Synthesis and characterization of a new family of energetic salts based on guanidinium cation containing furoxanyl functionality

Article abstract of DOI:10.1039/c4ra11732h

A new family of energetic salts based on a new guanidinium cation containing furoxanyl functionality, 1-(3′-methylfuroxanyl)methyleneamino guanidinium cation, were synthesized and well characterized by IR and multinuclear NMR spectroscopy, elemental analysis as well as differential scanning calorimetry. The structures of salts 1, 4, 5 and 6 were confirmed by single-crystal X-ray diffraction. Most of the salts decompose at temperatures over 180 °C. Furthermore, except for salts 7 and 9, the remaining energetic salts exhibit low impact sensitivities (15-40 J), friction sensitivities (120-360 N), and are insensitive to electrostatics. The detonation pressure values calculated for these salts range from 19.3 to 27.5 GPa, and the detonation velocities range from 7515 to 8402 m s^-1. These results make some energetic salts potential candidates for energetic materials with good thermal stabilities and low sensitivities. This journal is

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Synthesis and characterization of a new family of
energetic salts based on guanidinium cation
containing furoxanyl functionality
Cite this: DOI: 10.1039/x0xx00000x
Bo Wu, a Zhixin Wang,a Hongwei Yang,*a Qiuhan Lin,a,b Xuehai Ju,a Chunxu Lua
and Guangbin Cheng*a
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
A new family of energetic salts based on a new guanidinium cation containing furoxanyl
functionality, 1-(3'-methylfuroxanyl)methyleneamino guanidinium cation, were synthesized
and well characterized by IR and multinuclear NMR spectroscopy, elemental analysis as
www.rsc.org/
well as differential scanning calorimetry. The structures of salts
1, 4, 5 and 6 were
confirmed by single-crystal X-ray diffraction. Most of the salts decompose at temperatures
o
over 180 C. Furthermore, except for salts
7 and 9, the remaining energetic salts exhibit low
impact sensitivities (15-40 J), friction sensitivities (120-360 N), and are insensitive to
electrostatics. The detonation pressure values calculated for these salts range from 19.3 to
27.5 GPa, and the detonation velocities range from 7515 to 8402 m s-1. These results make
some energetic salts potential candidates for energetic materials with good thermal
stabilities and low sensitivities.
the NH moiety of azole, the highly aromatic azolate anion is
formed. The azolate anion pairs with various cations to form
Introduction
In recent years, high nitrogen content energetic compounds
offer distinct advantages over conventional carbon-based
energetic compounds.1 These high nitrogen content energetic
materials exhibit high enthalpy of formation, which is attributed
to a large number of C—N and N—N bonds within their
structures. Energetic compounds with high nitrogen, but low
hydrogen and carbon content also allow a good oxygen balance
to be achieved more easily. They are considered as prime
candidates for green energetic materials owing to their main
combustion products are molecular nitrogen. Among the most
exciting developments of high-energy density materials
(HEDMs), high nitrogen energetic salts continue to attract
azole-based energetic salts with good performance. Among the
various cations, the guanidinium cation (amino-, diamino- and
triaminoguanidinium cation) is one of the widely used cations
to synthesize novel energetic slats.6 To further enhance the
performance of energetic salts based on guanidinium cation,
introduce of energetic moieties into guanidinium frame is of
great interest. Classical energetic moieties such as nitro-,
nitramine- groups, possess strong electron-withdrawing effect,
which probably lead to the deprotonation of guanidinium. A N-
oxide derivative of furazan, furoxan, which has a ―latent‖ nitro
group within one side of its ring, is an effective structural unit
that is itself an explosive group. The aromatic character of
furoxan improves the thermal stability of molecules. By
introducing a furoxan ring into energetic molecules, the density
can be increased by ca. 0.06-0.08 g cm-3, and the detonation
velocity can also be increased by ca. 300m s-1.7 In the aspect of
energetic salts, as shown in Scheme 1, anions containing the
furoxan ring and other energetic groups or backbones bearing
acidic protons, have been investigated.8-11 In 2012, Z. Zhou et
al. synthesized a series of energetic monoanionic and dianionic
salts of 3,4-bis(1H-tetrazol-5-yl)furoxan with good thermal
stabilities and rather high densities.8, 9 In the next year, nine
1g, 1i,
2
considerable work.1c,
Principally, salt-based energetic
materials with high nitrogen content often possess advantages
over non-ionic molecules since these salts tend to exhibit lower
vapor pressures eliminating the risk of exposure through
inhalation. Moreover, they possess higher thermal stability than
their atomically similar nonionic analogues.
Azoles with energetic substituents such as nitro groups,3 azido
groups4 and nitramines,5 are important sources of anions to
design and synthesize energetic salts because of the practical
and theoretical significance of these unique compounds and the
diversity of their properties. Upon elimination of a proton from
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energetic salts based on 4-nitro-3-(5-tetrazolate)furoxan anion
4-10 were prepared from anion exchange of barium 5-
were also synthesized and fully characterized by them.10 These nitrotetrazolate, barium 5-nitrotetrazolate-2N-oxide, barium 4-
4-nitro-3-(5-tetrazole)furoxan-based energetic salts with amino-3-(5-tetrazolate)furazan, barium 5-azidotetrazolate,
relatively high densities are considered promising. In our barium 2,4-dinitroimiazolate, barium 5-nitroiaminotetrazolate
previous work, three energetic salts based on furoxanyl and barium 1,2-bis(4-(tetrazolato)-1,2,5-oxadiazol-3-yl)diazene
functionalized tetrazolate anion were synthesized and well with bis(1-(3'-methylfuroxanyl)methyleneamino guanidinium)
characterized.11 On the other hand, to the best of our knowledge, sulphate (
few energetic salts based on furoxanyl functionalized cation has
been reported in the literature.12 In the present work, a new
family of energetic salts based on a furoxanyl functionalized
aminoguanidinium cation (FAG cation) was synthesized. These
new energetic ionic salts were well characterized by IR and
multinuclear NMR spectroscopy, elemental analysis as well as
differential scanning calorimetry (DSC). Their key sensitivity
and explosive properties were investigated by experimental and
theoretical methods.
2) in water.
Scheme 2. Synthesis of salts 1-10.
NMR Spectroscopy
All compounds were characterized by 1H and 13C NMR
spectroscopic analysis in [D6]DMSO. Except for salts 6 and 8, all of
the hydrogen signals arise from the FAG cation. For FAG cation, the
proton signals of the methyl group are observed in a range from
2.34-2.37 ppm. The carbon resonance signals of the methyl group
are observed between 10.61 and 10.98 ppm. Their proton signals of -
CH=N- groups appear at δ = 8.11-8.33 ppm and the corresponding
resonance signals of the carbon atoms are observed between δ =
134.84 and 138.28 ppm. In addition, for compounds 1-10, the proton
signals of protonated guanidinium moieties are observed in a range
from δ = 7.00 to 8.14 ppm while the corresponding resonance
signals of the carbon atoms appear between δ = 156.42 and 159.25
ppm. For salts 4, 5 and 8, the proton signals of -NH- group are also
observed at δ = ca. 12 ppm. For salts 6 and 8, the proton signals
appearing at δ = 6.55 and 7.71 ppm, are assigned to the amino group
and –CH in the imidazole ring, respectively.
The 15N NMR spectra of salts 1, 4, 5 and 6 are shown as examples in
Figure 1. They were measured in [D6]DMSO solvent, and chemical
shifts are given with respect to CH3NO2 as external standard. The
assignments are based on the literature values of the similar
compounds.6a, 14 There are five nitrogen signals for the FAG cation
and the chemical shifts change little since the interactions between
FAG cation and those anions are similar. For FAG cation in 1, 4, 5
and 6, two nitrogen signals of furoxan ring are observed between δ =
-6.53 and -6.82 ppm, and between δ = -22.27 and -22.94 ppm,
respectively. The nitrogen signals of -CH=N- groups are observed in
a range from -53.62 to -55.16 ppm. The nitrogen signals of -NH-
groups range from -230.36 to -232.61 ppm. Furthermore, the
nitrogen signals of protonated guanidinium moieties are observed
Scheme 1. Energetic ionic salts containing furoxan
functionality
Results and discussion
Synthesis
The synthetic pathway to all of the new energetic salts is
depicted in Scheme 2. The starting material, 3-methyl-4-
furoxancarbaldehyde, can readily be prepared by treatment of
crotonaldehyde with sodium nitrite in acetic acid.13 1-(3'-
methylfuroxanyl)methyleneamino guanidinium salts
1 and 2
were synthesized via the condensation reactions of
aminoguanidine hydrochloride and bis(1-aminoguanidinium)
sulphate with 3-methyl-4-furoxancarbaldehyde in water
solution in high yield of 92% and 90%, respectively. Direct
reaction
guanidinium chloride (
pentahydrate resulted in the formation of salt
of
1-(3'-methylfuroxanyl)methyleneamino
) with disodium 5,5’-azotetrazolate
, which
1
3
deposited almost immediately in aqueous solution. As known,
one of the widely used methods for synthesis of the energetic
salts is based on metathesis reactions of the barium salts with
sulfates. The driving force of these reactions is the formation of
barium sulfate, which has a very low solubility in water and can
be easily removed by simple filtration. Herein, energetic salts
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between δ = -301.88 and -304.82 ppm. In the 15N NMR spectra of
and , the other nitrogen signals are from the nitrogen rich anions. significantly below the sum of van der Waals radii at 2.676(5)
4
,
hydrogen bonds, N5—H5b•••N3 and C3—H3a•••O2, are
5
6
Their chemical shift values are in good agreement with these of and 2.977(8) Å, respectively (rw(N) + rw(N) = 3.10 Å; rw(C) +
energetic ionic compounds with the same anions in the literature.14h, rw(O) = 3.21 Å).1f Furthermore, the D•••A distance of the
14i
hydrogen bonds N6—H6b•••O2iii (iii: 1+x, y, -1+z) are
significantly below the sum of van der Waals radii at 2.919(6)
Å (rw(N) + rw(O) = 3.07 Å).1f
1-(3'-Methylfuroxanyl)methyleneamino
guanidinium
5-
nitrotetrazolate (4) crystallizes in the monoclinic space group P21/c
with a cell volume of 1232.65(14) Å3 and four molecules in the unit
cell. The density from the X-ray crystal structure is 1.612 g cm-3. As
shown in Figure 2, the furoxan based aminoguanidinium cation is in
an E configuration. The protonated guanidinium moiety and furoxan
ring are planar with mean deviation of 0.0142 and 0.0081 Å,
respectively. The dihedral angle between them is 23.7°. The bond
lengths of the FAG cation are nearly indentical with that of salt 1. In
the 5-nitrotetrazolate anion, the nitro group is rotated by 11° out of
the plane of the tetrazole ring. The C—N and N—N bond lengths in
the tetrazolate ring vary from 1.3186(19) to 1.343(2) Å, which are in
good agreement with those in 5-nitrotetrazolate based energetic
salts.3b The crystal structure of 4 is strongly dominated by various
hydrogen bonds, illustrated in Figure 3 and the details are gathered
in the Supporting Information (see Table S6). The D•••A distances
of N9—H9•••N4i, N10—H10a•••N2ii, N11—H11a•••N1iii and
N11—H11b•••N8 (intra-molecular hydrogen bond) (i: 1-x, 1-y, -z;
ii: x, -1+y, z; iii: 1-x, -1/2+y, 1/2-z) are below the sum of van der
Waals radii at 2.8290(19), 2.988(2), 2.959(2) and 2.657(2) Å,
respectively (rw(N) + rw(N) = 3.10 Å).1f Furthermore, non-classical
intermolecular hydrogen bonds, C4—H4c•••O1iii and C5—H5•••O2i
(i: 1-x, 1-y, -z; iii: 1-x, -1/2+y, 1/2-z), involving the nitro group,
methyl group and -CH=N- group are observed.
Figure 1. 1, 4, 5 and 6
15N NMR spectrum of compounds
Single-Crystal X-ray Analysis
Single crystals of and 6, suitable for single-crystal X-ray
1
,
4
,
5
diffraction, were obtained by slow evaporation of aqueous
solutions at room temperature and normal pressure. Selected
crystallographic data are summarized in Table S2 in the
Supporting Information. The structures of
1
and
5
are presented
in Figure S1-S4. And the structures of
Figure 2-5.
4
and
6 are shown in
1-(3'-Methylfuroxanyl)methyleneamino guanidinium chloride
) crystallizes in the monoclinic space group P21 with a cell
(
1
volume of 480.18(7) Å3. A density of 1.526 g cm-3 was
determined from the X-ray crystal structure. As shown in
Figure S1, the molecules are in an E configuration. The furoxan
ring and C=N bonds are in a plane with mean deviation of
0.0143 Å resulting from the presence of large π-conjugation
system. The protonated guanidine moiety shows completely
planar assembly due to the electron delocalization effect in the
moiety. The dihedral angle between the two planes is 8.4°. The
bond length of C4-N3 is 1.277(6) Å, which lies in the range of
typical C-N double bond length values.15 Owing to the electron
delocalization effect, the C-N bond lengths of the protonated
guanidine moiety differ in a range of 1.317(6) Å to 1.337(6) Å,
Figure 2. Molecular structure of 4. Thermal ellipsoids are set to 50%
probability. Hydrogen atoms are included but are unlabelled for
clarity.
which are closed to those of C
—N bonds within the aromatic
furoxan ring. All hydrogen bonds observed in the structure of
1
can be considered moderately strong and the details of these
hydrogen bonds are summarized in Table S4 (Supporting
Information). As depicted in Figure S2, classical hydrogen
bonds involving the chloride anion and protonated guanidinium
moiety (N5—H5b•••Cl1, N6—H6a•••Cl1, N6—H6b•••Cl1i,
N4—H4a•••Cl1i, N5—H5b•••Cl1ii, i: 1-x, -0.5+y, -z, ii: 1+x, y,
z) are observed. Non-classical hydrogen bond C3—H3a•••Cl1ii
are also observed. The D•••A distances of intramolecular
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them of 5.9° and 2.3°. The exocyclic amine nitrogen atoms (N3,
N10) are out of the furazan plane by 0.0359 and 0.0104 Å,
respectively. As shown in Figure 5(a), wave-like layer structure of 6
was observed. The perpendicular distance between adjacent sheets is
3.385 Å, which is slightly shorter than the interplanar spacing in
graphite (3.4 Å).1a Because the asymmetric unit of 6 consists of two
independent sets of cations and anions, two different sets of
hydrogen bonds are formed for each pair within every single layer
(Figure 5(b)). These hydrogen bonds details are summarized in the
Table S10 in Supporting Information.
Figure 3. View along the b axes in the structure of 4.
1-(3'-Methylfuroxanyl)methyleneamino
guanidinium
5-
nitrotetrazolate-2N-oxide (5) crystallizes in the monoclinic space
group P21/n with a cell volume of 1252.67(17) Å3 (Figure S3). The
density of is 1.672 g cm-3. For the FAG cation in salt 5, the atoms in
protonated guanidinium moiety and furoxan ring are planar with the
mean deviation from their respective plane of 0.0085 and 0.0169 Å,
respectively. The dihedral angle between them is 17.9°. The bond
lengths of the C—C, C—N and N—N bonds within the FAG cation
are nearly identical with those in salts 1 and 4. For 5-nitrotetrazolate-
2N-oxide anion, the atoms in tetrazole ring and N-oxide oxygen
atom O1 are planar with the mean deviation of 0.0004 Å. The nitro
group is rotated by 4.3° out of the plane of the tetrazole ring. The
bond lengths of the C—N, N—N and N—O bonds are similar to the
known values from the literature.14i As shown in Figure S4, the
crystal structure of 5 is built up by various hydrogen bonds.
Classical N—H•••O and N—H•••N hydrogen bonds can be
considered strong hydrogen bonds with the D•••A distances of
N10—H10a•••O1i, N10—H10b•••O1ii, N11—11a•••N4iii, N11—
H11b•••N8 (i: -1/2-x, -3/2+y, 1/2-z; ii: 1/2+x, 1/2-y, 1/2+z; iii: x, -
1+y, z) at 2.930(3), 2.784(3), 2.956(3) and 2.641(3) Å, respectively,
which are shorter than the sum of van der Waals radii (rw(N) + rw(O)
= 3.07 Å; rw(N) + rw(N) = 3.10 Å).1f Additionally, non-classical
hydrogen bonds C4—H4a•••O2iv and C5—H5•••O3v (iv: x, -1+y, z;
v: 1/2+x, 1/2-y, 1/2+z) are also observed with D•••A distances of
3.296(3) and 3.398(3) Å, respectively. The details of hydrogen
bonds are summarized in Table S8 (Supporting Information).
Figure 4. Molecular structure of 6. Thermal ellipsoids are set to 50%
probability. Hydrogen atoms are included but are unlabelled for
clarity.
1-(3'-Methylfuroxanyl)methyleneamino guanidinium 4-amino-3-
(5-tetrazolate)furazan (6) crystallizes in the monoclinic space group
P21/c as a racemic twin. As presented in Figure 4, the asymmetric
unit consists of two crystallographically independent 4-amino-3-(5-
tetrazolate)furazan anions, two FAG cations as well as two water
molecules. The two FAG cations are in an E configuration. The
protonated guanidinium moiety and furoxan ring within the cation
are slightly twisted with the dihedral angles between them of 5.1°
and 9.9°. The atoms within either the protonated guanidinium
moieties or furoxan ring are planar with mean deviations from their
respective plane of 0.0036, 0.0111, and 0.0021, 0.0012 Å,
respectively. In two independent 4-amino-3-(5-tetrazolate)furazan
anions, the atoms in either tetrazolate anions or furazan rings are
planar with mean deviations from their respective plane of 0.0002,
0.0008, and 0.0011, 0.0033 Å, respectively. The tetrazole ring and
furazan ring are slightly twisted with the dihedral angles between
Figure 5. (a) A view of wave-like layer structure of 6. (b) View of
one layer in the structure of 6.
Thermal Behavior
The decomposition onset temperatures, sensitivities and energetic
data for 3–10 are summarized in Table 2. The decomposition onset
temperatures (Td, onset) of salts 3–10 were determined by differential
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scanning calorimetry (DSC) at a heating rate of 5 oC min-1. As oC, respectively, the decomposition onset temperatures of the other
shown in Table 2, only salts 8 and 10 have a melting process, energetic ionic compounds are higher than 180 oC. This lower
whereas the other compounds decompose directly. As known, a stability may be due to the decrease of hydrogen bonds network. In
thermal stability above 180 °C is an essential requirement for particular, the most stable energetic ionic compound was 3, whose
energetic compounds to adaptation for practical use.16, 17 Except for decomposition onset temperature is 213 oC.
compounds 6, 7 and 9, which decompose at 151.1, 138.9, and 168.5
Table 1. The physicochemical properties of 3–10 compared with 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and triaminotrinitrobenzene (TATB).
[a]
[c]
o [e]
[f]
Td
d1[b]/d2
ΔHco [d]
ΔHa
ΔHL
ΔHfo [g]
IS [h]
FS [i]
ESD [j]
P [k]
D [l]
Salts
[oC]
213.0
184.7
193.3
151.1
138.9
187.1
168.5
184.3
230
[g cm-3]
1.639/-
[kJ mol-1]
[kJ mol-1]
788.47
112.01
57.84
331.55
485.83
-129.87
402.04
1200.14
-
[kJ mol-1]
1045.45
462.31
457.42
446.42
459.72
446.83
1079.2
969.83
-
[kJ mol-1]
[J]
[N]
[J]
[GPa]
[m s-1]
3
961.93
961.93
961.93
961.93
961.93
961.93
961.93
961.93
-
704.95
611.63
562.35
847.06
988.04
385.23
284.77
1192.24
92.6
40
25
360
280
120
360
6
0.750
0.320
0.280
0.720
0.050
0.500
0.180
0.450
0.2[16]
-
19.3
26.3
27.5
23.8
24.7
24.7
20.6
21.9
35.2
30.5
7515
8312
8402
8082
8212
8016
7646
7768
8977
8176
4
1.700/1.612
1.718/1.672
1.670/1.547
1.641/-
5
15
6
38
7
2
8
9
1.700/-
32
300
<120
320
120
-
1.659/-
6
10
1.696/-
35
RDX[20]
TATB[17]
1.82
7.4
30-34
350
1.93
-
-
-
-139.7
[a] Decomposition onset temperature. [b] Density from calculation. [c] Density from single crystal structure. [d] Molar enthalpy of the formation of the
cation. [e] Molar enthalpy of the formation of the anion. [f] Lattice enthalpy. [g] Molar enthalpy of the formation of salt. [h] Impact sensitivity. [i] Friction
sensitivity. [j] Electrostatic discharge sensitivity. [k] Detonation pressure. [l] Detonation velocity.
presence of azido and nitramine groups within their structures,
Sensitivities
The sensitivities of the energetic salts
friction, and electrostatic discharge were tested by using
standard procedures.18 As summarized in Table 2, the impact
respectively. As illustrated in Table 2, the electrostatic
sensitivities of salts (0.750 J), (0.720 J), (0.500 J) and 10
(0.450 J) were significantly lower than that of RDX (0.200 J).16
The electrostatic sensitivity values of salts and were 0.280 J
3
6
8
3-10 towards impact,
5
9
and 0.180 J, respectively, which were comparable to that of
RDX (0.200 J).16 In agreement with other reports describing
sensitivity values were found to be in the range from 2 (
J ( and ). The friction sensitivity values differed in the range
from 6 ( ) to 360 N ( and ). Based on the classification
standard of sensitivities,19 salts
and are classified as less
sensitive due to their impact sensitivities of 40 and 38 J ,and
friction sensitivity of 360 N. The impact sensitivities of salts
7) to 40
3
6
sensitive azide4 compounds, salt
towards electrostatic discharge.
7 (0.050 J) was sensitive
7
3
6
3
6
Detonation Parameters
8
and 10 were 32 and 35 J, respectively, which were comparable The heat of formation of energetic salts is an important
to that of TATB (30 – 34 J).17 Salts
4 and 5 were less sensitive parameter when evaluating the performance of energetic salts.
to impact and friction than RDX (7.4 J, 120 N)16 due to their It can be calculated with good accuracy (including the heats of
impact sensitivities of 25 and 15 J, and friction sensitivities of formation of the FAG cation and anions, and the lattice energy
280 and 120 N, respectively. Salts
7 and 9 exhibited high of salts). The heats of formation of the cation and anions were
sensitivities towards impact and friction, because of the calculated by using the Gaussian 09 suite of programs.21 The
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geometric optimization of all the structures and frequency SHELXS-97 and expanded by using the Fourier technique. The non-
analyses for calculation of heats of formation was carried out hydrogen atoms were refined anisotropically. The hydrogenatoms
by using B3-LYP functional with 6-311+G** basis set.22 The were located and refined.
heat of formation of the furoxanyl fuctionalized guanidinium
cation (FAG cation) and anions were computed by using Caution: Although we experienced no difficulties in handling these
appropriate isodesmic reactions (Supporting information, energetic materials, small scale and best safety practices (leather
Scheme S1). The HOF of reference compounds are available gloves, face shield) are strongly recommended. Manipulation must
either from the experiments or from the high level computing be carried out in a hood behind a safety shield. Use of leather jacket,
like CBS-4M.23 The calculated heats of formation of salts
are summarized in Table 2, and that of the furoxanyl
fuctionalized aminoguanidinium cation (FAG cation) is 961.93 Starting Materials: 3-methyl-4-furoxancarbaldehyde,13 disodium
kJ mol-1. Energetic salts 10 exhibit positive heats of 5,5’-azotetrazolate pentahydrate,25 ammonium 5-nitrotetrazolate,3b
3-10 conductive equipment is strongly encouraged.
3
-
formation. Among them, salt 10 possess the highest at 1192.24 ammonium
5-nitrotetrazolate-2N-oxide,14i
4-amino-3-(5-
2,4-dinitro-1,3-
kJ mol-1 (RDX: 92.6 kJ mol-1, TATB: -139.7 kJ mol-1). To tetrazolyl)furazan,6c
5-azido-1H-tetrazole,4d
evaluate the performance of these new salts, the detonation imidazole,26 5-nitroiminotetrazole5d,
and 1,2-bis(4-(tetrazole)-
5e
velocity (D) and detonation pressure (P) were calculated by 1,2,5-oxadiazol-3-yl)diazene27 were synthesized according to
using the EXPLO5 v6.01 program.24 As summarized in Table 2, literature procedures.
the detonation velocities (D) of salts 3-10 are found in the range
from 7515 (comparable to TNT, 6881 m s-1) to 8402 m s-1
(comparable to TATB, 8176 m s-1). Detonation pressures (P) lie
in the range of 19.3–27.5 GPa, which is comparable with that of
TNT (2,4,6- trinitrotoluene, 19.53 GPa).
Synthesis
guanidinium chloride (1)
of
1-(3'-methylfuroxanyl)methyleneamino
A solution of aminoguanidine hydrochloride (5.0 mmol, 0.55 g) and
3-methyl-4-furoxancarbaldehyde (6.0 mmol, 0.77 g) in 20 mL H2O
Experimental
o
was stirred at 60 C for 12 h. The reaction mixture was cooled to 0
oC and the white precipitate was formed. Then the precipitated solid
was filtered off, washed with cold water and dried in vacuo to afford
General Methods
1
1H, 13C and 15N NMR spectra were recorded on 300 MHz (Bruker
AVANCE 300) nuclear magnetic resonance spectrometers operating
at 300, 75 and 30 MHz, respectively, by using [D6]DMSO as the
solvent and locking solvent unless otherwise stated. Chemical shifts
in 1H and 13C NMR spectra are reported relative to dimethyl
sulfoxide and those in 15N NMR spectra relative to CH3NO2. The
decomposition temperatures were determined by a differential
0.85 g of 1 as a colorless crystalline powder in a yield of 92%. H
NMR (300 MHz, [D6]DMSO): δ = 12.87 (s, 1H, -NH-), 8.39(s, 1H, -
CH=N-), 8.03 (s, 4H, -NH2), 2.37 (s, 3H, -CH3). 13C NMR (75 MHz,
[D6]DMSO): δ = 156.8 (-C(NH2)=NH2), 154.8 (-CONO), 137.8 (-
CH=N-), 113.2 (-CNO), 10.7 (-CH3) ppm. 15N NMR (30 MHz,
[D6]DMSO): δ = -6.82 (ONO), -22.44 (NO), -53.62 (-CH=N-), -
230.36 (-NH-), -301.88 (-NH2) ppm. IR (KBr): 3421 (s), 3166 (m),
2953 (w), 2840 (m) 1682 (s), 1616 (vs), 1538 (m), 1501 (w), 1460
(s), 1156 (m), 1038 (w), 1013 (w), 804 (w), 678 (w), 608 (m), 516
(w). Elemental analysis calcd (%) for C5H9ClN6O2 (220.62): C 27.22,
H 4.11, N 38.09; found C 27.11, H 4.09, N 37.91.
o
scanning calorimeter (DSC823e instruments) at a heat rate of 5 C
min-1. Infrared (IR) spectra were recorded on a Perkin-Elmer
Spectrum BX FT-IR instrument equipped with an ATR unit at 25 °C.
Analyses of C/H/N were performed with a Vario EL III Analyzer.
The electrostatic sensitivity tests were carried out with an Electric
Spark Tester ESD JGY-50 III. The sensitivities towards impact and
friction were determined by using a HGZ-1 drophammer and a BAM
friction tester.
Synthesis
guanidinium) sulphate (2)
of
bis(1-(3'-methylfuroxanyl)methyleneamino
A solution of bis(1-aminoguanidinium) sulphate (2.5 mmol, 0.62 g)
and 3-methyl-4-furoxancarbaldehyde (6.0 mmol, 0.77 g) in 20 mL
X-ray crystallography: The data for 1, 4, 5 and 6 were collected
with a Bruker three-circle platform diffractometer equipped with a
SMART APEX II CCD detector. A Kryo-Flex low-temperature
device was used to keep the crystals at a constant 173 K during the
data collection. The data collection and the initial unit cell
refinement was performed by using APEX2 (v2010.3-0). Data
Reduction was performed by using SAINT (v7.68A) and XPREP
(v2008/2). Corrections were applied for Lorentz, polarization, and
absorption effects by using SADABS (v2008/1). The structure was
solved and refined with the aid of the programs in the SHELXTL-
plus (v2008/4) system of programs. The full-matrix least-squares
refinement on F2 included atomic coordinates and anisotropic
thermal parameters for all non-H atoms. The H atoms were included
in a riding model. The structure was solved by direct methods with
o
H2O was stirred at 60 C for 12 h. The reaction mixture was cooled
o
to 0 C and the white precipitate was formed. Then the precipitated
solid was filtered off, washed with cold water and dried in vacuo to
afford 1.05 g of 2 as a colorless crystalline powder in a yield of 90%.
1H NMR (300 MHz, [D6]DMSO): δ = 8.14 (s, 5H, -CH=N-, -NH2),
2.35 (s, 3H, -CH3) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 157.2
(-C(NH2)=NH2), 155.0 (-CONO), 136.7 (-CH=N-), 113.1 (-CNO),
10.7 (-CH3) ppm. IR (KBr): 3452 (s), 3386 (s), 3156 (s), 3002 (s),
2171 (vw), 1691 (vs), 1612 (vs), 1459 (s), 1402 (m), 1382 (m), 1322
(w), 1198 (w), 1164 (s), 1082 (vs), 1037 (m), 971 (w), 922 (vw), 859
(w), 798 (w), 743 (w), 671 (w), 597 (w), 536 (w). Elemental analysis
calcd (%) for C10H18N12O8S (466.39): C 25.75, H 3.89, N 36.04;
found C 25.32, H 3.76, N 37.21.
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C4RA11732H
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Journal Name
RSC Advances
ARTICLE
Synthesis
guanidinium) 5,5’-azotetrazolate (3)
of
bis(1-(3'-methylfuroxanyl)methyleneamino
NH-), 8.28 (s, 1H, -CH=N-), 7.82 (s, 4H, -NH2), 2.36 (s, 3H, -CH3)
ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 158.64 (CNO2), 156.42
(-C(NH2)=NH2), 154.75 (-CONO), 138.28 (-CH=N-), 113.11(-CNO),
10.61 (-CH3) ppm. 15N NMR (30 MHz, [D6]DMSO): δ = -6.81
(ONO), -22.94 (NO),, -28.98 (N9), -30.07 (N11), -34.92 (N8), -55.16
(-CH=N-), -76.15 (N10), -102.67 (N7), -232.61 (-NH-), -304.82 (-
NH2) ppm. IR (KBr): 3424 (vs), 3239 (m), 3167 (m), 1686 (vs),
1605 (vs), 1548 (m), 1499 (w), 1474 (s), 1424 (s), 1382 (m), 1318
(s), 1229 (w), 1148 (m), 1058 (w), 1035 (w), 1000 (w), 853 (m), 730
(w), 666 (w), 607 (w). Elemental analysis calcd (%) for C6H9N11O5
(315.21): C 22.86, H 2.88, N 48.88; found C 21.39, H 2.71, N 50.11.
To
a
hot
solution
(~60
°C)
of
1-(3'-
methylfuroxanyl)methyleneamino guanidinium chloride (1) (0.146 g,
0.66 mmol ) in 10 mL of water was added a solution of sodium 5,5’-
azotetrazolate pentahydrate (0.100 g, 0.33 mmol ) in 10 mL of water.
The precipitate formed immediately. After 0.5 h later, the precipitate
was filtered, washed with H2O and dried in vacuo. 0.159 g of 3 was
afforded as orange solid in a yield of 90%. 1H NMR (300 MHz,
[D6]DMSO): δ = 8.33 (s, 1H, -CH=N-), 7.68 (s, 4H, -NH2), 2.37 (s,
3H, -CH3) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 173.65
(C2N10), 158.03 (-C(NH2)=NH2), 155.30 (-CONO), 136.96 (-CH=N-
), 113.24 (-CNO), 10.80 (-CH3) ppm. IR (KBr): 3448 (s), 3308 (m),
3128 (m), 2995 (m), 2857 (m), 2766 (w), 1689 (s), 1659 (vs), 1493
Synthesis
of
1-(3'-methylfuroxanyl)methyleneamino
guanidinium 4-amino-3-(5-tetrazolate)furazan (6)
(w), 1450 (s), 1394 (m), 1328 (w), 1195 (w), 1153 (m), 1040 (w), Barium hydroxide octahydrate (0.157 g, 0.5 mmol) was added to a
964 (w), 797 (w), 741 (w), 637 (w), 520 (w). Elemental analysis stirring aqueous solution of 4-amino-3-(5-tetrazolyl)furazan (0.153 g,
calcd (%) for C12H18N22O4 (534.42): C 26.97, H 3.39, N 57.66; 1 mmol) in 10 mL H2O. When the mixture was stirred for 0.5 h, the
found C 27.02, H 3.18, N 58.93.
aqueous solution of sulfate salt (2) (0.233 g, 0.5 mmol) in 10 mL
H2O was added dropwise resulting in the formation of a white
precipitate at room temperature. The solution was stirred for 1 h and
then filtered. Crystals suitable for X-ray structure determination
were obtained by slow evaporation of the resulting solution. 0.304 g
of 6 was obtained as block crystals in a yield of 90%. 1H NMR (300
MHz, [D6]DMSO): δ = 8.30 (s, 1H, -CH=N-), 7.86 (s, 4H, -NH2),
6.55 (s, 2H, -NH2), 2.35 (s, 3H, -CH3) ppm. 13C NMR (75 MHz,
[D6]DMSO): δ = 156.91 (-CN4), 156.67 (-C(NH2)=NH2), 154.81 (-
CONO), 152.04 (-CNO(CN4)), 141.26 (-CNO(NH2)), 138.13 (-
CH=N-), 113.13 (-CNO), 10.64 (-CH3) ppm. 15N NMR (30 MHz,
[D6]DMSO): δ = 19.50 (N8/N9), 7.03 (N11), -6.68 (ONO), -22.27
(NO (FAG cation)), -53.76 (-CH=N-), -64.04 (N7/N10), -65.64
(N12), -231.39 (-NH-), -303.29 (-NH2 (FAG cation)), -337.81 (-NH2
(furazan)) ppm. IR (KBr): 3462 (s), 32.7 (m), 2924 (m), 1701 (m),
1630 (vs), 1614 (w), 1562 (w), 1458 (m), 1433 (w), 1309 (w), 1151
(m), 1038 (w), 986 (w), 888 (w), 671 (w), 547 (w). Elemental
analysis calcd (%) for C8H10N13O3 (337.26): C 28.49, H 3.29, N
53.99; found C 28.21, H 3.22, N 54.67.
Synthesis of 1-(3'-methylfuroxanyl)methyleneamino
guanidinium 5-nitrotetrazolate (4)
Barium hydroxide octahydrate (0.237 g, 0.75 mmol) was added to a
stirring aqueous solution of ammonium 5-nitrotetrazolate (0.198 g,
1.5 mmol) in H2O (15 mL) and the resulting mixture was stirred at
25 oC for 0.5 h. The volume was then reduced to ∼5 mL on a rotary
evaporator with heating to remove as much ammonia as possible.
The pH was subsequently checked (7-8). Meanwhile, 0.350 g (0.75
mmol) of the sulfate salt (2) was dissolved in 10 mL of deionized
water at room temperature. Then, the barium 5-nitrotetrazolate
solution was added dropwise resulting in the formation of a white
precipitate. The solution was stirred for 1 h and then filtered.
Crystals suitable for X-ray structure determination were obtained by
slow evaporation of the resulting solution. 0.417 g of 4 was obtained
1
as colorless needle crystals in a yield of 93%. H NMR (300 MHz,
[D6]DMSO): δ = 11.96 (s, 1H, -NH-), 8.28 (s, 1H, -CH=N-), 7.82 (s,
4H, -NH2), 2.35 (s, 3H, -CH3) ppm. 13C NMR (75 MHz,
[D6]DMSO): δ = 170.17 (CNO2), 156.43 (-C(NH2)=NH2), 154.75 (-
CONO), 138.30 (-CH=N-), 113.10 (-CNO), 10.62 (-CH3) ppm. 15N
NMR (30 MHz, [D6]DMSO): δ = 18.11 (N8/N9), -6.53 (ONO), -
Synthesis
of
1-(3'-methylfuroxanyl)methyleneamino
guanidinium 5-azidotetrazolate (7)
22.32 (NO), -23.11 (NO2), -54.39 (-CH=N-), -62.77 (N7/N10), - A similar procedure was followed as that described above for 6. 5-
232.14 (-NH-), -303.45 (-NH2) ppm. IR (KBr): 3426 (s), 3359 (s), azido-1H-tetrazole (0.111 g, 1.0 mmol) was subjected to the method
3188 (m), 2854 (m), 1689 (vs), 1663 (m), 1616 (vs), 1543 (s), 1502 to give 0.269 g of 6 in a yield of 91%. 1H NMR (300 MHz,
(w), 1452 (s), 1424 (m), 1379 (w), 1322 (m), 1159 (s), 1008 (w), 840 [D6]DMSO): δ = 8.27 (s, 1H, -CH=N-), 7.86 (s, 4H, -NH2), 2.35 (s,
(m), 798 (w), 765 (w), 630 (w), 602 (w), 524 (w). Elemental analysis 3H, -CH3) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 159.04
calcd (%) for C6H9N11O4 (299.21): C 24.09, H 3.03, N 51.49; found (N3CN4), 156.81 (-C(NH2)=NH2), 154.89 (-CONO), 137.87 (-
C 24.22, H 3.8, N 52.93.
CH=N-), 113.19 (-CNO), 10.65 (-CH3) ppm. IR (KBr): 3486 (vs),
3443 (s), 2135 (s), 1698 (m), 1678 (m), 1639 (s), 1619 (vs), 1601
(vs), 1552 (w), 1464 (s), 1402 (m), 1379 (m), 1229 (w), 1197 (w),
1172 (w), 1039 (w), 801 (w), 744 (w), 707 (w), 600 (w), 472 (w).
Elemental analysis calcd (%) for C6H9N13O2 (295.22): C 24.41, H
3.07, N 61.68; found C 25.19, H 3.03, N 62.96.
Synthesis of
guanidinium 5-nitrotetrazolate-2N-oxide (5)
1-(3'-methylfuroxanyl)methyleneamino
A similar procedure was followed as that described above for 4.
Ammonium 5-nitrotetrazolate-2N-oxide (0.222 g, 1.5 mmol) was
subjected to the method to give 0.449 g of 5 as yellow crystals in a
Synthesis
of
1-(3'-methylfuroxanyl)methyleneamino
1
yield of 95%. H NMR (300 MHz, [D6]DMSO): δ = 11.96 (s, 1H, -
guanidinium 2,4-dinitro-1,3-imidazolate (8)
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7

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DOI: 10.1039/C4RA11732H
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ARTICLE
Journal Name
A similar procedure was followed as that described above for 6. 2,4- the most stable salt was
3
, which decomposed at 213 °C. Its
dinitro-1,3-imidazole (0.158 g, 1.0 mmol) was subjected to the decomposition onset temperature is higher than that of RDX (Td
1
o
method to give 0.315 g of 8 in a yield of 92%. H NMR (300 MHz, = 205 C). The impact sensitivity values of salts
3
-
10 lie in the
, the other
[D6]DMSO): δ = 11.99 (s, 1H, -NH-), 8.28 (s, 1H, -CH=N-), 7.79 (s, range between 2 and 40 J. Except for salts and
7
9
4H, -NH2), 7.71 (s, 1H, CH), 2.36 (s, 3H, -CH3) ppm. 13C NMR (75 salts were less sensitive to impact and friction than RDX (7.4 J,
MHz, [D6]DMSO): δ = 156.50 (-C(NH2)=NH2), 155.52 (-O2NCN2), 120 N). All salts possess positive heats of formation, whose
154.79 (-CONO), 148.32 (-O2NCNC), 138.20 (-CH=N-), 131.64 values lie in the range from 284.77 to 1192.24 kJ mol-1. With
(CH), 113.12 (-CNO), 10.63 (-CH3) ppm. IR (KBr): 3565 (m), 3501 the EXPLO5 v6.01 program, the detonation pressures and
(s), 3440 (s), 3394 (s), 3132 (w), 3008 (w), 2917 (w), 1697 (s), 1599 velocities were calculated. For energetic salts
(vs), 1516 (vs), 1470 (s), 1452 (s), 1398 (w), 1303 (s), 1224 (m), detonation pressures and velocities ranged from 19.3 to 27.5
1152 (m), 1041 (w), 1000 (w), 870 (w), 838 (w), 760 (w), 660 (w), GPa and 7515 to 8402 m s-1, respectively. Salt
had a
607 (w). Elemental analysis calcd (%) for C8H10N10O6 (342.23): C detonation pressure and velocity of 27.5 GPa and 8402 m s-1,
3-10, calculated
5
28.08, H 2.95, N 40.93; found C 28.66, H 2.82, N 41.38.
respectively, which was higher than that of TATB (D, 8176 m
s-1). Based on these results, some energetic salts based on the
FAG cation have the potential to be candidates for energetic
materials with good thermal stabilities and low sensitivities.
Synthesis of bis(1-(3'-methylfuroxanyl)methyleneamino
guanidinium) 5-nitroiminotetrazolate (9)
Acknowledgements
A similar procedure was followed as that described above for 6. 5-
nitroiminotetrazole (0.130 g, 1.0 mmol) was subjected to the method
to give 0.459 g of 9 in a yield of 92%. 1H NMR (300 MHz,
[D6]DMSO): δ = 8.11(s, 1H, -CH=N-), 7.00 (s, 4H, -NH2), 2.34 (s,
3H, -CH3) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 160.25 (-
C=N-NO2), 159.25 (-C(NH2)=NH2), 155.95 (-CONO), 134.84 (-
CH=N-), 113.32 (-CNO), 10.98 (-CH3) ppm. IR (KBr): 3470 (s),
3386 (s), 3148 (m), 2934 (m), 2855 (w), 1695 (m), 1611 (vs), 1500
(w), 1455 (s), 1394 (m), 1378 (m), 1301 (w), 1201, (w), 1158 (m),
1076 (w), 1037 (w), 801 (w), 602 (w), 530 (w). Elemental analysis
calcd (%) for C11H18N18O6 (498.38): C 26.51, H 3.64, N 50.59;
found C 27.15, H 3.59, N 52.06.
This work was supported by the Natural Science Foundation of
Jiangsu Province (BK2011696) and the National Natural
Science Foundation of China (No. 21376121).
Notes and references
a
School of Chemical Engineering, Nanjing University of Science and
Technology, Xiaolingwei 200, Nanjing, P. R. China, E-mail:
hyang@mail.njust.edu.cn (H. Yang); gcheng@mail.njust.ed.cn (G.
Cheng).
b
School of Materials Science & Engineering, Beijing Institute of
Technology, 5 South Zhongguancun Street, Beijing, P. R. China.
Electronic Supplementary Information (ESI) available: See
DOI: 10.1039/b000000x/
1
(a) D. E. Chavez, M. A. Hiskey, R. D. Gilardi, Angew. Chem. 2000,
112, 1861; Angew. Chem. Int. Ed. 2000, 39, 1791; (b) M. V. Huynh,
M. A. Hiskey, D. E. Chavez, D. L. Naud, R. D. Gilard, J. Am. Chem.
Soc. 2005, 127, 12537; (c) H. Gao, J. M. Shreeve, Chem. Rev. 2011,
111, 7377; (d) V. Thottempudi, J. M. Shreeve, J. Am. Chem. Soc.
2011, 133, 19982; (e) V. Thottempudi, F. Forohor, D. A. Parrish, J.
M. Shreeve, Angew. Chem. 2012, 124, 10019; Angew. Chem. Int. Ed.
2012, 51, 9881; (f) T. M. Klapötke, F. A. Martin, J. Stierstorfer,
Chem. Eur. J. 2012, 18, 1487; (g) A. A. Dippold, T. M. Klapötke, J.
Am. Chem. Soc. 2013, 135, 9931; (h) P. Yin, D. A. Parrish, J. M.
Shreeve, Chem. Eur. J. 2014, 20, 6707; (i) J. Zhang, J. M. Shreeve,
J. Am. Chem. Soc. 2014, 136, 4437.
Synthesis
of
bis(1-(3'-methylfuroxanyl)methyleneamino
guanidinium) 1,2-bis(4-(tetrazolato)-1,2,5-oxadiazol-3-yl)diazene
(10)
A similar procedure was followed as that described above for 6. 1,2-
Bis(4-(tetrazole)-1,2,5-oxadiazol-3-yl)diazene (0.302 g, 1.0 mmol)
was subjected to the method to give 0.570 g of 10 in a yield of 85%.
1H NMR (300 MHz, [D6]DMSO): δ = 8.27 (s, 1H, -CH=N-), 7.74 (s,
4H, -NH2), 2.36 (s, 3H, -CH3) ppm. 13C NMR (75 MHz,
[D6]DMSO): δ = 156.69 (-C(NH2)=NH2), 156.07 (-CN4), 154.83 (-
CONO), 151.30 (-CNO(CN4)), 150.43 (-CNO(N2)), 137.99 (-CH=N-
), 113.20 (-CNO), 10.62 (-CH3) ppm. IR (KBr): 3454 (vs), 2964 (w),
2821 (w), 1693 (s), 1614 (vs), 1551 (m), 1516 (m), 1455 (s), 1416
(m), 1386 (w), 1154 (m), 1082 (w), 1040 (w), 1002 (w), 867 (w),
807 (w), 598 (w). Elemental analysis calcd (%) for C16H18N26O6
(670.48): C 28.66, H 2.71, N 54.32; found C 29.02, H 2.69, N 55.81.
2
3
(a) D. Fischer, T. M. Klapötke, M. Reymann, J. Stierstorfer, Chem.
Eur. J. 2014, 20, 6401.
(a) H. Gao, C. Ye, O. D. Gupta, J. C. Xiao, M. A. Hiskey, B.
Twamley, J. M. Shreeve, Chem. Eur. J. 2007, 13, 3853; (b) T. M.
Klapötke, P. Mayer, C. M. Sabaté, J. M. Welch, N. Wiegand, Inorg.
Chem. 2008, 47, 6014; (c) Y. Zhang, Y. Guo, Y. H. Joo, D. A.
Parrish, J. M. Shreeve, Chem. Eur. J. 2010, 16, 10778; (d) Y. Zhang,
D. A. Parrish, J. M. Shreeve, Chem. Eur. J. 2012, 18, 987; (e) Y.
Conclusions
A new series of nitrogen-rich energetic salts based on furoxanyl
fuctionalized guanidinium cation (FAG cation) were prepared
and well characterized with NMR and IR spectra, differential
scanning calorimetry (DSC) and elemental analysis. Single
Zhang, D. A. Parrish, J. M. Shreeve, J. Mater. Chem. A 2013,
(a) T. M. Klapötke, J. Stierstorfer, J. Am. Chem. Soc. 2009, 131, 1122;
(b) K. Wang, D. A. Parrish, J. M. Shreeve, Chem. Eur. J. 2011, 17
1, 585.
4
,
14485; (c) T. M. Klapötke, D. G. Piercey, J. Stierstorfer, Chem. Eur.
J. 2011, 17, 13068; (d) D. Izsák, T. M. Klapötke, R. Scharf, J.
Stierstorfer, Z. Anorg. Allg. Chem. 2013, 639, 1746.
crystal X-ray measurements were accomplished for salts
1
,
4
,
5
7
and
and
6
9
. According to the DSC results, Except for the salts
, the decomposition onset temperatures (Td, onset) of the
6
,
remaining energetic salts are higher than 180 °C. In particular,
8 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C4RA11732H
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Journal Name
RSC Advances
ARTICLE
5
(a) H. Xue, H. Gao, B. Twamley, J. M. Shreeve, Chem. Mater. 2007, 19 Impact: insensitive > 40 J, less sensitive ≥ 35 J, sensitive ≥ 4 J, very
19, 1731; (b) H. Gao, Y. Huang, C. Ye, B. Twamley, J. M. Shreeve,
Chem. Eur. J. 2008, 14, 5596; (c) Y. H. Joo, J. M. Shreeve, Angew.
Chem. 2009, 121, 572; Angew. Chem. Int. Ed. 2009, 48, 564; (d) N.
Fischer, K. Karaghiosoff, T. M. Klapötke, J. Stierstorfer, Z. Anorg.
sensitive ≤ 3 J. Friction: insensitive > 360 N, less sensitive: 360 N,
sensitive < 360 N and > 80 N, very sensitive ≤ 80 N, extremely
sensitive ≤ 10 N; according to the UN Recommendations on the
Transport of Dangerous Goods.
Allg. Chem. 2010, 636, 735; (e) T. Fendt, N. Fischer, T. M. 20 Q. Zhang, C. He, P. Yin, J. M. Shreeve, Chem. Asian J. 2014,
9, 212.
Klapötke, J. Stierstorfer, Inorg. Chem. 2011, 50, 1447; (f) N. Fischer, 21 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
T. M. Klapötke, J. Stierstorfer, C. Wiedemann, Polyhedron 2011, 30
2374; (g) A. A. Dippold, T. M. Klapötke, F. A. Martin, S.
Wiedbrauk, Eur. J. Inorg. Chem. 2012, 2012, 2429; (h) N. Fischer,
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