Alkyl ammonium cation stabilized biocidal polyiodides with adaptable high density and low pressure

Article abstract of DOI:10.1002/chem.201402176

The effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high-temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine-rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I₂). Polyiodide anions, namely, I₃ ^-, I₅^-, which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm^-3 that are low-pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0-90.9 .

Full text of DOI:10.1002/chem.201402176

DOI: 10.1002/chem.201402176
Full Paper
&
Iodine Chemistry
Alkyl Ammonium Cation Stabilized Biocidal Polyiodides with
Adaptable High Density and Low Pressure
[a]
[b]
[a]
Chunlin He, Damon A. Parrish, and Jean’ne M. Shreeve*
Abstract: The effective application of biocidal species re-
quires building the active moiety into a molecular back
bone that can be delivered and decomposed on demand
under conditions of low pressure and prolonged high-tem-
perature detonation. The goal is to destroy storage facilities
and their contents while utilizing the biocidal products aris-
ing from the released energy to destroy any remaining
harmful airborne agents. Decomposition of carefully selected
iodine-rich compounds can produce large amounts of the
very active biocides, hydroiodic acid (HI) and iodine (I ). Poly-
2
À
À
iodide anions, namely, I3 , I5 , which are excellent sources of
such biocides, can be stabilized through interactions with
large, symmetric cations, such as alkyl ammonium salts. We
have designed and synthesized suitable compounds of
À3
adaptable high density up to 3.33 gcm that are low-pres-
sure polyiodides with various alkyl ammonium cations, deliv-
erable iodine contents of which range between 58.0–90.9%.
Introduction
Interest in polyhalides has con-
tinued to expand due to their
fascinating structural chemistry,
and also because of their wide
range of applications in the
fields of, for example, semicon-
ductors, superconductors, solar
Figure 1. Potential ingredients for ADWs.
cells, optical devices, porous ma-
[
1]
terials. The existence of hydro-
gen-bonding interactions in the
[
3]
molecules helps to stabilize the formation of interesting struc-
tures. The triiodide anion, which has been known for almost
Polyiodo compounds, such as triiodoimidazole, tetraiodo-
[4]
furan, tetraiodopyrrole, have high iodine contents, high den-
sities, and good thermal stabilities. However, there is no infor-
mation about properties, such as impact sensitivity, heat of for-
mation, and detonation properties. The expected low detona-
tion pressures and low energy of these polyiodo compounds
make them worthwhile candidates for ADWs (Figure 1).
[
2]
two centuries, is the most stable polyhalide. Recently, the
adaptable properties for polyiodide compounds with alkyl cat-
[
1b]
ions were reported; studies also showed that the decompo-
sition of iodine-rich compounds lead to large amounts of hy-
droiodic acid (HI) and iodine (I ), both of which exhibit strong
2
biocidal activity against biological agents, such as bacteria,
Polyiodide salts exhibit low or no vapor pressures, have high
densities, and high iodine content; furthermore, these materi-
als have been shown to be very effective against pathogenic
organisms in real-life situations, particularly, as chemical agents
that are effective in killing, for example, viruses, bacteria, and
[3]
fungi and yeasts, viruses, spores, and protozoan parasites.
Several iodine-rich compounds, which generate high percen-
tages of strong biocides, exhibit great potential as ingredients
for Agent Defeat Weapons (ADWs) have been reported by our
[
3b]
[4]
group (Figure 1).
eukaryotic parasites. However, there are a only a few poly-
iodide salts with heterocyclic cations, such as urotropinium
[5]
triiodide, bipyridinium triiodide, bipyridinium pentaiodide,
[
a] Dr. C. He, Prof. Dr. J. M. Shreeve
Department of Chemistry, University of Idaho
Moscow, ID 83844-2343 (USA)
[6]
and bipyridinium heptaiodide that have calculated densities
À3
of 2.73, 2.50, 2.95, and 3.37 gcm
(X-ray), respectively
E-mail: jshreeve@uidaho.edu
(
Figure 2). Unfortunately, the more interesting and more ener-
getic urotropinium triiodide is not very stable thermally, de-
[b] Dr. D. A. Parrish
Naval Research Laboratory
Code 6030, Washington DC, 20375-5001 (USA)
[5]
composing at 1298C.
In general, the thermal stability of polyiodides can be en-
hanced by both increasing the size and the symmetry of the
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201402176.
Chem. Eur. J. 2014, 20, 1 – 9
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anion. However, the longer carbon chain and the formation of
this cation would also decrease the oxygen balance dramatical-
ly. To explore the properties of such polyiodide salts, amines
1
6
–11 were selected as starting materials. The iodide salts 1a–
a and 8a–11 a were prepared from the corresponding amine
Figure 2. Polyiodides with N-heterocyclic cations.
with HI or iodomethane by controlling the stoichiometry of
the reaction. All of the iodide salts precipitated from ethanol
solvent and were collected by filtration and washed with cold
ethanol and dried under vacuum. Compound 7a was prepared
according to the literature from the corresponding chloride as
[
1e]
cation. Alkyl ammonium cations, such as N,N-dimethylhydra-
[
7]
[8]
zinium, 2,2-dimethyltriazanium, and some quaternized am-
[
9]
monium cation-based ionic liquids (with appropriate anions),
were shown to be hypergolic. Those N-containing alkyl cations
may help to increase the energy and also result in low pres-
sure when combining with polyiodide anions. It is known that
alkyl substituents reduce energy while concomitantly enhanc-
ing stability. The alkyl ammonium polyiodides should be ideal
materials to generate low-pressure detonations, as well as to
result in effective biocidal decomposition products. We believe
that polyiodide compounds have not been studied as ingredi-
ents in ADWs. Based on our continuing interest in seeking ef-
fective materials for bio-agent destruction, we synthesized and
characterized compounds of adaptable high density, low-pres-
sure polyiodides with various alkyl ammonium cations and
iodine percentages ranging from 58.0–90.9%.
[8]
shown in Scheme 2. With the pure iodide salts in hand, the
corresponding triiodide salts, 1b–8b, were prepared by react-
ing the iodides with stoichiometric amounts of elemental
iodine in ethanol, whereas triiodides, 9b–11 b, were obtained
in acetone in good yields and purities after removing acetone.
However, a mixture of triiodide (2b–5b, 7b, and 8b) salts and
the iodide starting materials were obtained likely arising from
the poor solubility of the iodides in ethanol solution. When the
reaction mixture in ethanol was heated at 508C and the sol-
vent was allowed to evaporate slowly to dryness, black triio-
dide salts (2b–5b, 7b, and 8b) were obtained in excellent
yields and pure enough to pass elemental analyses. Failure to
obtain 1b and 6b, with only the starting materials, 1a and 6a,
being recovered, may be due to their poor solubility in alcohol
or that the products were unstable under the conditions tried
Results and Discussion
(
Schemes 1 and 2).
The strongly basic properties of aliphatic amines allow them to
react easily with hydrogen iodide (HI) to form the correspond-
ing iodide salts. The reaction of alkyl dimethylamine with
methyl iodide should result in the formation of the N,N,N-tri-
methylammonium cation, which could stabilize the polyiodide
In a similar manner, when 2a–5a, 7a, and 8a were reacted
with additional two or more equivalents of elemental iodine,
only the corresponding triiodide salts rather than any higher
polyiodide salts were recovered. This may arise from the small
size of the cations, which may be incapable of stabilizing the
Scheme 1. Preparation of alkyl ammonium iodide and triiodide.
&
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In the packing diagram of
10b, the hydrogen bonds of
I···HÀC aid in the formation of
D network structure (Table 2).
3
Twin columns of triiodide anions
are pinned in position by the
networks of I···HÀC interactions
with the heads of cations as is
seen from the packing diagram
viewed along the a axis (Fig-
ure 4a). The two triiodide anions
are packed in a T-shaped pattern
with IÀI interactions (I1ÀI5
3.898 ꢁ) as shown in Figure 4b.
Further details are provided in
the Supporting Information.
The physical properties of all
iodide and polyiodide com-
pounds are listed in Tables 3 and
4
.
Most of the iodide com-
pounds with the exception of
a and 7b, which decompose at
76.0 and 111.28C, respectively,
7
1
have very good thermal stabili-
ties. The iodide salts, 1a–11 a,
have an iodine content ranging
from 60.70 (11 a) to 80.34% (1a),
whereas the polyiodide salts ex-
Scheme 2. Synthesis of quaternary ammonium iodides and polyiodides.
Table 1. Crystal data and structure refinement for 10b.
Empirical formula
9 24 6 2
C H I N
anticipated higher polyiodides. However, the di-pentaiodide,
1
0c, and tri-pentaiodide, 11 c, salts were prepared successfully
formula weight
temperature
wavelength
crystal system
space group
unit-cell dimensions
921.7
150(2) K
0.71073 ꢁ
monoclinic
1
P2 /m
a=9.489(2) ꢁ, a=908
b=7.7651(18) ꢁ, b=93.680(3)8
c=14.913(3) ꢁ, g=908
1096.6(4) ꢁ
2
perhaps benefiting from the stabilizing effect of the larger cat-
ions. Interestingly, in the case of 9a, the anion was found to
2
À
be I8 (confirmed by elemental analyses) rather than the di-
pentaiodide (Scheme 2). All the compounds obtained were
characterized by IR spectroscopy, differential scanning calorim-
1
etry (DSC), and elemental analysis. The same values for H and
3
volume
Z
13
C NMR chemical shifts in a common cation were found in the
À3
iodide and in the polyiodide salts. The structure of 10b was
further confirmed by X-ray single-crystal diffraction analysis.
A suitable crystal of 10b for X-ray analysis was grown from
acetone. Salt 10b crystallizes in the monoclinic space group
1 (À1238C)
2.791 mgm
2.724 mgm
8.488 mm
820
À3
1 (208C)
À1
absorption coefficient
F(000)
crystal size
3
0.21ꢂ0.06ꢂ0.01 mm
P2 /m (http://img.chem.ucl.ac.uk/sgp/large/011ay1.htm); the
q range for data collection
index ranges
2.15 to 26.378
1
crystal data and structure-refinement details are given in
Table 1, and the crystal structure is shown in Figure 3. The IÀI
bond lengths for I ÀI , I ÀI , I ÀI , and I ÀI are 2.8557(9),
À11 ꢀhꢀ11, À9ꢀkꢀ9, À17ꢀlꢀ18
reflections collected
independent reflections
completeness to q=26.378
absorption correction
max. and min. transmission
refinement method
data/restraints/parameters
9382
2409 [Rint =0.0454]
99.80%
Semi-empirical from equivalents
0.920 and 0.550
full-matrix least-squares on F
2409/0/118
1
2
2
3
4
5
5
6
2.9809(9), 2.9202(9), and 2.9116(9) ꢁ, respectively, which are
much shorter than the van der Waals (VDW) distance (4.3 ꢁ).
The two linear triiodide anions (I(1)-I(2)-I(3) 178.06(3), I(6)-I(5)-
I(4) 174.78(3)8) are located on both sides of the cation. The
atoms of I1, I2, I3, I4, I5, I6, C7, N1, C2, C3, C4, N5, and C8 are
co-planar; whereas the atoms of C6, C6A, C9, and C9A are
also located in another plane. Those two planes are perpendic-
ular to each other.
2
2
goodness-of-fit on F
0.981
final R indices [I>2s(I)]
R indices (all data)
largest diff. peak and hole
CCDC
1
R =0.0317, Rw =0.0716
2
R
1
=0.0443, Rw
2
=0.0776
À3
1.018 and À1.782 eꢁ
983933
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Figure 3. Crystal structure of 10b.
Table 2. Hydrogen bonds present in 10b.
DÀH···A
C7-H7A···I3
d(DÀH)
1.2400
d(H···A)
d(D···A)
<(DHA)
[
a]
2.7300
3.9105(9)
159.00
[a] Symmetrical operator codes : Àx, À1/2+y, Àz.
Figure 4. Packing diagram of 10b. Top: viewed from the a axis; bottom: in-
teractions between the two triiodide anions.
hibit an iodine content from 82.25 (11 b) to 90.91% (2b;
Table 5). An increase in iodine content destabilizes the corre-
sponding polyiodides (10a>10b>10c, 11 a >11 b >11 c).
The iodide compounds exhibit densities ranging from
2a could not be obtained due to the non-convergence of the
calculation. All the compounds exhibited low detonation pres-
À3
À3
1.73 gcm to 3.33 gcm . The introduction of the polyiodide
sures ranging from 0.94 to 10.05 GPa and velocities from 1800
À1
species results in an increase of density from 0.49 to
to 4610 ms . The increasing number of NÀNH moieties and
2
À3
1
.35 gcm compared to the corresponding precursor iodide
the number of nitrogen atoms present in the molecule result-
ed in increasing detonation velocity and pressure, whereas the
formation of polyiodide decreases the detonation pressure re-
sulting in the desired low pressure. Therefore, the energy and
iodine content for the polyiodide can be adapted and con-
trolled by choosing suitable cations in collaboration with the
anions of iodide, triiodide, or pentaiodide to achieve the ap-
propriate iodine content.
salt; furthermore, the formation of polyiodide also helps to im-
prove the oxygen balance and iodine content. The impact sen-
sitivity measurements were made by using standard Bundesan-
stalt fꢃr Materialforschung (BAM) techniques. All of the com-
pounds were found to be impact insensitive (>40 J). The heat
of formation of the cations for salts 1–10 were calculated by
employing Gaussian 03 (Revision D.01) by using the G2
[
10,11]
method.
The heat of formation of the cation for salts 11 a,
The decomposition products were calculated by using CHEE-
[15]
1
1 b, and 11 c was calculated via an isodesmic reaction (see the
TAH 6.0 by arbitrarily assuming the conditions of 1 atm at
298 K. The major products are listed in Table 5 in units of wt%.
By comparing the iodine content (column 9, Table 5) with the
[
12]
Supporting Information), and those of the iodide, triiodide,
[
13]
and pentaiodide anions were obtained from NIST. The heats
of formation for the salts can be obtained using Born–Haber
sum of I and HI in the products (column 10), it can be easily
2
[14]
energy cycles by using the lattice energy of the salts. How-
ever, the heat of formation for salt 9c could not be calculated
due to the lack of availability of a value for the heat of forma-
concluded that the anions in the salts were completely decom-
posed to I and HI; in most cases with the value of S(I +HI)
2
2
equal or slightly higher than that of % iodine due to the for-
2À
tion for I8
.
mation of HI. For 6a, 7a, 8a, 5b, and 7b, slightly lower S(I +
2
From the values of the heats of formation and experimental
HI) values were obtained because of the formation of CH I as
3
densities, the detonation pressures (P) and velocities (D) were
a product. The high percentage of effective biocides in the
products endows these compounds with great potential as an
ingredient for ADWs.
[
15]
calculated by using CHEETAH 6.0
in exhaust condition as
listed in Tables 3 and 4. The detonation properties of 1a and
&
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AVANCE 300) NMR spectrometer
operating at 300 and 75.48 MHz,
Table 3. Physical properties of iodide compounds.
[
a]
[b]
[c]
[d]
[e]
[f]
[g]
respectively, by using [D ]DMSO as
Comp. Structure
T
[
m
T
d
d
DH
f
8
DH
[kJg
f
8
OB
D
P
6
À3
À1
À1
À1
solvent and locking solvent unless
otherwise stated. The melting and
decomposition (onset) tempera-
tures were obtained on a differen-
tial scanning calorimeter (TA In-
struments Co., model Q10) at
8C]
[8C]
[gcm
]
[kJmol
]
]
[%]
[ms
]
[Gpa]
1
2
a
a
332.8 335.5 2.75
À319.5
À370.5
À1.01
À1.12
À40.5
À53.3
–
–
–
–
257.1
240.5
-
-
2.52
2.34
3
4
a
a
À348.7
À337.7
À0.97
À0.84
À64.6 2375
À63.6 3220
0.94
4.15
À1
a scan rate of 58Cmin . IR spectra
were recorded by using KBr pellets
for solids on a BIORAD model 3000
FTS spectrometer. Densities of the
polyiodide compounds were mea-
sured at 258C by employing a Mi-
192.3 312.4 2.07
318.1 322.5 2.44
5
6
a
a
À288.2
À0.54
À63.4 3310
À44.7 3370
4.76
6.58
cromeritics
AccuPyc 1330
gas
pycnometer. Elemental analyses
were obtained by using an Exeter
CE-440 elemental analyzer.
303.2 342.2 2.46
133.0 176.0 2.05
53.3
0.08
X-Ray analyses
7
8
a
a
45.2
0.22
À67.0 4610
À87.1 3920
10.05
6.58
A
purple plate of dimensions
3
0
.21ꢂ0.06ꢂ0.01 mm was mount-
[
h]
238.8 1.84
274.5 276.2 1.83
304.8 1.73
À60.8
-0.30
ed on a MiteGen MicroMesh using
a small amount of Cargille Immer-
sion Oil. Data were collected on
a Bruker three-circle platform dif-
9
1
a
À278.1
À328.8
À0.70
À0.79
À104.0 3480
À112.1 3400
4.41
4.00
0a
–
fractometer
equipped
with
a
SMART APEX II/Platinum 135
CCD detector. The crystals were ir-
radiated using graphite monochro-
[
h]
1
1 a
289.7 1.67
À180.9
À67
À117.1 3900
À31.7 6881
5.70
mated MoK radiation (l=0.71073).
a
An Oxford Cobra low temperature
device was used to maintain the
[
h]
TNT
–
295
1.65
À0.3
19.53
crystals at
a constant 150(2) K
during data collection. Data collec-
tion was performed and the unit
cell was initially refined using
[
a] Melting point. [b] Decomposition temperature. [c] Density measured by gas pycnometer (258C). [d] Heat of
formation calculated by using Gaussian 03. [e] Oxygen balance. [f] Calculated detonation velocity by using
Cheetah 6.0. [g] Calculated detonation pressure by using Cheetah 6.0. [h] Decomposes before melting.
[18]
APEX2 [v2010.3–0]. Data reduc-
tion was carried out using SAINT
[v7.68 A] and XPREP [v2008/2]. Corrections were applied for
[19]
[20]
Conclusion
Lorentz, polarization, and absorption effects using SADABS [v2008/
A series of polyiodide compounds with adaptable high-density,
low-pressure properties were synthesized, characterized, and
evaluated. The energies of the compounds are dominated by
[21]
1
]. The structure was solved and refined with the aid of the pro-
[22]
grams in the SHELXTL-plus [v2008/4] system of programs. The
full-matrix least-squares refinement on F2 included atomic coordi-
nates and anisotropic thermal parameters for all non-H atoms. The
H atoms were included using a riding model.
the cations; more NÀNH moieties and nitrogen atoms would
2
improve the detonation properties. The densities of the com-
À3
pounds were determined by the anion; a 0.49 to 1.35 gcm
density increase was obtained by the formation of polyiodide
General method for preparing iodide salts
(
triiodide and pentaiodide). The anions in these new salts are
For iodide salts 1a–6a, the corresponding amines 1–6 were react-
ed with stoichiometric amounts of HI in ethanol solvent at RT. The
precipitate formed was collected by filtration, washed with cold
ethanol, and dried under vacuum. Compound 7a was prepared by
using a similar method in the literature. Salts 8a–11 a were pre-
pared by quaternization of amines 8–11 in ethanol with iodome-
thane in stoichiometric quantities.
converted nearly completely to effective biocides, which make
them ideal candidates for ingredients used in ADWs.
[8]
Experimental Section
General methods
[
23]
Compound 1a
The commercially available amines 1–5 and 7–10, reagents from
[
16]
Alfa–Aesar and Acros Organics, were used as received. Amines 6
White plate shaped crystals, yield: 80%. M.p.: 332.88C; T
(onset): 335.58C. H NMR (300 MHz; [D ]DMSO): d=7.78 (6H, s,
NH ), 3.03 ppm (4H, s, CH ); C NMR (75.48 MHz; [D ]DMSO): d=
decomp
[17]
1
1
and 11 were prepared according to the literature procedures. H
6
1
3
13
and C NMR spectra were recorded on
a
300 MHz (Bruker
3
2
6
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[25]
Compound 4a
Table 4. Physical properties of polyiodide compounds.
White solid, yield: 64%. M.p.:
[
a]
[b]
[c]
[d]
[e]
[f]
[g]
Comp. Structure
T
[
m
T
d
d
DH
f
8
DH
[kJg
f
8
OB
[%]
D
P
1
92.38C; Tdecomp (onset): 312.48C.
À3
À1
À1
À1
8C]
[8C]
[gcm
]
[kJmol
]
]
[ms
]
[Gpa]
2.28
1
H NMR (300 MHz; [D ]DMSO): d=
6
[
[
h]
5.4 (6H, br, NH ), 2.91 (4H, t, CH ),
2
3
b
b
233.4 3.33
270.3 3.28
À188.8
À217.8
À0.23
À0.25
À17.2 1800
À23.1 2100
3
2
1
3
2
.60 ppm (4H, t, CH2); C NMR
h]
(75.48 MHz; [D ]DMSO): d=50.51,
6
2.56
3.56
3
6.51 ppm; IR (KBr): u˜ =3042,
2
932, 1574, 1484, 1314, 1288, 1194,
À1
4
5
b
b
138.6 253.9 2.67
120.0 283.7 3.21
À216.8
À0.24
À33.4 2350
À22.3 2630
1053, 992, 877, 807, 530, 501 cm
.
[25]
Compound 5a
63.8
0.05
4.78
White solid, yield: 81%. M.p.:
3
18.18C; Tdecomp (onset): 322.58C.
1
H NMR (300 MHz; [D ]DMSO): d=
[
h]
6
7
8
9
9
b
b
b
c
111.2 2.54
194.8 2.74
46.4
À83.2
À230.2
–
0.10
À0.18
À0.25
–
À26.3 2900
À35.1 2670
À42.3 2620
4.96
4.40
3.63
–
7
.53 (9H, s, NH ), 2.93 (6H, s, CH ),
3
2
1
3
2
.62 (6H, s, CH2);
C NMR
86.9
(75.48 MHz; [D ]DMSO): d=50.31,
6
3
1
7
6.4 ppm; IR (KBr): u˜ =3401, 1574,
191.8 220.8 2.88
146.9 214.0 2.95
448, 1125, 1080, 1051, 1007, 939,
À1
70, 529 cm ; elemental analysis
À31.7
–
calcd for C H N I (530.0): C 13.60,
6
21 4 3
H 3.99, N 10.57; found: C 13.40, H
.82, N 10.07.
1
1
0b
0c
207.5 272.3 2.75
142.4 178.0 3.10
À294.2
À182.0
À0.03
À0.13
À46.9 2560
À28.0 2360
3.28
3.29
3
Compound 6a
White solid, yield: 82%. M.p.:
11 b
135.9 275.0 2.45
À30.9
À0.02
À50.8 2800
4.23
303.28C; T
H NMR (300 MHz; [D ]DMSO): d=
(onset): 342.28C.
decomp
1
6
8
.02 (12H, s, NH ), 3.11ppm (6H, s,
2
13
CH2);
C NMR
(75.48 MHz;
[
D ]DMSO): d=38.8, 38.0 ppm; IR
6
(
1
9
KBr): u˜ =2982, 2904, 1572, 1487,
1
1 c
99.7
231.4 2.96
114.9
0.05
À30.8 2480
À31.7 6881
3.69
396, 1346, 1264, 1193, 1036, 966,
À1
42, 812, 540 cm ; elemental anal-
ysis calcd for C H N I (643.9): C
9.33, H 3.13, N 8.70; found: C
1
5
20 4 4
[
h]
TNT
–
295
1.65
À67
À0.3
19.53
0.09, H 3.03, N 8.60.
[a] Melting point. [b] Decomposition temperature. [c] Density measured by gas pycnometer (258C). [d] Heat of
formation calculated by using Gaussian 03. [e] Oxygen balance. [f] Calculated detonation velocity by using
Cheetah 6.0. [g] Calculated detonation pressure with Cheetah 6.0. [h] Decomposes before melting.
[8]
Compound 7a
White solid, yield: 57%. M.p.:
1
33.08C; Tdecomp (onset): 176.08C.
]DMSO): d=6.30 (4H, s, NH ), 3.43 ppm (6H,
]DMSO): d=60.1 ppm; IR (KBr):
1
3
1
6.33 ppm; IR (KBr): u˜ =3138, 2998, 2913, 1556, 1491, 1348, 1310,
026, 997, 789 cm .
H NMR (300 MHz; [D
6
2
À1
13
s, CH3); C NMR (75.48 MHz; [D
6
u˜ =3262, 3202, 3136, 3039, 3024, 2951, 1620, 1460, 1410, 1383,
À1
1
283, 1151, 1077, 957, 916, 839, 737, 504, 474 cm ; elemental anal-
[
24]
Compound 2a
ysis calcd for C H N I (203.0): C 11.83, H 4.96, N 20.70; found: C
2
10
3
1
White solid, yield: 73%. M.p.: 257.18C; H NMR (300 MHz;
D ]DMSO): d=7.70 (6H, s, NH); 2.88 (4H, s, CH ), 1.81 ppm (2H, t,
CH2); C NMR (75.48 MHz; [D ]DMSO): d=36.2, 25.0 ppm; IR (KBr):
11.99, H 4.88, N 19.72.
[
6
2
1
3
6
u˜ =3040, 2992, 2753, 2386, 1954, 1582, 1460, 1400, 1207, 1177,
À1
1153, 1090, 934, 768, 436 cm
.
Compound 8a
[
25]
Compound 3a
1
White solid, yield: 95%. Tdecomp (onset): 238.88C; H NMR (300 MHz;
1
13
White solid, yield: 76%. M.p.: 240.58C; H NMR (300 MHz;
D ]DMSO): d=4.35 (6H, s, NH ), 2.71 (2H, t, CH ), 2.60 ppm (2H, t,
[D ]DMSO): d=6.05 (2H, br, NH ), 3.25 ppm (9H, s, CH ); C NMR
(75.48 MHz; [D ]DMSO): d=57.3 ppm; IR (KBr): u˜ =3289, 3232,
3149, 3015, 2938, 1605, 1474, 1432, 1394, 1281, 1142, 1055, 941,
895, 743, 477 cm ; elemental analysis calcd for C H N I (202.0): C
6
2
3
[
6
3
2
6
1
3
CH2); C NMR (75.48 MHz; [D ]DMSO): d=48.64, 39.84 ppm; IR
6
À1
(
KBr) u˜ =3242, 3100, 3055, 1555, 1474, 1335, 1295, 1217, 1121,
3
11
2
À1
1
057, 1005, 965, 887, 864, 836, 768, 486 cm
.
17.83, H 5.49, N 13.87; found: C 17.71, H 5.36, N 13.35.
&
&
Chem. Eur. J. 2014, 20, 1 – 9
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6
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Full Paper
Compound 2b
Table 5. Major decomposition products of polyiodide salts [wt%,
kgkg ].
À1
Black solid, yield: 93%. Tdecomp (onset): 233.48C; IR (KBr): u˜ =3118,
À1
1
591, 1483, 1182, 1101, 926, 741, 569, 436 cm ; elemental analysis
Comp.
N
2
I
2
HI
(g)
CH
3
I C
(s)
CH
(g)
4
NH
(g)
3
Iodine S(I
[%] (%)
2
+HI)/
calcd for C H N I (837.6): C 4.30, H 1.44, N 3.34; found: C 4.38, H
3
12 2 6
(
g)
(g)
1
.56, N 3.21.
1
2
3
4
5
6
7
8
9
1
a
a
a
a
a
a
a
a
a
8.10 21.88 58.92 –
–
–
10.16 0.94 80.34 80.8
8.49 75.36 1.58
11.71 69.10 1.61
–
–
–
–
14.54
–
–
76.92 76.94
70.70 70.71
Compound 3b
0.87 16.71
10.26 3.43 16.94 63.13 63.13
1.74 15.84
–
63.08 0.05
Black solid, yield: 95%. Tdecomp (onset): 270.38C; IR (KBr) u˜ =3088,
10.71 70.26 1.59
71.84 71.85
7.31 78.84 78.13
À1
1
541, 1450, 1388, 1346, 1172, 1118, 1068, 993, 750, 514 cm ; ele-
2.69 51.65 26.48 0.76 3.86 4.38
4.27 38.74 23.19 0.75 7.56 3.07 19.97 62.51 61.93
1.91 44.97 17.59 0.42 8.56 7.64 14.54 62.81 62.56
mental analysis calcd for C H N I (866.6): C 5.54, H 1.74, N 4.85;
found: C 5.70, H 1.66, N 4.34.
4
15 3 6
7.02 61.78 1.67
6.77 59.63 1.67
8.54 56.38 1.65
0.48 90.77 0.14
4.85 86.63 1.25
6.16 82.37 1.34
–
–
–
–
–
–
7.54 22.00
8.74 23.19
9.65 23.78
1.81 3.16
0.38 6.90
1.35 8.78
–
–
–
63.44 63.45
61.29 61.3
58.02 58.03
0a
Compound 4b
11 a
2
3
4
5
7
8
9
1
1
b
b
b
b
b
b
b
0b
0c
3.48 90.91 90.91
Black solid, yield: 89%. M.p.: 138.68C; Tdecomp (onset): 253.98C; IR
–
–
87.86 87.88
83.70 83.71
(KBr): u˜ =3036, 1574, 1535 1447, 1346, 1292, 1130, 1076, 1000, 939,
À1
8
71, 772, 755, 528, 500 cm ; elemental analysis calcd for C H N I
6
20 4 6
1.47 70.48 17.57 0.25 2.69 2.61
6.19 53.69 28.77 0.82 0.99 4.22
3.49 88.44 88.05
(909.7): C 7.92, H 2.22, N 6.16; found: C 7.84, H 2.18, N 5.54.
–
–
–
–
–
–
–
83.34 82.46
83.52 83.52
83.89 83.91
82.61 82.62
88.79 87.70
80.57 80.57
87.36 87.37
6.14 82.14 1.38
3.09 82.54 1.37
3.04 81.24 1.38
2.15 86.46 1.24
3.95 79.17 1.40
2.57 86.14 1.23
–
–
–
-
–
–
0.69 9.64
3.34 9.68
3.94 10.40
2.80 7.35
4.48 10.99
2.92 7.14
Compound 5b
Black solid, yield: 91%. M.p.: 120.08C; Tdecomp (onset): 283.78C; IR
(KBr): u˜ =3102, 1566, 1499, 1460, 1433, 1292, 1080, 1047, 1011,
980, 907, 889, 784, 769, 567, 534 cm ; elemental analysis calcd for
11 b
À1
11 c
C H N I (1291.4): C 5.58, H 1.64, N 4.34; found: C 5.87, H 1.66, N
6
21 4 9
4
.31.
[
26]
Compound 9a
Compound 7b
White solid, yield: 52%. M.p.: 274.58C; T
(onset): 276.28C;
decomp
1
H NMR (300 MHz; [D ]DMSO): d=3.87 (4H, s, CH ), 3.16 ppm (18H,
Black, yield: 87%. Tdecomp (onset): 111.28C; IR (KBr): u˜ =3147, 1700,
1629, 1401, 1016, 616 cm ; elemental analysis calcd for C H N I
6
2
1
3
À1
s, CH3); C NMR (75.48 MHz; [D ]DMSO): d=57.1, 53.0 ppm; IR
6
2
10 3 3
(
9
KBr): u˜ =3004, 2970, 1630, 1488, 1472, 1448, 1403, 1219, 1129,
51, 920, 814, 745, 451 cm .
(456.8): C 5.26, H 2.21, N 9.20; found: C 5.29, H 2.27, N 8.85.
À1
Compound 8b
Black solid, yield: 94%. M.p.: 86.98C; Tdecomp (onset): 194.88C; IR
[
26]
Compound 10a
(
KBr): u˜ =3273, 3232, 3155, 3024, 1606, 1469, 1453, 1442, 1403,
À1
1
1277, 1247, 1142, 1072, 942, 909, 742, 482 cm ; elemental analysis
White solid, yield: 59%. M.p.: 304.88C; H NMR (300 MHz;
D ]DMSO): d=3.35 (4H, s, CH ), 3.14 (18H, s, CH ), 2.22 ppm (2H,
m, CH3); C NMR (75.48 MHz; [D ]DMSO): d=61.7, 52.6, 17.2 ppm;
calcd for C H N I (455.9): C 7.90, H 2.43, N 6.15; found: C 8.02, H
[
3
11 2 3
6
2
3
1
3
2.29, N 5.92.
6
IR (KBr): u˜ =3445, 3007, 2957, 1622, 1476, 1402, 1242, 1055, 972,
À1
9
44, 901, 761, 544 cm .
Compound 9b
Black solid, yield: 85%. M.p.: 191.88C; Tdecomp (onset): 220.88C; IR
(
KBr): u˜ =3019, 2988, 1473, 1466, 1456, 1432, 1407, 951, 917, 793,
[
17]
À1
Compound 11a
455 cm ; elemental analysis calcd for C H N I (907.7): C 10.59, H
8
22 2 6
2
.44, N 3.09; found: C 10.74, H 2.28, N 2.94.
1
White solid, yield: 63%. Tdecomp (onset): 289.78C; H NMR (300 MHz;
D ]DMSO): d=3.57 (6H, m, CH ), 3.17 (27H, s, CH ), 3.00 ppm (6H,
[
6
2
3
1
3
Compound 10b
m, CH2); C NMR (75.48 MHz; [D ]DMSO): d=61.3, 52.9, 46.2 ppm;
6
IR (KBr): u˜ =3456, 3005, 2972, 1478, 1353, 1281, 1234, 1177, 1118,
Orange solid, yield: 89%. M.p.: 207.58C; Tdecomp (onset): 272.38C; IR
À1
1
045, 967, 916, 866, 810, 795 cm ; elemental analysis calcd for
(
1
KBr): u˜ =3463, 3013, 1481, 1466, 1445, 1412, 1403, 1269, 1242,
140, 970, 941, 895, 764, 454 cm ; elemental analysis calcd for
C H N I (656.2): C 27.45, H 5.99, N 8.54; found: C 27.45, H 5.91, N
À1
1
5
39 4 3
8
.66.
C H N I (921.7): C 11.73, H 2.62, N 3.04; found: C 11.77, H 2.44, N
9
24 2 6
2
.99.
General method for preparing polyiodide salts
Compound 11b
For polyiodide salts, the respective iodide compounds were mixed
with elemental iodine in stoichiometric amounts in ethanol or ace-
tone; the mixture was stirred at 50–608C until all the solvent had
evaporated. The solid residue was dried under vacuum at 508C
overnight to obtain the corresponding polyiodide.
Orange solid, yield: 92%. M.p.: 135.98C; Tdecomp (onset) : 275.08C; IR
(KBr): u˜ =3452, 3013, 2951, 1470, 1442, 1416, 1231, 1173, 1109,
1038, 964, 946, 913, 793 cm ; elemental analysis calcd for
À1
C H N I (1417.6): C 12.71, H 2.77, N 3.95; found: C 12.94, H 2.64,
15
39 4 9
N 3.90.
Chem. Eur. J. 2014, 20, 1 – 9
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Compound 9c
[5] K. F. Tebbe, K. Nagel, Z. Anorg. Allg. Chem. 1995, 621, 225–228.
[
6] K. F. Tebbe, M. Bittner, Z. Anorg. Allg. Chem. 1995, 621, 218–224.
Black solid, yield: 85%. M.p.: 146.98C; Tdecomp (onset): 214.08C; IR
[7] Y. Zhang, H. Gao, Y. Guo, Y.-H. Joo, J. M. Shreeve, Chem. Eur. J. 2010, 16,
3114–3120.
À1
(
KBr): u˜ =3014, 2754, 1472, 1159, 1113, 983, 945 cm ; elemental
analysis calcd for C H N I (1161.5): C 8.27, H 1.91, N 2.41; found: C
[8] H. Gao, Y.-H. Joo, B. Twamley, Z. Zhou, J. M. Shreeve, Angew. Chem.
8
22 2 8
2
009, 121, 2830–2833; Angew. Chem. Int. Ed. 2009, 48, 2792–2795.
9] Y. Zhang, H. Gao, Y.-H. Joo, J. M. Shreeve, Angew. Chem. 2011, 123,
726–9734; Angew. Chem. Int. Ed. 2011, 50, 9554–9562.
8
.33, H 1.78, N 2.35.
[
9
Compound 10c
Black solid, yield: 84%. M.p.: 142.48C; Tdecomp (onset): 178.08C; IR
[
10] Gaussian 03, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.
Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven,
K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone,
B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsu-
ji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Na-
kajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P.
Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts,
R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Och-
terski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg,
V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K.
Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui,
A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko,
P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham,
C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford
CT, 2004.
(
8
KBr): u˜ =3018, 1477, 1464, 1410, 1271, 1241, 1139, 1053, 970, 941,
À1
99, 760, 456 cm ; elemental analysis calcd for C H N I (1429.3):
9
24 2 10
C 7.56, H 1.69, N 1.96; found: C 7.70, H 1.53, N 1.96.
Compound 11c
Black solid, yield: 90%. M.p.: 99.78C; Tdecomp (onset): 231.48C; IR
(
9
KBr): u˜ =3452, 3016, 1479, 1469, 1459, 1406, 1290, 1167, 1104, 961,
À1
18, 861 cm ; elemental analysis calcd for C H N I (2179.1): C
15
39 4 15
8
.27, H 1.80, N 2.57; found: C 8.33, H 1.62, N 2.51.
Acknowledgements
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Published online on && &&, 0000
&
&
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8
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ÝÝ These are not the final page numbers!

Full Paper
FULL PAPER
Agent defeat weapons: Adaptable
high-density and low-pressure poly-
iodides were prepared by the combina-
tion of alkyl ammonium salts with poly-
&
Iodine Chemistry
C. He, D. A. Parrish, J. M. Shreeve*
& – &&
&
À
À
iodide anions, namely, I3 , I5 . The
active biocides, hydroiodic acid (HI) and
Alkyl Ammonium Cation Stabilized
Biocidal Polyiodides with Adaptable
High Density and Low Pressure
iodine (I ) obtained from the decompo-
2
sition of those compounds are effective
to destroy storage facilities and their
contents (see figure).
Chem. Eur. J. 2014, 20, 1 – 9
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ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ