The reactivity of [C3H3+]ions; a thermochemical study1

JOHN L. HOLMES
Ottuit,tr, Onr., Cantidti K I N 9B4
C1iernistr.yDepa/.rrnent, Uni~,ersityqf'Ott~iivc~,
AND
F. P. LOSSING
Division of Chemistry, !Vutionril Resrnich Council qfCcinclela, Ottcitz>cr,O I I ~Cnncldtr
., K I A OR6
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Received July 26, 1978

JOHNL. HOLMES and F. P. Lossr~c.Can. J. Chem. 57.249 (1979).

The loss of halogen atom from the molecular ions of compounds of formulae C3H3CI and
C,H,Br produces the cyclopropeniun~cation as daughter ion. Each reaction takes place with
appreciable reverse activation energy, most of which is partitioned into translational degrees

daughter ions at the thermochemical threshold (i.e. Ere, for these fragmentations is -
of freedom of the products. In marked contrast, the iodo-analogues generate [propargyl]+ as
0). It is
proposed that the reason for this behaviour lies in a large activation energy for the reaction
[cyclo-C,H,]+ + I' + [C,H,I]+'.

JOHNL. HOLMES et F. P. LOSSING.Can. J. Chem. 57.249 (1979).

La perte de I'atome d'halogene par les ions molCculaires des composes de formule C,H,Cl
et C,H,Br conduit au cation cpclopropenium colnme ion-fille. Chaque reaction se produit avec
une energie d'activation inverse importante; 011 en attribue le maximum a des degres de liberte
Can. J. Chem. 1979.57:249-252.

de translation des produits. En opposition marquee, les analogues iodes donnent lieu au
[propargyle]+ conlrne ion-fille au seuil thermochimique (a savoir Ere,pour ces fragmentations
est -- 0). On croit que la raison de ce comportemelit est attribuable a une energie d'activation
ClevCe pour la reaction [cycle C,H,]+ + I * + [C3H31]+:
[Traduit par le journal]
Introduction cation and therefore were considered less likely to be
The siniplest aromatic cation, cyclopropeniurn encountered i n experiment.
[C,H,I', has attracted considerable interest in recent Metastable ion studies have shown that the forma-
years and its heat of fornlatio~lnow is well estab- tion of [C,tf,l' fro111 a variety of precursors fre-
lished. The appearance potentials (A.P.)for [C3H31f quently generates a Inetastable peak of compos-
fragmellt ions from a number of C,H, and C,H, ite shape (7, 9-12). For example, the reaction
hydrocarbons lead to AH, values of 11.21 eV alld [c~H,I+ + [C3H3li + H 2 , yields a composite
11.08 eV, respectively (1). These results, obtained by peak c o l l l ~ r i s i n gtwo dish-topped
impact of monoenergetic electrons, are in good agree- POnents. broad comPollent corresponds to the
merit results from photoionisation studies (2-5) fornlatioll of cyclopropeniuln wit11 a reverse activa-
and photoele~tron-photoion coincidence techniques tion ellergY of 1.2 eV and the other (narroi$) com-
(6). The slightly higher values for ~ f f , [ c , H , ] ' de- ponent froln the forlnation of the propargyl
rived froln C3H, isonlers arise froll1 the small, corn- cation, [flC=:CCH,]+, with a reverse activation
mon reverse activation energy of 0.1 eV (7) for the energy of -0.5 eV (1 1). Formation of these two
reactiol, [c,H,I+. -, [c,H,I+ + H., ~h~ mean dai~ghterions has also been reported i n a photoion-
AH, = 1 1 . 1 2 0.1 e~ almost certaillly corresponds photoelectron coincidence study of the fragmenta-
to the cy~lopropeniumstructure, because the iso- tions of propargyl bromide and chloride ( 1 3).
lneric propargy1 [CHECCH, I + , has been In the Present work we have measured the appear-
shown by experiment to have an appreciably higher ance potentials (A.P.) of [C3H31+ C3H,X
AH, = 12.2 i- 0.1 e i T ( l ) .Recent ah initio calculatio~ls precursor (where = C17 Br, I,
using LCAO-SCF molecular orbital theory (8) are in [ C ~ H S I= CW3CgC- Or HC~C-CE-12p). The
agreement as to the greater stability of cyclopro- translational energies released in the corresponding
peniurn, A H , [ ~ ~ ~ ~ / ~ +- C=, H10.98
, ~ e ~ with
, metastable fragmentations and the fraction of the
AHf[propargyl]' 1.5 eV higher. These authors also reverse activation energy, E,,,, partitioned into
calculated AN,. for six other [ c 3 H 3 ] + structures, all translational degrees of freedom have been deter-
of which were much less stable than the propargyl mined.
Results and Discussion
'NRCC No. 17066. The ionisation potentials (1.P.f of C,H,X mole-
0008-4042/79/020249-O4$O1.OOIO
1979 National Research Council of CanadalConseil national de recherches du Canada
 CAN. J . CHEM. VOL. 57. 1979

cules and A.P. values for the C,H,+ ions produced

therefson? are presented in Table I , together with the
rnetastable peak n?easurements. The metastable
peaks are shown in Fig. I .
The observed 1 . p . ' ~are characteristic of' electron
removal from an acetylenic triple bond (14) for pro-
pargyl co~npounds(e.g. I.P.(CH,Cl=CH) = 10.36 eV,
I.P.(CH,CH,C::CH) = 10.18 eV) and for halogen
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ionisation in the case of the I-halopropynes. For the

apparent exception, propargyl iodide. the observed
I.P. is no doubt too lolv because of the difficulty of
preparing a sample of this co~llpound completely
free of its isomer, iodoal!ene (see Experimental); this
impurity would certainly be expected to have an I.P.
of ca. 9.1 eV.
The A.P. results for propargyl chloride agree well
-
+
with previous data (13); it is the same for both
- chlorocornpounds and lies well below that calculated
- for the propargyl ior? and 0.32 eV above the calcu-
lated threshold for generation of [cj~clo-C,H,]', see
-
2
.I
-J
Fig. 2. The metastable peak for C1' loss is basically
Can. J. Chem. 1979.57:249-252.

.
I
J the same for both compounds and that for propargyl
.- chloride is shown in Fig. I . It should be noted that
-- the metastable peak for I-chloropropyne is of lower
- intensity than the above and also appears to contain
-g a second (Gaussian) component situated in the
centres of each 'dish'. However, this additional peak
<5 2
,-
arises from a contribution from [M-HIf-Cl from

FIG.1. Metastable peak shapes for the reaction [C3H3XIt

-* +
C3H3+ X'. The x-axes do not have a common scale.
 HOLMES AND LOSSmTG
['3CC,H2Cl]+. The normal mass spectrum of
1-chloropropyne has an ion of appreciable abun-
dance at tnle 73, [C3H,Cl]+, and an intense meta-
stable peak arises from the fragmentation [C,H2Cl]+
4 [ C , H 2 ] I a + CI'. The apparent second component
described above also has a higher A.P. than tlie
dished chlorine-atom-loss peak. The above observa-
tions may also account for the composite inetastable
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peak reported by Sen-Sharma et 01. (12) in their
observations on propargyl chloride. although under
our experimental conditions none was observable.
The minimum energy released in the metastable
fragmentation, 0.28 eV, was evaluated from tlie dis-
tribution of released energies (as described elsewhere
(15)). It can be seen from the energy levels s h o n n in
Fig. 2 that the threshold daughter ion must be the
cyclopropeniun~ cation: and furthermore that the
fi-agnientation has a reverse activation energy, E,,,,
of 0.32 eV: about 90: of which is partitioned into
translational energy of the products.
Can. J. Chem. 1979.57:249-252.
The bromo c o n ~ p o u n d salso behaved similarly.
generating a cornInoii dish-topped metastable peak
and having a conlmon A.P. for [C,FJ13]'. Here,
Ere, = 0.83 el/ and a s ~ ~ i a l l efraction
r (-45";) is
partitioned illto product tra~lslationalenergy. Cyclo-
propeniunl again must be the threshold daughter ion
(see Figs. 1 and 2).
In marked contrast, the A.P. for [C,H,]+ from the
iodo compounds corresponds very closely to the cal-
culated threshold for [propargyll-. Furthermore,
AHt i C 3 ~ ; + X * )
A One of us (J.H.) thanks the National Research
: Erev
14.0
FIG.2. Energy diagram for the reactions [C3H3X]+'+
+
C 3 H 3 + X'. Metastable peak shapes are as illustrated above
the transition arrows.
25 1
both metastable peaks are of Gaussian type (Fig. 2)
and are associated with small energy releases; charac-
teristic indeed, of fragme~ltationshaving zero E,,,.
An explanation for the fragnientation behaviour of
these molecules which fits all the observations is
as follo\is.
Note from Table I that the a c t i ~ a t i o nenergy for
the reaction
[halogen]' + [cyclo-C3H,]+ + [C3H,X]+'
increases in the order E , > E ,,, > E,,,,,,. It is
suggested that E,,,, is so lrrrge that the fragmentatio~l
pathway of louest energy for the C,H31 iso~ners
becomes that leading to the propargyl cation, rather
than that producing the more stable [cyclopro-
peniuml+.
Experimental
Ionisation and appearance energies were measured using
energy selected electrons in an apparatus which has previously
been described (16, 17). Metastable peaks \\.ere measured on a
Kratos-AEI MS902S Mass Spectrometer under conditions of
good energy resolution (7). Propargyl chloride and bromide were
obtained from Aldrich Co. Propargyl iodide was prepared by
treating propargyl chloride with Nal in acetone (18), the
Finkelstein reaction. This reaction was carried out at 0-C and
purification was performed at the same temperature. In spite
of these precautions a small amount of iodoallene (2-3%) was
always produced. Any attempts to distill the product led to
polymet.isation and/or production of larger proportions of
iodoallene. The haloproppnes were prepared by the method of
Smith and ~McLeod(19) (chloride), Cleveland and Murray (20)
(bromide), and Grignard and Perichon (21) (iodide).
Cou~lcllof Canada for financ~aldsalstance for thls
research The authors are ~ndebtedto Dr. J. Krause
and Dr. M . Dakubu for ~ n \ a l u a b l eexper~mental
ass~stance.
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(1969).
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Spectrom. Ion Phys. 26,23 (1978).
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