ⋅ loss preferentially to 1 rather than 5 (CH 3 OS + ). Nine CH 3 OS + isomers, that is 1, 2, (HCS…OH 2 ) + (3), + CH 2 S(O)H (4), 5, HC(SH)OH + (9), CH 2 OSH + (10), CH 2 + OSH (11), and (HCO…SH 2 ) + (14), were found as true minima on the RHF/6–31G(d,p) potential‐energy surface, and some of their isomerization barriers and dissociation thresholds were estimated. Tandem and multiple‐stage (MS 3 ) mass spectrometric experiments show that non‐dissociating DMSO +· ions produce, upon collision‐induced dissociation (CID), a mixture of approximately 40% of 1 and 60% of 2, whereas the CID chemistry of 1 and 2 is affected considerably by the collision energies employed. Both the experimental and theoretical results on 1 and 2 allow a detailed interpretation of their complex dissociation chemistry, which clarifies the nature of most of their indirect fragments. Such fragments are proposed to be formed via the common isomerization/dissociation sequences 1 → 2 → 9 ⇌ 3 → HCS + ( m / z 45) + H 2 O, and 1 → 2 → [7, HOCH 2 S + ] → S + CH 2 OH + ( m / z 31). These processes are favored at lower collision energies, whereas direct dissociation of 1 to CH 3 + ( m / z 15) and SO +· ( m / z 48), and of 2 to CH 2 S +· ( m / z 46) occurs to greater extents at higher collision energies.