JOURNAL OF MASS SPECTROMETRY, VOL.

32, 71È80 (1997)

Investigation of Group Migration in the

Fragmentation of Bis(trimethylsilyl) Ethers of
Diols Separated by Rigid Groups

Jaeman Byun,1 Michael L. Gross,1* Mathai George,2 David M. Parees,3 Ann Z. Kamzelski,3
Dennis F. H. Swijter3” and Dale A. Willcox3
1 Department of Chemistry, Washington University, St. Louis, MO, 63130 (USA)
2 Midwest Center for Mass Spectrometry, Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588-0304
(USA)
3 Air Products and Chemicals, Inc., Allentown, PA 18195 (USA)

Two fragmentations of (CH ) SiO-CR -X-CR -OSi(CH ) , where X is a rigid group such as a triple bond or an
33 2 2 33
aromatic ring, are losses of a methyl or R group (where R is H or alkyl). The metastable-ion dissociations of
[ M Ô R ] ‘ and [ M Ô CH ] ‘ ions include the rearrangement of a trimethylsilyl (TMS) cation and a
3
(CH ) SixO neutral species through an ion–neutral complex. On the basis of tandem mass spectrometry
32
(MS/MS), exact mass measurement and isotopic labeling experiments, it has been established that the two tri-
methylsilyloxy groups in the TMS ethers interact across a wide range of distances via an ion–neutral complex. The
migration of a TMS cation occurs when the group that is bound to carbon is expelled as a radical by an oxygen-
directed cleavage to give a trimethylsilylated oxonium ion. If, on the other hand, a methyl radical is lost from the
silicon atom, then (CH ) SixO migrates. The mobilities of the TMS cation and the neutral (CH ) SixO are
32 32
governed by the capability of the rigid group to delocalize charge.
J. Mass Spectrom. 32, 71È80 (1997)
No. of Figures : 14 No. of Tables : 2 No. of Refs : 44
KEYWORDS : diols ; TMS ethers ; group migration ; fragmentation mechanisms ; ionÈneutral complexes ; tandem mass spec-
trometry

INTRODUCTION In addition, TMS cations from tetramethylsilane

have been used as a reagent gas in chemical ionization
(CI) mass spectrometry because these cations bind well
The trimethylsilylation of diols reduces hydrogen- with a variety of compounds that have atoms with non-
bonding interactions and polarity and also increases bonding electron pairs (e.g. N, O).12h18 Many studies of
thermal stability and volatility, thereby making the deri- the TMS cation as a CI reagent gas have provided
vatized diols suitable for determination by gas important information with regard to fragmentation
chromatography/mass spectrometry.1 The formation of mechanisms and thermodynamic data. Moreover, the
the ion of m/z 147 [(CH ) SiwO`xSi(CH ) ] and strong SiwO bond is a driving force for the CI reac-
33 3 2 of ter- tion.19
related ions from ionized bis(trimethylsilyl) ethers
minal diols that have the general structure The capability of the TMS cation group to migrate
HOw(CH ) wOH was reported previously.2h5 A over a wide range of distances in semi-rigid or rigid
2n molecules was demonstrated not only for metastable-
McLa†erty-type rearrangement of the trimethylsilyl
(TMS) group produces predominant odd-electron ions ion decompositions of radical cations that are produced
from TMS derivatives of hydroxy dicarboxylic acids.6,7 by electron impact (EI) ionization, but also for
For TMS ether derivatives of some steroid compounds, bimolecular reactions.10,11,20,21 Although the mechan-
the predominant fragment ions are produced by the isms were not proved, these migrations may take place
migration of the TMS cation or a related group to an by means of ionÈneutral complexes. Metastable disso-
oxygen located elsewhere on the semi-rigid steroid ring ciations that take place through a weakly bonded
system.5,8h11 complex were recognized as intermediates in the frag-
mentation of closed-shell ions by Bowen and co-
workers22,23 in 1978 and were termed ionÈneutral
* Correspondence to : M. L. Gross. complexes by Morton24 in his classic review article in
” Current address : International Flavors and Fragrance, 1515 State 1982. In recent reviews, the binding forces, transition
Highway 36, Union Beach, NJ 07735 (USA). states for decomposition of complexes and the distinc-
Contract grant sponsor : National Science Foundation ; Contract
grant number : CHE9017205. tion between ionÈneutral complexes and other reaction
Contract grant sponsor : National Institutes of Health ; Contract intermediates were described.25,26 An additional inter-
grant number : P41RR0954. esting and signiÐcant observation made in numerous

CCC 1076È5174/97/010071È10 Received 27 August 1996

( 1997 by John Wiley & Sons, Ltd. Accepted 17 September 1996
72 J. BYUN ET AL .

studies is that in EI-induced metastable-ion decomposi- Canada). 2,5-Dimethylhex-3-yne-2,5-diol and 3,6-

tions of TMS ethers, the TMS cation is likely to transfer dimethyloct-4-yne-3,6-diol were provided by Air Pro-
to electron-rich sites at a remote posi- ducts and Chemicals (Allentown, PA, USA).
tion.3,6,7,20,21,27h29
The migration of Me Si` in the systems reported in Synthesis
3
this paper may occur by either p or n complexes. In the
former, the bonding between Si and C is stronger and
TMS ether derivatives were synthesized by dissolving
the positive charge is delocalized onto the carbon skele-
3 mmol of the diol in distilled dichloromethane fol-
ton. In the latter, the binding between the Si and the
lowed by adding 6.3 mmol of 1-(trimethylsilyl)imid-
n-center is weak and there is considerable positive
azole. The reaction mixture was stirred for 2 h at room
charge on Si. The distinction between these two pictures
temperature. Argon was used to provide an oxygen-free
was recently the subject of intense debate in the liter-
and moisture-free atmosphere because most TMS ether
ature.30h33
derivatives investigated in this study were sensitive to
The primary goal of this study was to determine
moisture. The Ðnal TMS ether was isolated by remo-
whether two trimethylsilyloxy groups separated by a
ving the solvent at 30 ¡C under vacuum. Thin-layer
rigid function (e.g. benzene ring or triple bond) interact
chromatography and NMR spectrometry of all the
with each other via an ionÈneutral complex. The
TMS ether derivatives showed that the purity of the
metastable-ion and collisionally activated dissociation
product was greater than 98%.
(CAD) mass spectra of [M [ R]` (R \ H, CH or
3 To prepare the isotopically labeled compound, 20 ml
C H ) and [M [ CH ]` produced from the molecular
2 5 3 of a solution of distilled diethyl ether containing
ions containing aromatic, IÈIII and aliphatic, IVÈVI,
0.01 mol of dimethyl phthalate was added to 100 ml of
groups were examined. The Ðrst-generation fragment
distilled diethyl ether containing 0.04 mol of lithium
ions were chosen for study because molecular ions are
aluminum deuteride. The mixture was stirred overnight
of low relative abundance or are non-detectable.
and the reaction was quenched by adding water until
The secondary goal was to identify the fragmentation
the remaining LiAlD and the water formed a gray
pathways of the selected TMS ethers and determine the 4 magnesium sulfate and Ðltering
paste. After drying with
structure of fragment ions from speciÐc precursors (e.g.
the salts, the solvent was evaporated and the liquid
[M [ R]` and [M [ CH ]`). Fragmentation path-
3 residue was used to synthesize the TMS ether of d -1,2-
ways and structures for fragment ions of m/z 119 or 147,
benzenedimethanol. The TMS-d ether was synthesized 4
which form from various precursors in metastable-ion 4
by using the same procedure except benzenedimethanol
processes, were determined on the basis of exact mass
was substituted for d -1,2-benzenedimethanol. A 10 ml
measurement, tandem mass spectrometry (MS/MS) and 4 of dried CH Cl , 2 mmol of
volume of a solution
isotopic labeling experiments. 2 2and 2.1 mmol
chloromethylsilane-d , 1 mmol of the diol
9
of imidazole were mixed and then stirred for 12 h. The
TMS-d ether was isolated as a slightly yellow liquid
18
by evaporating the solvent.

NMR spectroscopy

1H NMR spectra were acquired in CDCl at 25 ¡C on a

Nicolet 360 MHz spectrometer. Chemical 3 shifts are
reported relative to tetramethylsilane (internal
reference).
1,4-Bis(trimethylsilyloxymethyl)benzene : 1H NMR, d
0.34 (s, 18H, 6 CH on the Si), 4.86 (s, 4H, 2 benzylic
3
CH ) and 7.37 (s, 4 ring H).
2
1,3-Bis(trimethylsilyloxymethyl)benzene : 1H NMR, d
0.40 (s, 18H, 6 CH on the Si), 4.94 (s, 4H, 2 benzylic
3 on the benzene), 7.45 (d, 1H, 5-H
CH ), 7.24 (s, H, 2-H
2
on the benzene) and 7.52 (d, 2H, 4-H and 6-H on the
benzene).
EXPERIMENTAL SECTION 1,2-Bis(trimethylsilyloxymethyl)benzene : 1H NMR, d
0.26 (s, 18H, 6 CH on the Si), 4.85 (s, 4H, 2 benzylic
CH ), 7.35 (m, 2H,34-H and 5-H on the benzene) and
7.492(m, 2H, 3-H and 6-H on the benzene).
Reagents 1,4-Bis(trimethylsilyloxy)-but-2-yne : 1H NMR, d 0.16
(s, 18H, on the Si) and 4.30 (s, 4H, 2CH of the C-1 and
Benzenedimethanol isomers, but-2-yne-1,4-diol, but-2- 2
C-4).
ene-1,4-diol, butane-1,4-diol, lithium aluminum deuter- 2,5-Dimethyl-2,5-bis(trimethylsilyloxy)-hex-3-yne : 1H
ide, 1-(trimethylsilane)imidazole dimethyl phthalate and NMR, d 0.16 (s, 18H, on the Si) and 1.47 (s, 12H, 4CH
dimethyl fumarate were purchased from Aldrich Chemi- 3
on the C-2 and C-5).
cal (Milwaukee, WI, USA). Chlorotrimethylsilane-d 3,6-Dimethyl-3,6-bis(trimethylsilyloxy)-oct-4-yne : 1H
was purchased from MSD Isotopes (Pointe Claire,9 NMR, d 0.17 (s, 18H, on the Si), 1.43 (s, 6H, 2 CH on
3
 FRAGMENTATION OF TMS ETHERS OF DIOLS 73

the C-3 and C-6), 0.96 (t, 6H, 2 CH of the C-1 and C-8) from the CH group or by the loss of a methyl radical
3 2
and 1.63 (q, 4H, 2 CH of the C-2 and C-7). that is bound to the silicon atom are more abundant
2 than are the molecular radical cations.
For aliphatic TMS ethers, the [M [ R]` ion, which
Instrumentation and procedures is generated by the loss of a hydrogen, methyl or ethyl
radical from the carbon backbone, is barely observable.
A Kratos MS-50 tandem mass spectrometer was used The ion [M [ CH ]`, produced by the loss of a methyl
to acquire the tandem mass spectra.34 The Ðrst-stage 3
group from the silicon atom, however, is of higher
mass spectrometer was a high-resolution, double- abundance. For the hexyne TMS ether V, one cannot
focusing instrument of normal geometry ; the second determine the origin of the expelled methyl group
stage was an electrostatic analyzer. An ion accelerating without isotopic labeling experiments, which will be
voltage of 8 kV and an electron energy of 70 eV were described later.
used for these experiments. All samples were introduced
into the source through a room temperature liquid inlet.
For MS/MS experiments, precursor ions were selected [ M Ô H ] ‘ ions from aromatic TMS ethers
at a resolving power of 1500 with MS-1 and product-
ion mass spectra were obtained by scanning the electric The signiÐcant fragment ions produced from the
Ðeld of the second electrostatic analyzer (ESA). Helium [M [ H]` species and their relative abundances in the
was employed as a collision gas for activating ions for EI-induced metastable-ion mass spectra are sum-
collisionally activated decomposition (CAD), and its marized in Table 1. The three principal fragments are of
pressure was increased until the intensity of the selected m/z 147, 119 and 73. The formation of the ion of m/z
ion beam was reduced by 50%. For metastable-ion 119 from the [M [ H]` ion is the major metastable-ion
experiments, the same procedure was employed in decomposition process and may occur via an ionÈ
acquiring tandem mass spectra except that no collision neutral complex. Details of the fragmentation pathways
gas was used. In MS/MS/MS experiments, the ions pro- will be presented later. The relative abundances of the
duced in the source were activated in the Ðrst collision ion of m/z 73 vary depending on substitution positions
cell, which is located between the source and the Ðrst between the two trimethylsilyloxy groups. A possible
ESA. A speciÐc fragment ion was chosen by adjusting explanation of this dependence is that major fragments
the Ðrst ESA and the magnetic sector to the appropriate from the ion of I and II are produced via an ionÈneutral
values, and the ion of interest was transmitted at a complex as an intermediate. Substitution at the ortho
resolving power that was sufficient to separate ions that position (III), however, allows the two TMS groups to
are one mass unit apart to the second collision cell ; the interact directly en route to producing fragments.
CAD spectrum was then obtained by scanning the The decompositions of metastable [M [ H]` ions
second ESA. A more detailed explanation of the tandem from 1,4-bis(trimethylsilyloxymethyl)benzene, I, produce
mass spectrometric experimental procedures was a number of fragment ions (see Fig. 1). The ion of m/z
published previously.35 251 is generated by the loss of CH O. The ions of m/z
2
207 and 193 are produced by a hydride and methide
group abstraction by a TMS cation, leading to the
RESULTS AND DISCUSSION losses of HSi(CH ) and Si(CH ) , respectively. A TMS
3 3 by simple 3 4cleavage of the SiwC
cation is also formed
bond. The dissociation of metastable [M [ H]` ions
The molecular ions of aliphatic and aromatic com- from the meta, II and ortho, III, isomers also produces
pounds I [ VI are of low abundance or are not detect- an ion of m/z 119 as the major fragment. The formation
able. For the aromatic TMS ethers, I [ III, the ions of the fragment ions of m/z 119 and 147, which occur in
that are generated by the loss of a hydrogen radical the mass spectra of the aromatic ethers, I, II and III,

Table 1. Fragment ions and their relative abundances produced from

[ M Ô H ] ‘ and [ M Ô CH ] ‘ ions from aromatic TMS ethers during
3 process
the EI-induced metastable-ion
ÍM É H˽ a ÍM É CH ˽ b
3
Molecular
Compound ion m /z m /z 147 m /z 119 m /z 73 m /z 237 m /z 147 m /z 119

I 282 3 100 25 100 17 3

II 282 5 100 8 43 7 100
III 282 2 100 NDc 5 30 100
III-d 286 100d 27 100e
4
III-d 300 32f 100g
18
a ÍM É D˽ in III-d .
b ÍM É CD ˽ in III- 4d .
3 18
c Not detected.
d m /z 122 in III-d .
e m /z 123 in III-d 4 .
f m /z 162 in III-d 4 .
g m /z 122 in III-d18 .
18
74 J. BYUN ET AL .

Figure 1. Metastable ion spectrum of the ÍM É H˽ ion obtained

from 1,4-bis (trimethylsilyloxymethyl)benzene (magnified 1000
times with respect to the precursor relative abundance of 100%).

must involve shifts of the rearranging group over the

rigid spacer. If an intermediate ionÈneutral complex is
involved, the reactivity of the [M [ H]` ion is govern-
ed by the charge delocalization capability of the
benzene ring and the ionÈdipole interaction. High-
resolution peak matching of the source-produced m/z
119 ions revealed that there are two isobaric ions,
C H O` and C H` and that the ion of m/z 147 has
8 formula
7
C H9 Si
11 O. The atom combination for the
the
5 15
m/z 147 ion must result 2 by long-range interaction of Figure 2. CAD spectra of (A) C H O½ and (B) metastably pro-
8 7
two trimethylsilyloxy groups. duced ion of m /z 119 from 1,2- bis (trimethylsilyloxymethyl)-
An MS/MS/MS experiment was performed to deter- benzene.
mine the formula of the ion of m/z 119 that is produced
in the metastable-ion and collisionally activated decom-
positions. The ion of m/z 281, [M [ H]`, produced in TMS ethers give the ion of m/z 73 as the major frag-
the source, was allowed to undergo metastable-ion ment. This process is kinetically simple and hence is
decomposition in the Ðrst Ðeld-free region. The product favored when the ion internal energy is high. The d
ion of m/z 119 was transmitted by adjusting the Ðrst analog of III undergoes the expected fragmentation to4
ESA and magnetic sector to the third Ðeld-free region yield ions of m/z 122. This indicates that three deute-
for activation in the second collision cell. The CAD rium atoms remain in the ion of m/z 122, consistent
mass spectrum was obtained by scanning the second with the proposed mechanism of a TMS cation
ESA. The CAD spectrum of the source-produced rearrangement through an ionÈneutral complex.
C H O` ion (mass selected at a resolving power of We proposed that the intermediate in the migration
108000)
7 [Fig. 2(A)] and that of the metastably produced of Si(CH )` is an ionÈneutral or n complex. An alterna-
33
tive intermediate is a set of p complexes produced by
ion of m/z 119 from the [M [ H]` ion (Fig. 2(B)) for III
are similar except for the expected poorer resolving migration of the Si(CH )` and bonding to the aromatic
3 3 question of p vs n complexes
power seen in Fig. 2(B). Because the spectra are nearly ring (see structure 6). The
identical, the metastably produced ion of m/z 119 that is of Si(CH )` and aromatic rings has a long and colorful
3 3 early work by Wojtyniak and Stone,41 the
generated from the ion of m/z 281 must have the history. In
formula C H O. silylation adduct that forms as a result of the attack of a
8 7 in a position to propose a mechanism for TMS cation on the aromatic substrates in the gas phase
We are now
the formation of the ion of m/z 119 from I (see Scheme was proposed to have a n-bonded structure rather than
1). Similar mechanisms for the decompositions of II and an p-bonded structure because they were unable to dep-
III are expected. The SiwO bond is stretched in the rotonate it. A radiolytic study, however, suggested that
[M [ H]` ion, 1, and the ionÈdipole interaction the classical p-bonded complex is stable, but its depro-
between the TMS cation and the n electrons of the aro- tonation was prevented by a more competitive desilyla-
matic ring, 2, allows for the formation of an ionÈneutral tion by the nucleophilic oxygenated acceptors.38h40
complex. Similar complexes were proposed by GruŽtz- When stronger bases than those used by Wojtyniak and
macher and co-workers36,37 to account for migration of Stone41 were used, deprotonation could be achieved in
H` and other positively charged groups across aro- accord with an p complex.
matic rings. The migration across the benzene ring of Lambert et al.42 reported the bond distance between
the TMS cation, which is stabilized by hypercon- Si and the C-4 of toluene in the crystal structure of tri-
jugation, can also take place easily through this ethylsilyl tetrakis(pentaÑuorophenyl)borate prepared
complex. The ion of m/z 119, 5, which is formed by the
loss of (CH ) SiOSi(CH ) , is most favored in the
3 3 dissociations.
3 3 Upon collisional activa-
metastable-ion
tion, however, the [M [ H]` ions of all the aromatic
 FRAGMENTATION OF TMS ETHERS OF DIOLS 75

Scheme 1.

from toluene solution is too long for p bonding. The

x-ray results agree well with the calculated bond lengths
and bond angles, which were obtained by the use of a
Gaussian-92 series of programs.43 Reed et al.44 also cal-
culated the charge density on Si in the gas-phase
complex of (CH ) Si` and toluene. The amount of
charge in toluene3 3was also experimentally determined
from the 13C NMR shift.32 All these results, in our
opinion, favor a n complex in which the toluene ring is
nearly planar and the charge is predominantly on the
silicon atom.

[ M Ô CH ] ‘ ion from aromatic TMS ethers

3
The decompositions of metastable [M [ CH ]` ions
from the three aromatic TMS ethers, IÈIII, yield 3 three
principal fragment ions of m/z 237, 147 and 119 (Fig. 3).
The ion of m/z 237 is produced by the loss of a neutral
formaldehyde, involving the cleavage of the CwC and
SiwO bonds and the formation of a CwSi and a CwO
bond (see Scheme 2). Production of the m/z 237 ion is
the major metastable dissociation process for the para
isomer whereas formation of the m/z 119 ion is the
major metastable decomposition process for ortho and
meta isomers.
The decompositions of metastable [Fig. 4(A)] and
collisionally activated [Fig. 4(B)] m/z 237 ions for I
were investigated to establish the relationship of precur- Figure 3. Metastable ion spectra of the ÍM É CH ˽ ions for (A)
3
sor and product ions. This ion may be a silicon analog 1,4-(B) 1,3- and (C) 1,2-bis (trimethylsilyloxymethyl)benzene.
76 J. BYUN ET AL .

Scheme 2.
Scheme 3.
of a tropylium ion, 9, which decomposes to ions of m/z
221, 147 and 133. The ion of m/z 147, 10, which is a
di†erent species that is produced directly from the ion A fragmentation mechanism for the formation of the
ion of m/z 147, 16, from the [M [ CH ]` ion (m/z 267)
of m/z 267, contains only one silicon atom (see Scheme
of the para isomer (see Scheme 3) begins 3 with stretching
2).
the bond between neutral (CH ) SixO and the incipi-
ent cation. Resonance charge3 2delocalization in the
cation allows the (CH ) SixO species to interact at
various positions of the3 aromatic
2
ring, opening a reac-
tion channel for the migration of (CH ) SixO and for-
32
mation of the m/z 147 ion. The rearrangement of
(CH ) SixO across the rigid group may occur via an
32
ionÈneutral complex and ultimately a Ðve-membered
ring intermediate is formed. For the case of the meta
isomer, a six-membered ring intermediate would be
formed to accommodate the di†erent charge delocal-
ization of the benzene ring.
The principal fragment ions generated from the [M
[ CH ]` ions from the three isomers and their relative
3
abundances in the metastable-ion spectra are sum-
marized in Table 1. The formation of the ion of m/z 119
from the [M [ CH ]` ion is the most favorable meta-
3 process for II and III, whereas the
stable decomposition
formation of this ion is less favored for I. This m/z 119
ion has a di†erent elemental composition from an iso-
baric fragment that is produced from the [M [ H]`
ion. The formation of the ion of m/z 147 is less favorable
than formation of the m/z 237 of I (Fig. 3(A)) or of the
ion of m/z 119 of II and III isomers (Fig. 3(B) and (C)).
The relative abundances of fragment ions of m/z 119
and 147 indicate that the ion of m/z 147 from I is more
favored than the ion of m/z 119, whereas the ion of m/z
147 from II or III is less favored. The proposed mecha-
nism for decomposition of I (Scheme 3) shows that
Figure 4. Metastable-ion (A) and CAD (B) mass spectra of the CwO and SiwO bond cleavages followed by CwO
ion of m /z 237 for 1,4-bis (trimethylsilyloxymethyl)benzene. and SiwO bond formations are required to generate the
 FRAGMENTATION OF TMS ETHERS OF DIOLS 77

m/z 147 ion. The production of the ion of m/z 119 also
requires CwO and SiwC bond cleavages, CwC and
SiwO bond formations, as well as SiwO bond break-
ing.
The CAD mass spectrum for the ortho isomer was
examined to determine whether the two tri-
methylsilyloxy groups interact with each other to
produce the ions of m/z 119 and 147. The metastable-ion
[Fig. 3(C)] and the CAD (Fig. 5) mass spectra show
that the reactions to form these two ions are competi-
tive. The generation of ion of m/z 147 by an SiwO bond
cleavage in the Ðve-membered ring intermediate, 19 in
Scheme 4, is a kinetically favored simple cleavage
process. Direct interaction of the two trimethylsilyloxy
groups, which is not possible for the meta and para
isomers, allows transfer of a trimethylsilyloxy group to
an oxygen of the neighboring TMS group. An alterna-
tive explanation is that this isomer also fragments via
an ionÈneutral complex ; this explanation is consistent
with the similar fragmentation chemistry that occurs for
the three isomers.
The metastable-ion mass spectra of [M [ CH ]` ion
3 ion is
from isomeric TMS ethers shows that the m/z 119

Figure 6. CAD spectra of (A) the C H ½ produced in the ion

9 11
source and (B) the C H ½ produced in a metastable-ion decom-
9 11
position of 1,2-bis (trimethylsilyloxymethyl)benzene.

commonly formed. This ion is the most abundant meta-

stable fragment ion for the ortho TMS isomer. On the
basis of the proposed mechanism (Scheme 4), the
formula of the ion is C H . An MS/MS/MS experi-
ment was carried out to 9conÐrm
11 the formula of this ion
and to determine whether the fragment is di†erent than
that of the [M [ H]` ion. The CAD mass spectrum
Figure 5. CAD mass spectrum of the ÍM É CH ˽ ions for 1,2-
3 [Fig. 6(A)] of the source-produced C H` ion (selected
bis (trimethylsilyloxymethyl)benzene. 9 11
at a resolving power of 10 000) and that of the metasta-
bly produced ion of m/z 119 from the [M [ CH ]` ion
(Fig. 6(B)) from the ortho isomer are similar. 3This is
good evidence that the latter ion has the formula C H
9 11
and is probably produced by the loss of the neutral,
OxSi(CH )OSi(CH ) , which is formed directly or via
3 33
an ionÈneutral complex.

Aliphatic ethers

The collisionally activated decompositions of the frag-

ment ions produced by the losses of R (R \ H, CH and
3
C H ) from the carbon atom or of a methyl radical
2 5
linked to the silicon atom for di-TMS ethers that were
synthesized from but-2-yne-1,4-diol, 2,5-dimethylhex-3-
yne-2,5-diol and 3,6-dimethyloct-4-yne-3,6-diol (IVÈVI)
were examined to investigate the generality of the frag-
mentation mechanisms. It was not possible to investi-
gate the molecular radical cation of these aliphatic
ethers because they are not detected. Important
common fragment ions and their relative abundances
are summarized in Table 2.
As observed for aromatic TMS ethers, the formation
Scheme 4. of the ion of m/z 147 is an important metastable
78 J. BYUN ET AL .

Table 2. Fragment ions and their relative abundances produced from

[ M Ô R ] ‘, where R is the group bonded to the carbon skeleton,
and [ M Ô CH ] ‘ ions from the aliphatic TMS ethers
3
Precursor Compound
ion Fragment ion IV V V-d VI
18
ÍM É R˽ ÍM É R É (CH ) SiOH˽ NDa
3 3
R ¼H
ÍM É R É (CD ) SiOH˽ 100
3 3
R ¼ CH
3
ÍM É R É (CH ) SiOH˽
3 3
R ¼C H 100
2 5
m /z 147 ion 100 47b 15
ÍM É CH ˽ ÍM É CH É (CD ) SiOH˽ 20
3 3 3 3
ÍM É CH É (CH ) SiOH˽ ND
3 3 3
m /z 147 ion 100 100b
ÍM É R˽ c ÍM É CH É (CH ) SiOH˽ 100 100
3 3 3
and
ÍM É CH ˽ m /z 147 ion 70 28
3
a Not detected.
b m /z 162 in V-d .
18
c Loss of R and CH from M½~ cannot be distinguished.
3

process, indicating that this predominant ion is formed stand the fragmentation pathways of the di†erent [M
by a low-energy reaction. The m/z 147 ion is also pro- [ CH ]` ions, the metastable-ion mass spectra of the
duced readily in the ion source. Exact mass measure- 3
d -labeled analog was examined [Fig. 8(B) and (C)].
18
ment for the source-produced m/z 147 ion showed that The fragments from the [M [ CH ]` ion generated by
its formula is C H Si O. The relative abundances of A, the loss of methyl radical bound 3to the carbon atom
A ] 1 and A ]52 15 2 147, 148 149, respectively, are
at m/z between the triple bond and oxygen are of m/z 190 and
also consistent with the formula. The structure of the 162 [see Fig. 8(B)]. The ion of m/z 190, [M [ CH
m/z 147 ion was conÐrmed by its CAD spectrum, which [ (CD ) SiOH], is formed by the major metastable3
is nearly identical with that of the [M [ CH ]` frag- 33
decomposition. The ion of m/z 147 now shifts to m/z
ment of hexamethyldisiloxane (see Fig. 7). Upon 3 col- 162.
lisional activation, the two ions of m/z 147, which have
two di†erent sources, produce abundant common frag-
ments at m/z 131, 117, and 73.
The abundances of [M [ R]` ions that are formed in
the ion source from aliphatic TMS ethers are greater for
losses of the large alkyl than the small alkyl radicals.
The [M [ H]` ion from 1,4-bis(trimethylsilyloxy)-but-
2-yne is of low abundance and decomposes to produce
the ions of m/z 201, 147 and 73. The metastable-ion
decompositions of the ions formed by the losses of
either methyl from the molecular ion of V or ethyl from
the molecular ion of VI produce the m/z 147 ion and the
[M [ R [ 90]` ion. The neutral of mass 90 is
(CH ) SiwOH, which may be expelled from the
3 3R]` ion by means of a charge-remote process.
[M [
The formation of this ion is a dominant metastable-ion
decomposition of the [M [ R]`.
The [M [ CH ]` ion from 2,5-dimethyl-2,5-bis(tri-
3
methylsilyloxy)-hex-3-yne dissociates by a metastable-
ion process to produce major fragment ions of m/z 197
and 181 in addition to that of 147 [see Fig. 8(A)]. The
ion of m/z 197 is produced by the migration across the
triple bond of the trimethylsilyl ion, which then
abstracts a hydride from a methyl group linked to the
carbon. The ion of m/z 181 from the two di†erent [M
[ CH ]` precursors is formed by the loss of
(CH ) 3SiwOH, possibly by means of a charge-remote
33
fragmentation. Figure 7. CAD spectra of (A) m /z 147 ion produced from hexa-
There are two possible sites in the hexyne compound methyldisiloxane and (B) m /z 147 ion generated in the source
(V) for the elimination of the methyl radical. To under- from 2,5-dimethyl-2,5-bis (trimethylsilyloxy)hex-3-yne.
 FRAGMENTATION OF TMS ETHERS OF DIOLS 79

On the other hand, the product ion from loss of the

deuterated methyl radical from the silicon atom is of
m/z 286 for V-d . The fragments from the [M
18
[ CD ]` ion are of m/z 187, 162 and 107 [see Fig.
3
8(C)]. The ion of m/z 187, [M [ CD [ (CD ) SiOH],
3 33
is produced by a metastable-ion loss of (CD ) SiOH,
33
possibly through a charge-remote fragmentation. The
shift of the m/z 147 ion to m/z 162 for the TMS-d
18
ether of hexynediol establishes that the ion contains Ðve
methyl groups, two silicons and one oxygen. The ion of
m/z 107, having only carbons and hydrogens, is produc-
ed by the loss of C HD Si O . The CAD mass spec-
5 15 2 2
trum for the (M [ CD )` ion indicates that the
3
formation of the ion of m/z 162 is kinetically favored.
The formation of the ion of m/z 109 from the [M
[ CH ]` ion from the d -labeled analog is also
3 18
expected to be a metastable dissociation. This ion may
be produced by the loss of neutral hexamethylsiloxane-
d . The reaction is likely to be a one-step process
18
involving interaction of the two trimethylsilyloxy
groups. The ions of m/z 119 from [M [ H]` ions of
aromatic TMS ethers are produced by a similar disso-
ciation process except that the production of the m/z
109 ion in VI is less favored than that of m/z 119 in Scheme 5.
aromatic TMS ethers. Because a triple bond has lower
charge delocalization capability than does a benzene A mechanism for the formation of the ion of m/z 147
ring, the production of the [M [ CH that is generated from the fragment produced by the
[ (CD ) SiwOwSi(CD ) ]` ion for the hexyne com-3 loss of methyl radical bound to the silicon atom is pro-
pound 3is3 less favorable 3than
3 the ion formed from the
posed in Scheme 5 to involve the migration of
same loss from the analogs containing an aromatic ring. (CH ) SixO to give a Ðve-membered ring intermediate,
24. 3The
2 electropositive silicon atom in (CH ) SixO
bonds strongly with the electronegative oxygen3 atom
2 of
a remote trimethysilyloxy group. On the basis of the
proposed mechanism, the SiwO and CwO bonds are
formed and broken to produce the ion of m/z 147. As in
the case of aromatic TMS ethers, the m/z 147 ion from
the aliphatic compounds may form by means of an
intermediate ionÈneutral complex, 23.
If the methyl radical is lost from the carbon atom of
the molecular ion, an SiwO bond can be broken (28)

Figure 8. Metastable-ion spectra of (A) the ÍM É CH ˽ ion for

2,5-dimethyl-2,5-bis (trimethylsilyloxy)hex-3-yne, 3
(B) ÍM
É CH ˽ and (C) the ÍM É CD ˽ ion for 2,5-dimethyl-2,5-bis-
3 3
(trimethylsilyloxy)hex-3-yne-d . Scheme 6.
18
80 J. BYUN ET AL .

and the Si(CH )` ion migrates to the trimethylsilyloxy For the aromatic compounds, the metastable-ion
33 spectra of the [M [ H]` ion strongly support a TMS
group through either an ionÈneutral or p complex
(Scheme 6). If the latter were involved, positive charge cation migration by means of an intermediate ionÈ
moves on to the carbon skeleton to give a vinyl carbo- neutral complex. Futhermore, spectra of metastable [M
cation, a p complex that is less favored than that in an [ CH ]` ions show that the (CH ) SixO group
3 32
aromatic system. In the n complex, however, the posi- migrates, possibly through an ionÈneutral complex, en
tive charge remains principally on silicon, which should route to fragment ions of m/z 119 and 147.
be even more favored for these systems than those with For aliphatic TMS ethers, the ions generated by the
aromatic systems. The Ðnal product is then favored by loss of hydrogen, methyl and ethyl radicals from the
transfer of a methyl group to one of the carbons of the carbon backbones of various butyne, hexyne and octyne
triple bond, 29. This transfer should be facile because TMS diethers, respectively, also undergo the TMS
the siliconÈmethyl carbon bond is unusually long and cation rearrangement whereas the [M [ CH ]` ion
3
weak. that is produced by the loss of a methyl group linked to
the silicon atom undergoes (CH ) SixO migration.
32
These migration/rearrangements are likely to occur via
CONCLUSION ionÈneutral complexes.

The rearrangement of the trimethylsilyl (TMS) cation

during the EI-induced metastable-ion decomposition of
Acknowledgement
trimethylsilyl ethers leads to an interaction of the tri-
methylsilyloxy groups in the TMS ethers of aromatic This work was supported by the National Science Foundation (Grant
and aliphatic compounds. This long-distance inter- No. CHE9017250), National Institutes of Health (Grant No.
action occurs via intermediate ionÈneutral complexes. P41RR0954) and Air Products and Chemicals Inc.

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