16 CHAPTER 1 MASS SPECTROMETRY
weights of all natural isotopes of an element (e.g., C =
12.01,0 = 15.999).
Table 1.4 gives the masses to four or five decimal
places for the common nuclides; it also gives the familiar
atomic weights (average weights for the elements).
Appendix A lists molecular and fragment formulas
in order of the unit masses. Under each unit mass, the
formulas are listed in the standard Chemical Abstract
system. lbe formula mass (FM) to four decimal places
is given for each formula. Appendix A is designed for
browsing, on the assumption that the student has a unit
molecular mass from a unit-resolution mass spectrome-
ter and clues from other spectra. Note that the table
includes only C, H, N, and O.
1.5.3 Use of the Molecular Formula.
Index of Hydrogen Deficiency
If organic chemists had to choose a single item of infor-
mation above all others that are usually available from
spectra or from chemical manipulations, they would
certainly choose the molecular formula.
In addition to the kinds and numbers of atoms, the
molecular formula gives the" index of hydrogen defi-
ciency. The index of hydrogen deficiency is the number of
pairs of hydrogen atoms that must be removed from the
corresponding "saturated" formula to produce the mo-
lecular formula of the compound of interest. The index of
hydrogen deficiency is also called the number of "sites
(or degrees) of unsaturation"; this description is incom-
plete since hydrogen deficiency can result from cyclic
structures as well as from multiple bonds. The index is
thus the sum of the number of rings, the number of dou-
ble bonds, and twice the number of triple bonds.
lbe index of hydrogen deficiency can be calculated
for compounds containing carbon, hydrogen, nitrogen,
halogen, oxygen, and sulfur having the generalized
molecular formula, CnHmXxNyO" from the equation
Index = (n) (mI2) - (xI2) + (yI2) + 1
Thus, the compound C7H7NO has an index of
7 - 3.5 + 0.5 + 1 = 5. Note that divalent atoms (oxy-
gen and sulfur) are not counted in the formula.
For the generalized molecular formula O',f3l1'YlIJO,V,
the index = (rV) - (I12) + (IIII2) + 1, where 0' is H, D,
or halogen (i.e., any monovalent atom), f3 is 0, S, or any
other bivalent atom, 'Y is N, P, or any other trivalent
atom, and 0 is C, Si, or any other tetravalent atom. The
numerals I-IV designate the numbers of the mono-,
di-, tri-, and tetravalent atoms, respectively.
For simple molecular formulas, we can arrive at the
index by comparison of the formula of interest with the
molecular formula of the corresponding saturated com-
pound. Compare CoH6 and C6H 14 ; the index is 4 for the
former and 0 for the latter.
0- o
I II
NT
S+
H3 C
/"-CHI HC/ "0-
3
Dimethyl nitromethanc triphenylphosphine
sulfoxide oxide
FIGURE 1.12 "Polar" Lewis structures of dimethyl
sulfoxide, nitromethane, and triphenylphosphine
oxide that correctly account for the index of hydro-
gen deficiency.
lbe index for C7H7NO is 5, and a possible structure
is benzamide (see Figure 1.1). Of course, other isomers
(i.e., compounds with the same molecular formula) are
possible, such as
Note that the benzene ring itself accounts for four
"sites of unsaturation": three for the double bonds and
one for the ring.
Polar structures must be used for compounds con-
taining an atom in a higher valence state, such as sulfur
or phosphorus. Thus, if we treat sulfur in dimethyl
sulfoxide (DMSO) formally as a divalent atom, the
calculated index, 0, is compatible with the structure in
Figure 1.12. We must use only formulas with filled
valence shells; that is, the Lewis octet rule must be
obeyed.
Similarly, if we treat the nitrogen in nitromethane
as a trivalent atom, the index is 1, which is com-
patible with Figure 1.12. If we treat phosphorus in
triphenylphosphine oxide as trivalent, the index is 12,
which fits the Lewis structure in Figure 1.12. As an
example, let us consider the molecular formula
C 13H 9N20 4 BrS. The index of hydrogen deficiency
would be 13 - 10/2 + 2/2 + 1 = 10 and a consistent
structure would be
NO"
O,N~ >-~-f~ H
)-Bf
(Index of hydrogen deficiency 4 per benzene ring
and 1 per N02 group.)
The formula above for the index can be applied to
fragment ions as well as to the molecular ion. When it is
applied to even-electron (all electrons paired) ions, the
result is always an odd multiple of 0.5. As an example,
consider C7H sO+ with an index of 5.5. A reasonable
structure is

since 5 112 pairs of hydrogen atoms would be necessary
to obtain the corresponding saturated formula C 7H I60
(C nH2n+20). Odd-electron fragment ions will always
give integer values of the index.
Terpenes often present a choice between a
double bond and a ring structure. This question can
readily be resolved on a microgram scale by
catalytically hydrogenating the compound and rerun-
ning the mass spectrum. If no other easily reducible
groups are present, the increase in the mass of the
molecular ion peak is a measure of the number of
double bonds and other "unsaturated sites" must
be rings.
Such simple considerations give the chemist
very ready information about structure. As another
example, a compound containing a single oxygen atom
might quickly be determined to be an ether or a
carbonyl compound simply by counting "unsat-
urated sites."
1.5.4 Fragmentation
As a first impression, fragmenting a molecule with a
huge excess of energy would seem a brute-force
approach to molecular structure. The rationalizations
used to correlate spectral patterns with structure,
however, can only be described as elegant, though
sometimes arbitrary. The insight of such pioneers as
McLafferty, Beynon, Stenhagen, Ryhage, and Meyer-
son led to a number of rational mechanisms for
fragmentation. These were masterfully summarized
and elaborated by Biemann (1962), Budzikiewicz
(1967), and others.
Generally, the tendency is to represent the molecu-
lar ion with a localized charge. Budzikiewicz et a1.
(1967) approach is to localize the positive charge on
either a 7T bond (except in conjugated systems), or on a
heteroatom. Whether or not this concept is totally
rigorous, it is, at the least, a pedagogic tour de force. We
shall use such locally charged molecular ions in this
book.
Structures A, B, and C in Figure 1.13, for example,
represent the molecular ion of cyclohexadiene.
Compound A is a delocalized structure with one less
electron than the original uncharged diene; both the
electron and the positive charge are delocalized over
[or o' o·
A B c energy transitions, and to the stability of the fragments,
FIGURE 1.13 Different representa-
tions of the radical cation of cyclohexa-
diene.
1.5 INTERPRETATION OF EI MASS SPECTRA 17
the 7T system. Since the electron removed to form the
molecular ion is a 7T electron, other structures, such as
B or C (valence bond structures) can be used. Struc-
tures such as Band C localize the electron and the
positive charge and thus are useful for describing frag-
mentation processes.
Fragmentation is initiated by electron impact. Only
a small part of the driving force for fragmentation is
energy transferred as the result of the impact. The
major driving force is the cation-radical character that
is imposed upon the structure.
Fragmentation of the odd-electron molecular ion
(radical-cation, M' +) may occur by homolytic or
heterolytic cleavage of a single bond. In homolytic
cleavage (Scheme 1.3, I) each electron "moves" inde-
pendently as shown by a (single-barbed) fishhook: the
fragments are an even-electron cation and a free
radical (odd electron). To prevent clutter, only one of
each pair of fishhooks need be shown (Scheme 1.3, II).
In heterolytic cleavage, a pair of electrons "move"
together toward the charged site as shown by the
conventional curved arrow; the fragments are again
an even-electron cation and a radical, but here the final
charge site is on the alkyl product. (Scheme 1.3,///)
I
~ +. • +
II CH}-CH2 -O-R----7CH 3 +HzC=O-R
(;T .
III CH3 -CH2-CH2-Br CH 3-CH2-CH;+Br
CH3-~-CHr
IV CHj+H2C=CH
(Sch 1.3)
In the absence of rings (whose fragmenta-
tion requires cleavage of two or more bonds), most
of the prominent fragments in a mass spectrum are
even-electron cations formed as above by a single
cleavage. Further fragmentation of an even-electron
cation usually results in another even-electron cation
and an-even-electron neutral molecule or fragment
(Scheme 1.3, IV).
Simultaneous or consecutive cleavage of several
bonds may occur when energy benefits accrue from
formation of a highly stabilized cation and/or a stable
radical, or a neutral molecule, often through a well-
defined low-energy pathway. These are treated in
Section 1.5.5 (rearrangements) and in Section 1.6
under individual chemical classes.
The probability of cleavage of a particular bond is
related to the bond strength, to the possibility of low
both charged and uncharged, formed in the fragmenta-
tion process. Our knowledge of pyrolytic cleavages can
be used, to some extent, to predict likely modes of