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1396

J . Chem. SOC. (A), 1969


Chemistry of Ni t ryl Chloride. Part 1.
By Ram Chand Paul," Darshan Singh, and K. C. Mal hot r a, Department of Chemistry, Panjab University,
Chandigarh-14, India
Nitryl chloride dissolves readily in sulphuric and disulphuric acids. Cryoscopic, conductometric, and Raman and
i.r. spectral studies of its solutions haveconfirmed that it gives nitronium ions. It forms complexes with strong
electron acceptors like boron trichloride and anti.mony pentachloride. Fromtheir conductance in nitromethane and
i.r. spectra the complexes havebeen found to beionic. Nitryl chloride also forms complexes with organic tertiary
bases. The ionic nature of these complexes has also been confirmed by conductances and i.r. spectra. We con-
clude that nitryl chloride is a source of nitroniumions rather than positivechlorine, as was postulated earlier.
AN improved method of preparation of nitryl chloride
and its convenient working range (m.p. -145" ; b.p.
-15") have increased its importance in organic syn-
tl ~esi s. ~~~ It is easily hydrolysed and from the products
it has been concluded5 that chlorine is bonded to
oxygen. However, microwave 6 and i.r. spectra 7 indi-
cated it to be a Y-shaped planar molecule in which
chlorine is attached to nitrogen. The N-Cl bond length
of 1.98 is longer than the sum of two covalent radii.
The N-Cl bond energy8 is 30.0 kcal./mole which is
considerably lower than the normal N-C1 covalent bond
energy of 38.4 kcal./mole. Thus the N-Cl bond in
nitryl chloride is weaker than normal. Nitryl chloride
has a low specific conductivity (<lo-' ohm-l cm.-l
at -40"), almost of the order of that of water. I ts
large quadrupole coupling constant and low dipole
moment make it interesting to study its chemistry.
This may throw some light on its structure and on the
overlap effect which determines the strength of this N-C1
bond.
EXPERIMENTAL
Conductance was measured in sulphuric and disulphuric
acids in cells similar to those used by Gillespie and his co-
worker~,~ having cell constants of 20-40 cm.-1. Molar
conductances in nitromethane and nitrobenzene were
determined in a cell with a constant of 3.84 cm.-l. The
cell was placed in an oil thermostat (25.0' & 0.02O) and a
precision measuring bridge type WBR No. 108 with
logarithmic indicator amplifier type TAV. IKC No. 034
(Wissenschaftliche Technische Werkstatten, Weilheim/Oby,
Germany) was used. The conductometric y factors were
obtained by comparison of the conductance at various
concentrations of the solute with that of potassium hydrogen
sulphate in the case of sulphuric acid and nitromethane in
the case of disulphuric acid.10
Cryoscopy was as by Gillespie and his co-workers.1
The value of v, the number of particles or ions produced per
mole of the solute, for both acids were calculated by well
established equations.l0? l1
1.r. spectra were recorded on a Perkin-Elmer No. 337
1 Hand Book of Preparative Inorganic Chemistry,' vol. I, p.
8 H. J . Schumacher and G. Sprenger, 2. anorg. Chem., 1929,
3 M, J . Collis and D. R. Goddard, J. Chem. SOC., 1958, 1952.
4 M. J . Collis, I;. P. Gintz, D. R. Goddard, and E. A. Hebdon,
5 F. See1 and J . Nogradi, 2. anorg. Chem., 1952, 269, 188.
L. Clayton, Q. Williams, and T. L. Weatherly, J . Chem.
513, Academic Press, New York, 1963.
182, 139.
Chem. a d Ind., 1955, 1742.
Phys., 1959, 30, 1328.
double beam grating spectrophotometer and emulsions
of the solids in mineral oils were pressed between sodium
chloride plates. For solids, sodium chloride plates were
used, but for solutions of nitryl chloride in strongly acidic
media thin Teflon sheets were used. The spectra were
recorded from 3800 to 600 cm.-l. Potassium bromide
plates reacted with these complexes and therefore could
not be used. All operations were carried out in a dry-box.
Nitryl chloride was prepared by the action of chloro-
sulphuric acid on anhydrous nitric acid, and purified by
passage through 3 or 4 traps of 96% sulphuric acid. It was
collected in a trap at - SO", and then fractionally distilled.
The straw-coloured samples had a conductance of less than
4 x lo-' ohm-l cin.-l at -40".
Antimony pentachloride (B.D.H.) and boron trichloride
(B.D.H.) were used without purification. Organic tertiary
bases were purified as usual. The exact composition of
100% sulphuric and disulphuric acids were adjusted from
their conductance and freezing points.
Concentrated solutions of nitryl chloride in sulphuric
and disulphuric acids were prepared by passing a slow
stream of nitryl chloride through weighed amounts of these
acids for 2 hr. These solutions were weighed to find the
amount of nitryl chloride dissolved. The loss of sulphur
trioxide in disulphuric acid during the passage of nitryl
chloride must be very low as nitryl chloride is highly soluble
in disulphuric acid and hardly any bubbles escaped.
Conductance and cryoscopic studies of nitryl chloride solu-
tions were carried out by adding small weighed amounts of
these solutions in the respective solvents. Conductometric
titrations between nitryl chloride and organic tertiary
bases were carried out in nitromethane. A weighed amount
of the base dissolved in nitromethane was put in the con-
ductivity cell and a fresh concentrated solution of nitryl
chloride in nitromethane of known concentration was used
as titrant. A microburette fitted with a silica-gel guard tube
was used for the addition of the titrant to avoid moisture.
Powdered solid solutes were added with a weight burette
with a wide-bore tap. All transferences, where possible,
were carried out in a dry-box.
Preparation of the Complexes of Nitryl Chloride with
Antimony Pentachloride and Boron Trich1oride.-Antimony
pentachloride (0.6 g.) was dissolved in sulphur dioxide at
-40" and excess of nitryl chloride was added. The
mixture was left for 1 hr. at -40, then slowly brought to
R. Ryason and M. K. Wilson, J. Chem. Phys., 1954, 22,
2000.
8 H. IT. Gordes and H. S. J ohnston, J . Amer. Chem. SOC., 1954,
'76, 4264.
K. J . Gillespie and J . B. Senior, Inorg. Chem., 1964, 3, 440.
lo K. J . Gillespie and I<. C. Malhotra, J . Chem. SOC. ( A) , 1967,
l1 S. J . Bass, R. J . Gillespie, and E. A. Robinson, J . Chem.
1994.
SOC., 1960, 821.
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Inorg. Phys. Theor. 1397
room temperature. Excess of nitryl chloride and the
solvent was allowed to escape, leaving pale crystals (0.8 g.).
These were repeatedly washed with dry carbon tetrachloride
to remove traces of nitryl chloride and were dried in ucccuu.
They decomposed at 112" (Found: Sb, 31.1; C1, 55.6.
KO,Cl,SbCl, requires Sb 31-92; C1, 55.94%). All attempts
to purify the compound failed as it was insoluble in most
solvents or reacted with them.
in a trap at -40'. Excess of nitryl chloride was added.
chloride can behave as in reactions (3), (a), or (5) depend-
No&1 -k 2H~S~o, -
N02C1 + 5H2S20, --).
N0,Cl + 3H2Sz07-
NO(OH)+Cl + HS3010- + H,SO,
(3)
C1++ NO++ 2HS,O,- + 4H,SO, (4)
NO2++ HS03C1+HS,Olo- + 2H,SO, (5)
Boron trichloride (1.0 g.) was dissolved in sulphur dioxide
The mixture was left at -40" for 2 hr. and then brought to
room temperature. The excess of nitryl chloride and
sulphur dioxide was allowed to escape leaving white crystals
(decomp. 86'). These were repeatedly washed with carbon
tetrachloride and dried i n uucuo. The cowplex could not be
recrystallised as it is insoluble in the conventional solvents
(Found: B, 5.1; C1, 71.7. NO,Cl,BCl, requires B, 5- 52;
C1, 7 1.35%).
Complexes of nitryl chloride with organic tertiary bases
were prepared as usual. A known weight of nitryl chloride
was dissolved in acetonitrile and to this excess of the base
in acetonitrile was added dropwise with constant stirring.
Pale yellow compounds separated in most cases but some-
times carbon tetrachloride or light petroleum had to be
added to isolate them. The mixtures were left for 1 hr.
and filtered in a dry atmosphere. The solids were re-
peatedly washed with dry carbon tetrachloride and dried
in. VUCUO. Analyses are given in Table 3. Molar conduct-
ances were measured at 25'.
RESULTS AND DISCUSSION
By analogy with nitrosyl chloride l2 (NOC1+ NO+
+ Cl-) one would expect nitryl chloride to yield positive
nitronium ion and negative chloride ion, yet at low
temperatures in the solid, liquid, and gaseous state it
reacts with ammonia to yield chloramine and ammonium
nitrite,13J4 suggesting that it gives positive chlorine and
negative nitrite ions. As nitronium is a strongly
electrophilic cation, it cannot be stabilised in a strongly
nucleophilic medium. Therefore the behaviour of
nitrylcliloride was studied in the weakly nucleophilic
sulphuric and disulphuric acids, which can stabilise such
cations.15J6
Nitryl chloride dissolves exothermically in these acids
to give highly conducting solutions. Its solubility is
much higher in disulphuric than in sulphuric acid.
Disulphuric acid is itself strongly dissociated and
ionised, and in it the bases are completely protonated
as l 7 in (l), and the ionisable chlorides are quantitatively
B + 2HzS20, -w
BH++ HS3OI0- + H,SO,
(1)
converted into chlorosulphuric acid as in (2). Nitryl
KC1 + 3HzS207-+
K+ + HS3010- + HS0,Cl + 2H,SO,
(2)
A. 3. Burg and G. W. Campbell, J . Amer. Chem. Soc., 1948,
13 NI. Schmeisser, 2. anorg. Chem., 1948, 255, 33.
14 H. H. Batey and H. H. Sisler, J . Amer. Chew. Suc., 1952,
15 R. J . Gillespie and J . B. Milne, Inovg. Chem., 1966, 5, 1577.
16 J . Ban, R. J . Gillespie, R. Kapoor, and K. C. Malhotra,
70, 1964.
74, 3408.
Canad. J . Chern., 1968, 46, 149.
ing upon its nature. If it has sufficiently basic oxygen it
may be protonated by strong acids (equation 3), or if it
is a source of positive chlorine ions it may react by
equation (4), or if a source of positive nitronium ion
by equation ( 5) . Conductometric and cryoscopic studies
in disulphuric acid show that nitryl chloride behaves
as in reaction (5), so it is a source of nitronium ions
rather than positive chlorine ions. Cryoscopic titrations
of these solutions against sulphur trioxide show that two
moles of sulphuric acid are formed per mole of nitryl
chloride, in agreement with reaction (5). The Raman
spectrum of a concentrated solution of nitryl chloride in
disulphuric acid shows a sharp absorption band at 1400
cm.2 which is characteristic of the nitronium ion in
strongly acidic media.l* The i.r. spectrum of this solu-
tion shows a sharp band at 2350 cm.-l indicating nitron-
ium ions. No other i.r.-active bands could be observed
for nitronium ions owing to the complicated spectrum of
disulphuric acid. These observations confirm that
nitryl chloride behaves like potassium chloride in
disulphuric acid.
TABLE 1
Conductivities at 25" and freezing points of solutions
of nitryl chloride
In R,S,O, I n H2S0,
102(Molality) (ohm-f crm-1) F.p. (ohm-1 cm.-l) F.p.
1.0 3.9826 34.98" 1.1426 10.17"
2.0 4.2792 34-88 1.3184 9-92
3-0 4.5580 34.73 1.6220 9.64
4.0 4.8826 34.60 1.7646 9.35
5.0 5.2383 34-46 1.9888 9-06
6-0 5.5626 34.29 2.2260 8-78
7.0 5,9324 34.12 2.4388 8.46
8.0 6.3045 33-96 2.6400 8.15
9.0 6.6098 33-61 2.7433 7. 80
10.0 6.9523 33.40 2-9406 7.58
12.0 7.6504 33.22 3.1488
14.0 8-2366 32-85
16.0 8.8580 32.43
18.0 9.43 16 32.03
20.0 9-8958 31.60
103~ 10' K
Unlike nitryl fluoride,lg the solubility of nitryl chloride
in lOOyosulphuric acid is limited, so conductance and
cryoscopic studies have been confined (Table 1) to dilute
solutions (0.12 molal). At low concentration, nitryl
chloride produces ca. 5 particles (V = 5) and two ions of
R. J . Gillespie and K. C. Malhotra, J . CJzem. SOC. ( A) , 1968,
18 R. J . Gillespie, J . B. Milne, and J . B. Senior, Inorg. Chem.,
l9 G. Hetherington, D. R. Hub, and P. L. Robinson, J . Ch e m
1933.
1966, 5, 1233.
SOC., 1955, 4041.
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1398
J . Chem. SOC. (A), 1969
high mobility (y = 2) in sulphuric acid. (The value of
v is never 5 and y is two only at lower concentrations.)
These values steadily decrease at higher concentration
which can be explained if the reaction takes place in
two stages (6) and (7). Reaction (6) is irreversible and
N0,Cl +- H2S04 + NO,++ HC1 + HSOd-
(6)
HC1+ 2H,SO, ----L H3T0 + HS0,Cl + HSO,- (7)
reaction (7) reversible. Gillespie and his co-workers 2o
have shown that hydrogen chloride can be quantitatively
removed from sulphuric acid by a stream of dry nitrogen.
Thus reaction (7) is never complete so values of v and y
are low. These low values cannot be attributed to the
formation of ion pairs (e.g., reaction 8) because the
NO2+ + HSO,- _+NO,HSO,
(8)
dielectric constant of sulphuric acid is high and the
solutions are dilute. There is no evidence that nitryl
chloride reacts (9) with hydrogen sulphate to form sul-
phate ions, as postulated by Robinson and his co-
N0,Cl +- HSO,- + NO," +- HC1 + SO: - (9)
workers l9 for nitryl fluoride in sulphuric acid. Since
our solutions are dilute, y is not significantly lower than 2.
Dissociation of nitryl chloride as 2N0,Cl _t N204 -k
C1, in these strong acids is ruled out as it would lead to
higher values of v and y in sulphuric acid owing to
reaction (10). We conclude that nitryl chloride ionises
N,O, -+3H2S04--t
NO2+ + NOi + H3+0 + 3HS0,-
(10)
in strongly acidic media to produce nitronium ions.
Further information on the nitryl chloride molecule
comes from a study of the coniplexes of nitryl chloride
with Lewis acids and bases. An attempt to isolate its
complexes with Lewis acids at -75" failed l4 but the
strong electron acceptor sulphur trioxide forms a complex
NOc,C1,S206, whose structure has not been studied. We
have isolated complexes with boron trichloride and
antimony pent achloride in liquid sulphur dioxide.
These complexes are moisture-sensitive and decompose
before melting. Their conductance in nitrobenzene
changes with time, either because of dissociation or
further nitration of the solvent. Their solutions in
nitromethane are fairly stable and their molar con-
ductance, comparable with those of uni-univalent
electrolytes, suggests that they are ionic. Seel and his
co-workers21 obtained similar results for a complex of
nitryl chloride and antimony pentachloride in liquid
chlorine. 1.r. spectra also support the ionic nature of
these complexes. The strong fundamental bands 361,
795, and 1685 cm.-l due to the NO, group are absent
while two new bands at 2355 and 3760 cm.-l are present.
The band2, at 2355 crn.-l is due to the asymmetric
20 R. J . Gillespie and E. ,4. Robinson, J . Amev. Cheilz. SOC.,
i 965, s7, 2428.
2 1 IT. F. Seel, J . Norgradi, and R. Posse, 2. anovg. Chern., 1952,
269, 198.
stretching vibration of nitronium ion (Table 2). The
bending mode (v2) at 540 cm.-l has not been observed on
a spectrometer having sodium chloride optics. Accord-
ing to Raman selection rule, nitronium ion must have
TABLE 2
Principal bands in the i.r. spectra of complexes of nitryl
chloride and Lewis acids
NO,+BCl,- NO,+SbCI,-
v1 +v3( N0, +) ......... 3760 w 3750
v,(NO,+) ............... 2360 \-.s. 2355
2v3(BC14)- ............ 1460
vl +vp +vQ ......... 1380
2vl +2v, ............... 1275
vi3 ........................ 690 670
one i.r.-inactive and Raman-active symmetrical stretch-
ing mode at 1400 cm.-l which is absent from the present
spectrum, but the band at 3760 cm.-l may be the com-
bination tone of this band and v3 (1400 + 2360). Simi-
lar observations have been made by Marcus and Fresco 23
in the spectrum of nitric acid and its solutions in various
solvents. The absence of an absorption band at 650
shows the absence of N-Cl bonds. All these
absorption bands confirm the presence of nitronium
ions in these complexes. The other bands present are
due to the anions. The broad and strong bands at
1455, 1380, 1275, and 690 cm.-l are due to the tetra-
chloroborate ions (BC1J-.24 However, for hexachloro-
antiinonate ion (SbClJ-, except for one sharp band at
670 cm.-l (v3) no other band was observed because of the
limited transparency of the optical window. We con-
clude that boron trichloride and antimony pentachloride
form ionic complexes by accepting chloride ions from
nitryl chloride e.g., reactions (1 1) and (12), confirming
that nitryl chloride is a source of nitronium ion.
N0,Cl + SbC1, + (NO,Cl,SbClJ -+
K0&1 + BC1, __t (N0,C1,BC13) -+
NOZ+-+SbC1,- (11)
KO,- + BC1,- (12)
Though acid halides are well known to form addition
complexes with organic tertiary bases, yet no complex
of nitryl chloride with organic tertiary bases has been
reported. 1.r. spectra of complexes of acid halides and
tertiary bases further support the mode of ionisation of
acid halides. We therefore prepared a number of coin-
plexes of nitryl chloride with organic tertiary bases and
oxygenated bases (Table 3). Conductometric titrations
between pyridine, quinoline, rx-picoline, morpholine, and
piperidine and nitryl chloride have been carried out in
acetonitrile to ascertain the stoicheiometry of these com-
plexes. There are two breaks in the conductance-
composition curve at molar ratio 1 : 1 and 1 : 2, cor-
responding to NO,Cl,B and NO,C1,2B. The initial
22 D. Cook, S. J . Kuhn, and G. A. Olah, J . Chenz. Phys., 1960,
33, 1669.
23 R. A. Marcus and J . M. Fresco, J. Chem. Phys., 1957, 27,
564.
24 T. C. Waddington and F. Klanberg, J . Chem. SOL, 1960,
2339.
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Inorg. Phys. Theor. 1399
increase in the conductance of the solution is due to the
solubility of the 1 : 1 complex, which may be ionic,
and the decrease beyond 1 : 1 composition is due to the
insolubility of 1 : 2 coniplexes. Molar conductances of
these complexes in various solvents (where solubility
permitted) indicate that the complexes are ionic. How-
ever urea and dimethyl sulphoxide complexes have
conductances below those for 1 : 1 electrolytes, so these
complexes are only weakly ionic.
formation of pyridiniuin chloride (PyH) +Cl-,=and in the
complexes of pyridine with selenium tetrachloride 26
and acetyl chloride.27 The bands at 1620, 1520, 1480,
1360, 1260, 1060, and 760 cm.-l are due to the free
pyridinium ion. A broad band at 2360 cm.-l due
to NO," has shifted to 2150 cm.-l owing to combination
with base. The band at 1670 cm.-l, which is one of the
fundamental bands of the NO, group, has completely
disappeared. We conclude that pyridine combines (13)
TABLE 3
Complexes of nitryl chloride with bases
Colour aiid Molar conductance
physical ALP. at 25" C1(%) C1("/) Base (%) Base (yo)
Base Stoicheionietry state (decomp.) (ohm-1 cm. mole-l) Found Required Found Required
P yridine
Pyridine
Quinoline
a-Picoline
Piperidine
Diethylamine
Triethylamine
Morpholine
Ethylene-
diamine
Dimethyl
sulphoxide
Urea
NO,Cl, (C5H,N)2 Yellow solid
2N0,Cl,C,H5N Pale yellow
NO,CI, (C,H,N) , Yellowish orange
NO,CI,C,H,N Yellow solid
NO,Cl, (C,H,,N) , Yellow solid
NO,Cl[(C,H,),NH], White solid
NO,Cl[(C,H,),N], Pale yellow
NO,Cl, (C,H,NO) Pale yellow
NO,CI(C,H,N,), Dark red liquid
NO,CI, (C,H,SO) I'ellow liquid
SO,CI, (N,H,CO), Sellow liquid
solid
solid
solid
solid
148'
58
156
164
116
102
90
124
-
-
-
* I n nitroinethane.
Further support of the ionic nature of nitryl chloride is
provided by the spectra of its complexes with organic
tertiary bases. For brevity, only the spectrum of the
pyridine compound (C,H,N),,N02C1 is reported (Table
4). The spectra of all these complexes indicate that
TABLE 4
1.r. spectra (cm.-l) of the complex of nitryl chloride
with pyridine
P yridine
3005s
1583m
1483
1439s
1370vw
1220s
1152s
1072s
1034s
995s
784s
705s
-2ssignnient
C-H
C=C and C=N
Stretch
C=C and C=X
C-H in plane deforniatioii
Pyridine ring breathing
Out-of-ring deformation
NO,Cl, (C,H,K)
2940s
2 150111
1620s
1520s
1480s
1360s
1260s
1200s
1 170w
1060s
1030w
1010s
930
855vs
7 6 0 ~ s
spectral bands of pure components change on complex
formation. I n these complexes absorption bands of
pyridine change similarly to those which occur on the
z5 N. N. Greenwood and I<. W7ade, J . Chem. Soc., 1958, 1671.
z6 A. W, Cordes and T. V. Hughes, Inorg. Chem., 1964, 3.
1640.
40.8 * 14.68 14.85 65.10 65.98
- 29.18 29.30 32.18 32.64
75.6 t 11-02 10.46 74.08 76.06
69-5 t 19.83 20.3 58-72 59-08
77. 8 t 13.48 14.16 66-88 67.59
62.7 t 16.72 15.68 64.06 64-18
36.6 * 21.44 22.05 '70.86 7 1-25
43.5 * 13-55 13.88 68-52 88.14
l i . 98 58.96 69-55 - 17.56
8.8 * 17.36 18.20 46.58 48-90
13. i 24.24 25.08 43.60 42.78
t I n acetonitriles.
with nitryl chloride to forin an ionic complex.
N02Cl + 2C,H5N -+NO,Cl,(C,H,N),
trends of perturbation in the vibration frequency of
groups in other tertiary bases occur on complex form-
ation with nitryl chloride. Since the i.r.-active bands
due to pyridinium ions and nitronium ions are present,
these complexes can be represented as resonance hybrids
of (I) and (11). As the complexes are ionic and have
Similar
[NO,(C5H$)z]+ + C1- (13)
ionizable chloride ions, it was of interest to study their
behaviour in disulphuric acid where they should behave
like other chloride ion donors (14). However, cryoscopic
(NO,B)Cl+ 3H&,07
and coiiductometric studies in disulphuric acid show
that they behave as in (15). Perhaps in disulphuric
(N0,B)Cl + 5H,S& +
NO2++ BH+ + ZHS,O,,- + HS0,Cl + 3H,SO, (15)
(NO,B)++ HS0,Cl - k HS,O,,- + 2H,SO,
(14)
27 R. C. Paul and S. L. Chadha, Spectvorhi?n. Acta, 1966, 22,
616.
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1400 J . Chem. SOC. (A), 1969
acid the proton (H+) is a far stronger acid than NO,+and
hence NO,+is replaced by the proton in these complexes.
Nitryl chloride can be represented by structures
(111)-(V). Structure (VI) is not reasonable as it
CI CI
I 1
CI i-
ll
violates Paulings adjacent charge rule and the N-Cl
bond is even longer than ordinary single bonds. Struc-
ture (111) (IV) would be expected to have a dipole
moment of 2.5 D. This could be reduced to the reported
0.53 D if there is a significant contribution of structure
(V) . sp Hybridisation of the chlorine-nitrogen bond
would produce a dipole moment opposite to that of the
NO, group, which is contrary to the observed value.
Though we cannot draw definite conclusions about the
structure of nitryl chloride from the chemical evidence,
yet we believe that there must be a significant contribu-
tion of structure (V) to the bond polarities. This is sup-
ported by calculations by Millen and Sinnott 28 of
quadrupole coupling constants, who found that the N-C1
bond in nitryl chloride is 12% ionic. Therefore, nitryl
chloride can be represented to a fair approximation as
(111) f--p (IV) +-+(V). The chlorine atom in nitrosyl
chloride is clearly negative. In nitryl chloride the
addition of a second oxygen atom to the nitrogen atom
considerably reduces its polarity but we conclude that
it has not made it positive.
[8/1751 Received, November 18th, 19681
D. J . Millen and K. M. Sinnott, J . Chew. SOL, 1958, 350.
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