M. M.

Campbell
Heriot-Watt University
Edinburgh, Scotland
and 0. Runquist
Hamline Universitv
I1 Fragmentation Mechanisms
in Mass Spe~fr~metry
St. Paul, Minnesota
I
M a n y students have difficulty under- The conceptual utility of the above conventions will
standing and rationalizing the fragmentation mech- he illustrated by some fragmentation processes com-
anisms as commonly depicted in the literature and monly encountered.
textbooks dealing with mass spectrometry; at least
part of this difficulty is related to the imprecise nature Alkanes
of the conventions used and the resulting difficulties Ionization of the ethane molecule may result in loss of
in electronic book-keeping. I n this paper, we wish an electron from the C-C bond. One electron is left in
to illustrate a precise mechanistic notation which we the bonding sigma molecular orbital in 11. Localizing
have found useful in teaching fragmentation processes. this electron on C ( l ) a t the moment of fragmentation
During the process of ionization of a molecule in a results in seven electrons around C(1) and six electrons
mass spectrometer, an electron is lost and a molecular around C(2). C(1) can therefore be thought of as a
ion which is hoth radical and cation is formed. The radical and C(2) as a cation.
radical cation is commonly shown as, for example, I We thereforesuggest that the ethane radical cation,
indicating that the species formed has a positive charge which is encountered in the chemical literature as 111,
and an unpaired electron; no attempt is made in this would be more precisely illustrated as IV.3 Fragmen-
designation to locate the charge or radical. Such no- tation of IV, affording methyl cation and methyl rad-
tations for the radical cations are not useful in teaching ical, can thus be explained by hemGheterolysis.
the fragmentation mechanisms that occur. The frag-
mentations as depicted in the literature can be con-
fusing to students who attempt to follow the bond-
breaking process that occurs. Consider for example
the fragmentation of radical cation I as is commonly
illustrated. The percipient student may question this
representation, pointing out that although a hond has
been ionized, all bonds in the molecule are formally
depicted as covalent, two-electron, sigma bonds. Fur-
thermore, the arrow indicating the fragmentation pro-
cess may represent either a one-electron shift or a two-
electron shift.
Because of these conceptual problems, we suggest
that in teaching mass spectrometry the following con-
ventions he adopted' H H
1. that in expanded formulae used t o illustrate fragmentation CH: 15
m/e + CH;
processes, a two-electron sigma bond be represented by a line
between two atoms, i.e., A-B bf.pfH]
2. that an ionized hond, which contains me electron, be repre-
+
sented by the symbol .,i.e., A . +B or A+ .B w
3. that a one-electron shift be indicated by '
single-headed Fragmentation of radical cation V which is formed
arrow and a two-electron shift be indicated by a double- by ionization of 2-methylpentane, can similarly be ex-
headed arrow
4. that fragmentation types be defined as ' This convention is based upon the widely-used notation intro-
duced by Shannon (Proe. Royal Austral. Chem. Inst., 328, (1964))
Homolgsis. Cleavage of a two-electron sigma bond, one and more reeentlv emoloved bvDierassiet al. (H. Buozr~usw~cz.
electron stayingwith each fragment, i.e. C. D ~ m n s s AND
~ , D.'H."WIL~IAMS"Maas Spectrometry of or:

r?P
X-Y - X' + Y'
Heterolysis. Cleavage of a two-electron sigma bond, hoth
ganic Compounds,'' Holden-Day Inc., San Francisco, 1967).
Certain modifications are introduced with theobjective of facilita-
ting the teaching of mass spectral fragmentation processes.
%Thisterm has not, t o our knowledge, been used in mass
electrons staying with one or other fragment, i.e. spectrometry. We consider that i t is necessary to define the
process of fission by which an ionized bond is cleaved, and there-
fore, propose "hemi-heterolysis." "Homolysis" and "heteralysis"
are, of course, accepted terms in mass spectroscopy.
'The structure is represented as I V solely as a conciptual aid
Hemi-Heterolysis.2 Cleavage of an ionized sigma.bond, i.e. in understanding the origin of the radical cation charge and the
subsequent fragmentations. The true physical state probably
involves the co-existence of several ionized species.

104 / Journal o f Chemical Education

 Allylic Cleavage
Allylic cleavage can he considered as homolytic, or
heterolytic fragmentation of the allylic hond. Thus,
by invoking homolytic cleavage of the allylic bond in
XIII, a resonance stabiized allylic cation XV, and a

neutral fragment, are formed. Heterolytic cleavage

plained by invoking hemi-heterolysis of the ioniaed
hond. Note that a t the very high electron voltage
used in mass spectrometry it is probable that other
radical cations of 2-methylpentane are formed. For
example, radical cation VI is a possible precursor of
the fragment which appears at m/e 43.
Unlike 2-methylpentane, long-chain hydrocarbons
do not have a point of chain branching at which pref-
erential cleavage would occur. Consequently, they
tend to lose the terminal alkyl group by hemi-heter-
of the allylic hond in the alternative radical cation
XIV affordsan allylic radical XVI and an alkyl cation
XVII.
Mdafferfy Rearrangement
The McLafferty Rearrangement is usually illus-
trated in the literature as shown for XVII. Allylic
oleavage of XVII accompanied by hydrogen transfer,
results in formation of neutral ethylene and ionized
propylene XVIII. The faults implicit in this mode of
representation are again operative.
The McLafferty Rearrangement of 1-pentene can

-
olytio cleavage, with subsequent losses of neutral
methylene units by heterolytic cleavage, e.g., VII + he more clearly understood by using the suggested con-
ventions. Thus, the radical cation XI11 may be
VIII IX etc.
shown to undergo two consecutive heterolytic cleav-
A common fragmentation process of cyclic alkanes
involves extrusion of a neutral olefinic moiety. This ages,' leading to propene radical cation XIX and neu-
tral ethylene. Alternatively, radical cation XIV may
fragmentation may he described mechanistically as
hemi-heterolysis of an ionized molecule X with con- undergo two homolytic cleavages, affording XX, ares-
onance form of XIX.
comitant heterolysis of the sigma hond which is & r
to the site of ionization. Note that the resultant
charged fragment XI is aradical cation.
r . -7 r' 7

X W XVm mle 42

Alkenes
Radical cations formed by removal of a pi-electron
from an olefin are often depicted in the literature as,
for example, XII. Again, conceptual difficulties oper-
ate when the student uses this convention to explain
fragmentations.
However, fragmentations of some olefins have been
adequately described in the literature by considering
the radical cation site to be localized. For example,
1-pentene is best represented to the student as XI11 Note that those fragmentations which result in rad-
or XIV. (The origin of the radical cation charge is ical cation charge residing in the C(B):C(r) moiety can
readily understood by considering all the valence elec- he rationalized by postulating heterolysis of C(y)-H
trons, and localizing the single pi-electron on one of followed by homolysis of C(a)-C@).
the carbon atoms). We wish to emphasize the utility
'Two consecutive steps hsve been invoked for clarity. Those
of this convention, and will demonstrate that the prin- who prefer to present the rearrangement as a synchronous process
ciple fragmentations of olefins are consequently easily can concert the two cleavage steps and eliminate the inter-
taught. mediate radical cation.

Volume 49, Number 2, February 1972 / 105

 L I I A LII
XXXM
McLofferty Rwrrongement

-
involves elimination of a neutral molecule (e.g., HzO
or HBr). This process may be envisaged (XXXIX When a y-H is available, the ubiquitous McLafferty
XL) as a concerted extrnsion involving heterolysis rearrangement occurs. Ionized di-n-propyl ketone
of the C-heteroatom bond with simultaneous homo- XLIX affordsradical cation LIII and neutral ethylene
lytic H-transfer through a cyclic transition state (n = by a concerted elect~rocyclicrearrangement,. In an
0, 1, 2). The elimination product is a radical cation. alternative representation (LIV -t LV), resonance
structures of XLIX and LIII are invoked.
Complex Fission in Cyclic Systems
m,@-fission in a cyclic system XLI affords a ring-
opened radical cation XLII which undergoes H-trans-
fer and bond cleavage as shown, to give the oxonium
ion XLIV. The alternative a,p-fission process can be
XLM LIII -
shown to give oxonium ion XLV. t t

XLI XLII XLm

Complex Fission in Cyclic Systems

XLN XLV
Ketones and Aldehydes
Fragmentations of aldehydes and ketones have been
adequately explained by assuming localization of rad-
ical cation charge in the carbonyl group. Under the
high energy conditions of mass spectroscopy, radical
cation XLVI, which is formed by removal of a lone-
pair electron, has resonance forms XLVII and XLVIII.
XLM XLVII XLVIII
The consequent fragmentation processes can be de-
picted logically as follows.
Fragment,at,ionof the carbonyl-C(or) bond (a-cleav-
age) is the predominant process in the mass spectra of
ketones and aldehydes. Homolysis of radical cation
XLIX affords oxonium ion I,. Subsequent loss of
neutral CO from L is rationalized by invoking heter-
Cyclopentanone and cyclohexanone radical cations
fragment by a sequence of homolytic fissions (LVI
LVIX), yielding a resonance-st,abilized oxonium ion
-
LVIX. Note that t,his process parallels those of cyclic
alcohols, ethers, and halides.
LVI LVII LVEI Lvrm
Esters, Acids, and Amides
Fragmentation processes parallel those of ketones,
i.e., or-fission processes and McLafferty rearrangements
are conspicuous.
Fvnclional Group Derivatives
Mass spectrometric examination of derivatives of
functional groups has become increasingly important
in structure elucidation. The fragmentation processes
of these derivatives can be explained logically accord-
ing to the principles laid out in the earlier sections.
Alcohol Derivatives
Although acet,ates may be the most common alco-

-
hol derivatives, they are seldom diagnostically useful
olytic scission of resonance form LI. in mass spectrometry. Acetate radical cat,ions uu-
dergo facile ext,rusion of acetic acid (LX LXI).

XLM

G&-C=O
r+ + CsH,C + CO
LI m/e 43

The characteristic fragment at M-1 ( M is molecular

weight,) in the spectra of aldehydes is due to a-cleav-
age of the aldehyde proton (LII -t L).
Volume 49, Number 2, February 1972 / 107
 Consequently the molecular ion may be weak. The
radical cation LXI undergoes subsequent Retro-Diels
Alder fragmentation.
I n contrast, trimethylsilyl ether derivatives of al-
-
cohols afford significant molecular ions. In addition,
they undergo predictable a,/%cleavage and complex
rearrangement processes, e.g., (LXII LXV) and
give intense fragment ions.
LXII
I
~~sii'z;
LXV
Ketone Derivatives
The mass spectrum of a ketone may afford some
structural data. However, by forming a derivative
such as an ethylene lietal (or thioketal) complementary
data may be obtained, affording additional inform*
tion about the functional group environment. The
most spectacular example involves the ethylene lietal
of androstan-3-0ne.~ The radical cation LXVI frag-
ments by a logical sequence of homolyses and H-trans-
fers resulting in a highly-abundant resonance stabilized
108 / Journol o f Chemical Edvcotion
fragment LXVII. The alternative a,&fission of
LXVI can be shown to yield the stable fragment ion
LXVIII by a similar pathway.
LXVI
Summary
The commonly encountered radical cation repre-
sentation, in which the charge is not localized, may
confuse students. The alternative teaching conven-
tions suggested in this paper have a dist,inct advantage
in that electronic "book-keeping" is possible, and
mechanisms can be illustrat,ed as natural extensions of
previously-encountered cation and radical mecha-
nisms.
2. Per.nH, n. IT. WILLI.AMS, 1%.BUDZII~IEWICZ,
AND C. DJIS-
n a s s ~ ,J . Amer Chem. Sac., 86, 3722 (1964). a. V. IMUTZEN-
sccwm, Z. PIIL~H, D. H. WILLIAMS,I I . BUDZII~I,:WICZ,
and
C.DJI:IIASSI, Steroids, 2,475 (1963).