Interaction of 1,3,2,4-benzodithiadiazines and their 1-Se congeners with Ph3P and some properties of the iminophosphorane products

Article abstract of DOI:10.1021/ic102565x

Interaction between Ph₃P and 1,3,2,4-benzodithiadiazine (1); its 6,7-difluoro (2), 5,6,8-trifluoro (3) and 5,6,7,8-tetrafluoro (4) derivatives; and 5,6,8-trifluoro-3,1,2,4-benzothiaselenadiazine (5) proceeded via a 1:1 condensation to give Ph₃P=N-R iminophosphoranes (1a-5a, R = corresponding 1,2,3-benzodichalcogenazol-2-yls), which are inaccessible by general approaches based on the Staudinger and Kirsanov reactions. In contrast, neither Ph₃As nor Ph₃Sb reacted with 1 and 4. Molecular structures of 1a-5a and 5 were confirmed by X-ray diffraction (XRD). The crystals formed by chiral molecules of 2a-5a were racemic, whereas the crystal of 1a was formed by a single enantiomer. In all of the Ph₃P=N-R derivatives, one of the Ph rings is oriented face-to-face to the hetero ring, R. Upon heating to ～120 °C in squalane (1a, 3a, 4a) or dissolving in chloroform at ambient temperatures (1a, 2a, 4a), the Ph₃P=N-R derivatives generated the 1,2,3-benzodithiazolyls (1b-4b, respectively) whose identity was confirmed by electron paramagnetic resonance (EPR). 2,1,3-Benzothiaselenazolyls 5b and 6b were detected by EPR as the main paramagnetic products of solution thermolysis of 5 and its 5,6,7,8-tetrafluoro congener (6), respectively. Passing a chloroform solution of 4a through silica column unexpectedly gave 5-6-6-6 tetracyclic (9) and 6-10-6 tricyclic (10) sulfur-nitrogen compounds, which were characterized by XRD.

Full text of DOI:10.1021/ic102565x

ARTICLE
pubs.acs.org/IC
Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners
with Ph3P and Some Properties of the Iminophosphorane Products
Alexander Yu. Makarov,† Vladimir V. Zhivonitko,‡ Arkady G. Makarov,† Samat B. Zikirin,§,‡
Irina Yu. Bagryanskaya,† Victor A. Bagryansky,§ Yuri V. Gatilov,† Irina G. Irtegova,† Makhmut M. Shakirov,†
and Andrey V. Zibarev*,†,‡
†Institute of Organic Chemistry, ‡International Tomography Center, and §Institute of Chemical Kinetics & Combustion,
Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
‡Department of Physics, National Research University—Novosibirsk State University, Novosibirsk, Russia
S Supporting Information
b
ABSTRACT: Interaction between Ph3P and 1,3,2,4-benzodithia-
diazine (1); its 6,7-difluoro (2), 5,6,8-trifluoro (3) and 5,6,7,8-
tetrafluoro (4) derivatives; and 5,6,8-trifluoro-3,1,2,4-benzothiase-
lenadiazine (5) proceeded via a 1:1 condensation to give Ph3PdN-
R iminophosphoranes (1a-5a, R = corresponding 1,2,3-benzodi-
chalcogenazol-2-yls), which are inaccessible by general approaches
based on the Staudinger and Kirsanov reactions. In contrast, neither
Ph3As nor Ph3Sb reacted with 1 and 4. Molecular structures of 1a-5a and 5 were confirmed by X-ray diffraction (XRD). The
crystals formed by chiral molecules of 2a-5a were racemic, whereas the crystal of 1a was formed by a single enantiomer. In all of the
Ph3PdN-R derivatives, one of the Ph rings is oriented face-to-face to the hetero ring, R. Upon heating to ∼120 °C in squalane (1a,
3a, 4a) or dissolving in chloroform at ambient temperatures (1a, 2a, 4a), the Ph3PdN-R derivatives generated the 1,2,3-
benzodithiazolyls (1b-4b, respectively) whose identity was confirmed by electron paramagnetic resonance (EPR). 2,1,3-
Benzothiaselenazolyls 5b and 6b were detected by EPR as the main paramagnetic products of solution thermolysis of 5 and its
5,6,7,8-tetrafluoro congener (6), respectively. Passing a chloroform solution of 4a through silica column unexpectedly gave 5-6-6-6
tetracyclic (9) and 6-10-6 tricyclic (10) sulfur-nitrogen compounds, which were characterized by XRD.
’ INTRODUCTION
based, in particular, on the Staudinger reaction or on the
Kirsanov reaction.6 Their molecules are chiral. Importantly, these
iminophosphoranes revealed interesting heteroatom reactivity. It
was found that they readily form 1,2,3-benzodithiazolyls R3
(Herz radicals) and other uncommon heterocyclic derivatives
such as 5-6-6-6 tetracyclic and 6-10-6 tricyclic sulfur-nitrogen
compounds (Chart 1, 9 and 10). Currently, Herz radicals7 and
their heavier chalcogen congeners8 attract much attention as
building blocks in the design and synthesis of molecular magnets
and conductors.9
1,3,2,4-Benzodithiadiazines are 12π-electron, i.e., formally
antiaromatic, compounds featuring high and varied heteroatom
reactivity of fundamental interest.1,2 In particular, polyfluori-
nated 1,3,2,4-benzodithiadiazine (Chart 1, 4) oxidatively imi-
nates Ph3P to give Ph3PdN-R iminophosphorane (Chart 1, 4a;
R = 4,5,6,7-tetrafluoro-1,2,3-benzodithiazol-2-yl).3 This reaction
is the first example of imination of phosphines with π-hetero-
cycles. As relevant reactions, those between Ar3X (X = P, As) and
inorganic cages S4N4 and RCS3N5 affording Ar3XdN-R0 deri-
vatives (R0 = S3N3 and RCS3N4, respectively) can only be
mentioned;4,5 the reaction of S4N4 is solvent-dependent, and
in MeCN instead of benzene, S4N4 and Ph3P produce
1,5-(Ph3PdN-)2S4N4.4
To elucidate the scope of the aforementioned unusual imina-
tion, in the present work, an interaction between Ph3P and
1,3,2,4-benzodithiadiazine (1), its 6,7-difluoro (2) and 5,6,8-
trifluoro (3) derivatives, and 5,6,8-trifluoro-3,1,2,4-benzothiase-
lenadiazine (5) (Chart 1) was studied. In all cases, corresponding
Ph3PdN-R iminophosphoranes were obtained (Chart 1; 1a-
3a, 5a). At the same time, it was found that neither Ph3As nor
Ph3Sb react with 1 and 4.
’ EXPERIMENTAL AND COMPUTATIONAL DETAILS
General Procedures. 1H, 13C, 14N, 15N, 29Si, 31P, and 77Se NMR
spectra were measured using CDCl3 solutions on a Bruker DRX-500
machine operating at frequencies of 500.13, 125.76, 36.13, 50.68, 99.36,
202.46, and 95.38 MHz, respectively, and 19F NMR spectra on Bruker
AC-200 and Bruker AV-300 instruments at frequencies of 188.28 and
282.4 MHz, respectively. The standards were TMS (1H, 13C, 29Si), NH3
(liq.; 14N, 15N), C6F6 (19F; δ -162.2 with respect to CFCl3), H3PO4
(31P), and Me2Se (77Se). UV-vis spectra were recorded on a Hewlett-
Packard 8453 spectrophotometer. IR spectra were taken on a Bruker
The synthesized Ph3PdN-R iminophosphoranes are inac-
cessible by the standard approaches to this class of compounds
Received: December 24, 2010
Published: March 08, 2011
r
2011 American Chemical Society
3017
dx.doi.org/10.1021/ic102565x Inorg. Chem. 2011, 50, 3017–3027
|

Inorganic Chemistry
ARTICLE
Chart 1
Table 1. Spectral Characterization of Compoundsa
NMR, δ
13C
compound
1H
19F
31P 77Se
1a
2a
7.57, 7.52, 7.39, 7.14, 7.02, 6.90, 6.58
7.60-7.53 (9H), 7.42 (6H), 7.33
(3H, C6H6), 6.78 (1H), 6.63 (1H)
7.62-7.54 (9H), 7.42 (6H), 6.06 (1H)
6.55
156.6, 132.6, 132.4, 128.4, 126.7, 125.0, 124.9, 119.7, 116.9, 115.3
153.3, 148.4, 142.6, 132.7,b 128.6, 128.1 (C6H6), 126.5,
119.8, 107.5, 102.6
17.2
19.1
18.5, 9.8
3a
5c
150.6, 148.6, 148.5, 137.2, 132.9, 132.8, 128.7, 126.1, 110.1, 92.2 51.9, 19.6, 2.6
20.9
152.0, 151.2, 138.8, 126.5, 107.2, 90.8
46.8, 30.4, 10.4
60.1, 20.0, 4.7
758
5a
7.65 (6H), 7.55 (3H), 7.41 (6H), 6.08 (1H) 152.7, 150.5, 149.1, 137.7, 132.9,b 128.6, 125.9, 111.0, 92.1
21.8 894
7c
7.39 (1H), 7.26 (1), 6.77 (2H), 4.24 (2H)
147.2, 133.5, 132.8, 118.8, 116.1, 116.0
10
11c,d
12
13
14c
5.28
33.8, 15.9, 12.0, 3.2
59.8, 43.7, 34.0, -1.0
63.8, 47.6, 38.7, 0.4
60.5, 44.7, 34.5, -0.2
60.9, 30.5, 0.0
6.91
156.5, 152.6, 150.9, 137.3, 104.6, 101.0, 1.3
158.5, 155.2, 152.7, 138.1, 105.5, 102.3
806
805
360
318
6.96
6.85
6.28 (2H), 4.62 (4H)
159.1, 151.9, 140.0, 135.3, 98.2, 92.9
a UV-vis, λmax., nm (log ε): 1a (CH3CN), 338 (4.65), 307 (3.55), 226 (3.45); 2a (CCl4), 317 (3.59); 3a (CHCl3), 243 (4.53); 5 (heptane), 588 (2.60),
357 (3.43), 265 (4.12); 5a (CHCl3), 243 (4.37). b Two overlapping doublets. c δ15N: 5, 251.0, 241.6. δ14N: 7, 343, 57; 11, 325, 302; 14, 56. d δ29Si: 4.6.
Vector 22 spectrometer and Raman spectra on a Bruker IFS 66
spectrometer equipped with Nd/YAG laser with an excitation line of
1064 nm. The NMR and UV-vis data of newly synthesized compounds
are given in Table 1.
High-resolution mass-spectra (IE, 70 eV) were obtained using
Finnigan MAT MS-8200 and Thermo DFS mass spectrometers.
The GLC-MS determinations were performed with a Hewlett-Packard
G1800A GDC apparatus.
EPR Measurements. EPR spectra of Herz radicals produced in
CHCl3 solutions at ambient temperature were acquired using a Bruker
ESP-300 spectrometer (MW power, 265 mW; modulation frequency,
100 kHz; and modulation amplitude, 0.005 mT). Simulations of the
experimental EPR spectra were performed with the Winsim 200210
program using the Simplex algorithm for many-parametric optimization
of hfc values and line widths. The accuracy of the a calculation was
(0.001 mT. The g values were measured using a MnO standard with an
accuracy of (0.00002. EPR spectra of Herz radicals produced by
thermolysis in squalane solutions were acquired using a Bruker EMX
All utilized solvents were distilled under argon over common drying
agents. CsF was calcinated directly before use.
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Inorganic Chemistry
ARTICLE
Table 2. Crystal Data and Structure Refinement for Compounds
compound
1a
2a
3a
empirical formula
fw
C
24H19N2PS2
C24H17F2N2PS2þ 1/2(C6H6)
C24H16F3N2PS2
484.50
430.50
293(2)
0.71073
monoclinic
Cc
505.54
temperature [K]
wavelength [Å]
cryst syst
293(2)
150
0.71073
monoclinic
P21/n
0.71073
monoclinic
C2/c
space group
unit cell dimensions
a [Å]
9.715(5)
16.042(9)
13.639(7)
93.66(4)
2121.3(18)
4
13.6280(10)
9.2143(7)
21.8034(12)
9.0335(5)
22.1020(14)
98.383(3)
4306.7(4)
8
b [Å]
c [Å]
19.3762(13)
96.730(5)
β [deg]
vol [Å 3]
2416.4(3)
Z
4
density (calcd) [mg m-3
]
1.348
1.390
1.495
abs. coeff [mm-1
cryst size [mm3]
reflns collected
]
0.340
0.321
0.363
0.50 ꢀ 0.30 ꢀ 0.20
2070
0.50 ꢀ 0.44 ꢀ 0.26
5789
0.05 ꢀ 0.20 ꢀ 0.90
21693
independent reflns
1991 (R(int.) = 0.080)
R1 = 0.0500, wR2 = 0.1020
R1 = 0.0801, wR2 = 0.1169
5545 (R(int.) = 0.018)
R1 = 0.0419, wR2 = 0.1036
R1 = 0.0604, wR2 = 0.1145
6258 (R(int.) = 0.059)
R1 = 0.0430, wR2 = 0.1076
R1 = 0.0570, wR2 = 0.1190
final R indices [I > 2σ(I)]
R indices (all data)
compound
5a
5
7
empirical formula
fw
C24H16F3N2PSSe
531.39
C6HF3N2SSe
269.11
C6H6N2OS2
186.25
temperature [K]
wavelength [Å]
cryst syst
space group
unit cell dimensions
a [Å]
173(2)
150(2)
203(2)
0.71073
0.71073
0.71073
monoclinic
P21
monoclinic
C2/c
orthorhombic
Pca21
22.3041(15)
9.0226(6)
25.520(3)
3.8358(5)
31.309(4)
9.106(3)
b [Å]
4.7383(14)
c [Å]
21.9604(15)
98.950(3)
10.307(3)
β [deg]
vol [Å 3]
115.677(15)
400.78(19)
4365.5(5)
3064.8(7)
Z
8
16
2
density (calcd) [mg m-3
]
1.617
2.333
1.543
abs. coeff [mm-1
cryst size [mm3]
reflns collected
]
1.930
5.171
0.603
0.10 ꢀ 0.30 ꢀ 0.30
21281
0.38 ꢀ 0.06 ꢀ 0.04
27424
0.98 ꢀ 0.20 ꢀ 0.04
1384
independent reflns
6224 (R(int.) = 0.051)
R1 = 0.0364, wR2 = 0.0934
R1 = 0.0459, wR2 = 0.0992
7988 (R(int.) = 0.115)
R1 = 0.0430, wR2 = 0.0923
R1 = 0.0698, wR2 = 0.1091
1312 (R(int) = 0.033)
R1 = 0.0437,wR2 = 0.1010
R1 = 0.0573,wR2 = 0.1132
final R indices [I > 2σ(I)]
R indices (all data)
compound
8
10
empirical formula
fw
C6N6S3
C12H2F8N2S4
454.40
252.30
temp [K]
wavelength [Å]
cryst syst
173(2)
293(2)
0.71073
orthorhombic
Pmn21
0.71073
monoclinic
P21/n
space group
unit cell dimensions
a [Å]
14.2167(8)
3.6810(2)
7.8017(4)
12.166(3)
5.389(1)
12.325(3)
b [Å]
c [Å]
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Inorganic Chemistry
ARTICLE
Table 2. Continued
compound
8
10
β [deg]
vol [Å 3]
Z
111.33(1)
752.7(3)
2
408.28(4)
2
density (calcd.) [Mg m-3
]
2.052
2.005
abs. coeff [mm-1
cryst size [mm3]
reflns collected
]
0.873
0.722
0.01 ꢀ 0.03 ꢀ 0.30
5418
0.06 ꢀ 0.16 ꢀ 1.10
1799
independent reflns
1179 (R(int.) = 0.049)
R1 = 0.0256, wR2 = 0.0600
R1 = 0.0280, wR2 = 0.0608
1722 (R(int.) = 0.036)
R1 = 0.0401, wR2 = 0.1024
R1 = 0.0580, wR2 = 0.1122
final R indices [I > 2σ(I)]
R indices (all data)
Scheme 1
spectrometer (MW power 2.07 mW, modulation frequency 100 kHz,
and modulation amplitude 0.01 mT). The spectra integration and
simulation were performed with the WIN-EPR and Winsim10 programs.
The accuracy of the a calculation was (0.001 mT. The g values were
measured using a DPPH standard with an accuracy of (0.0001.
Crystallographic Analysis. The XRD data (Table 2) for 1a and 7
were collected on a Syntex P21 diffractometer, for 2a and 10 on a Bruker P4
diffractometer, and for 3a, 5, 5a, and 8 on a Bruker Kappa Apex II
diffractometer, using Mo KR(λ= 0.71073 Å) radiation with a graphite mono-
chromator. The structures were solved by direct methods using the SHELXS-
97 program11 and refined by the least-squares method in the full-matrix
anisotropic (isotropic for H atoms) approximation using the SHELXL-97
program.11 The H atom positions were located from difference Fourier maps.
The obtained structures were analyzed for exposing shortened contacts bet-
ween nonbonded atoms with the PLATON12 and MERCURY13 programs.
CCDC-769830 (for 1a), -769831 (for 2a), -798764 (for 3a), -769833
(for 5), -769832 (for 5a), -769834 (for 7), -769835 (for 8), and -769836
(for 10) contain supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
Compounds 1a, 2a, 3a, and 5a. At -70 °C and under argon, a
solution of 0.262 g (0.001 mol) of Ph3P in 5 mL of toluene was added,
dropwise and over a period of 0.5 h, to a stirred solution of 0.001 mol of
1,1 2,16 3,16 or 5 (this work) in 5 mL of the same solvent. After an
additional 1 h at -70 °C, the reaction mixture was warmed up to 20 °C,
and the solvent was distilled off under reduced pressure. The residue
was dissolved in 3 mL of benzene, and 3 mL of hexane was added to
produce a two-layered system. The system was kept at 5 °C until
mutual diffusion of solvents ceased. The crystalline precipitate was
filtered off. Compounds 1a, 2a (as 2a 0.5C6H6 solvate), 3a, and 5a
3
were obtained in the form of orange crystals. 1a: yield, 0.070 g (16%);
mp, 124-125 °C. 2a 0.5C6H: yield, 0.100 g (20%); mp, 122-123 °C
3
(loss of benzene at 68-70 °C). 3a: yield, 0.254 g (52%); mp, 145-
147 °C. 5a: yield, 0.380 g (72%);mp, 164-166 °C. MS, m/z, orelemental
analyses: 1a, found 430.0733 (calculated for C24H19N2PS2, 430.0727);
2a, found 466.0538 (calculated for C24H17F2N2PS2, 466.0538); 3a, found
(calculatedfor C24H16F3N2PS2) C, 59.54 (59.50); H, 3.32 (3.33); N, 5.86
(5.78); F, 11.77 (11.76); P, 6.32 (6.39); S, 13.24 (13.25). 5a, found
529.9887 (calculated for C24H16F3N2PS78Se, 529.9888).
Compound 5 via Compounds 11-13.
Quantum Chemical Calculations. The DFT/UB3LYP/6-31G-
(d) calculations on Herz radicals were performed with the GAMESS
program.14 It should be noted that other tried methods (PBE/6-31G(d),
B3LYP/cc-pVDZ and PBE/cc-pVDZ) had worse performance.
Preparations: Improved Synthesis of Compound 4a. At
-70 °C and under argon, solutions of 0.240 g (0.001 mol) of 415 and
0.262 g (0.001 mol) of Ph3P, each in 5 mL of toluene, were simulta-
neously and dropwise added under stirring, over a period of 0.5 h, to
5 mL of toluene. After an additional 1 h at -70 °C, the reaction mixture
was warmed up to 20 °C, and 15 mL of hexane was added to produce a
two-layered system. The system was kept at 5 °C until mutual diffusion
of solvents ceased. The crystalline precipitate was filtered off. Com-
pound 4a3 was obtained in the form of orange crystals, yield 0.305 g
(60%), mp 144-145 °C.
a. At -60 °C and under argon, 50 mL of a 2.0 M solution of n-BuLi in
hexane was added dropwise over a period of 0.5 h to a stirred
solution of 15.0 g (0.1 mol) of 1,2,3,5-tetrafluorobenzene in
150 mL of Et2O. After an additional 0.5 h, 7.90 g (0.1 mol) of
finely powdered elemental selenium was added in small portions.
The reaction mixture was warmed up slowly to 20 °C, and 12.7 g
(0.1 mol) of elemental iodine was added. The reaction solution
was then washed with aqueous sodium thiosulfate and the organic
layer separated and dried over CaCl2. The solvent was distilled off
under reduced pressure, and the residue was recrystallized from
EtOH. 2,20,3,30,4,40,6,60-Octafluorodiphenyl diselenide (13) was
obtained in the form of orange-yellow crystals, yield, 13.68 g
(60%); mp, 46-47 °C. MS, m/z, found: 457.8358 (calculated for
3020
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Inorganic Chemistry
ARTICLE
C12H2F880Se2, 457.8359). Found (calculated for C12H2F8Se2): C,
31.68 (31.60); H, 0.53 (0.44); F, 33.29 (33.33).
c. At -30 °C and under argon, a solution of 6.88 g (0.025 mol) of
compound 12 in 10 mL of hexane was added dropwise over a
period of 1 h to a stirred solution of 5.12 g (0.025 mol) of
(Me3SiNd)2S17 in 20 mL of hexane. Over 1 h, the reaction
solution was warmed up to 20 °C and then filtered. The solvent
was distilled off under reduced pressure. 1-(2,3,4,6-Tetra-
fluorophenyl)-4-trimethylsilyl-2,4-diaza-1-selena-3-thia-2,3-buta-
diene (11) was obtained in the form of orange oil, yield, 8.57 g
(95%). MS, m/z, found: 361.9435 (calculated for C9H10F4N2-
S80SeSi, 361.9435). Found (calculated for C9H10F3N2SSeSi): C,
29.98 (29.92); H, 3.00 (2.79); F, 20.99 (21.03). Compound 11 was
used without further purification since distillation of Ar-Se-NdSd
N-SiMe3 derivatives leads to partial decomposition even in high vacuo.
d. Under argon, a solution of 1.80 g (0.005 mol) of 11 in 20 mL of
MeCN was added for 1 h to a refluxed and stirred suspension of
0.76 g (0.005 mol) of CsF in 80 mL of MeCN. After an additional 1
h, the reaction mixture was cooled to 20 °C and filtered, the
solvent distilled off under reduced pressure, and the residue
sublimed in vacuo and recrystallized from hexane. Compound 5
was obtained in the form of black crystals, yield, 0.67 g (50%); mp,
73-74 °C. MS, m/z, found: 269.8978 (calculated for
C6HF3N2S80Se, 269.8978). IR (KBr), ν (cm-1): 3083 (w),
1602 (s), 1482 (vs), 1413 (vs), 1355 (m), 1268 (w), 1236 (s),
1163 (vs), 1149 (s), 1026 (s), 898 (m), 855 (s), 828 (m), 702 (w),
619 (m), 581 (m), 570 (m), 537 (m), 470 (w). Raman, ν (cm-1):
3085 (w), 1603 (m), 1414 (m), 1356 (vs), 1269 (m), 1230 (m),
1166 (m), 1075 (m), 1041 (s), 1028 (vs), 899 (s), 620 (w), 538
(m), 471 (s), 430 (m), 349 (m), 270 (s), 149 (w).
b. A mixture of 4.58 g (0.01 mol) of compound 13 and 2.5 g (1.5 mL,
0.02 mol) of SO2Cl2 was refluxed for 1 h, the excess of SO2Cl2
distilled off, and the residue redistilled under reduced pressure.
2,3,4,6-Tetrafluorophenylselenenyl chloride (12) was obtained in
the form of dark red oil, yield, 3.90 g (74%); bp, 76-77 °C/3 mm.
Found (calculated for C6HClF4Se): C, 28.89 (28.35); H, 0.56
(0.38); Cl, 13.02 (13.46); F, 28.79 (28.84).
Table 3. Selected Bond Distances (Å) and Angles (deg) of the
Iminophosphoranes
bond/angle
1a (X = S) 2a (X = S)
3a (X = S)
5a (X = Se)
X1-S2
2.173(3)
1.582(6)
1.391(9)
1.387(10)
1.753(7)
1.597(5)
1.603(5)
90.7(2)
2.1811(8)
1.589(2)
1.387(3)
1.411(3)
1.746(2)
1.597(2)
1.607(2)
90.44(7)
96.30(7)
2.1933(6)
1.5980(14)
1.367(2)
2.3505(5)
1.5933(16)
1.369(2)
S2-N3
N3-C3a
C3a-C7a
C7a-X1
S2-N8
1.412(3)
1.411(3)
1.7419(19)
1.5906(14)
1.6162(14)
90.28(7)
1.886(2)
1.5913(16)
1.6168(16)
85.70(6)
N8-P9
C7a-X1-S2
X1-S2-N3
95.7(2)
96.65(5)
96.70(6)
S2-N3-C3a 117.7(5)
N3-C3a-C7a 118.5(6)
C3a-C7a-X1 114.9(5)
116.21(14) 116.66(11)
119.00(17) 120.16(15)
114.63(14) 114.87(13)
119.37(13)
121.67(16)
115.46(13)
110.82(6)
111.95(8)
129.53(10)
X1-S2-N8
N3-S2-N8
S2-N8-P9
111.1(2)
113.5(3)
132.8(3)
107.18(7)
114.92(9)
110.15(5)
112.35(7)
The residue from sublimation of compound 5 was chromatographed
on a silica column with CHCl3 and sublimed in vacuo. Compound 818
was obtained in the form of dark needles, yield, 3 mg; mp, 300 °C. The
131.76(11) 129.89(9)
Figure 1. XRD structures of iminophosphoranes 1a-3a and 5a. Color code: gray, C; light gray, H; green, F; blue, N; brown, P; yellow, S; pink, Se (for
2a characterized as 2a 0.5C6H6, omitted benzene molecules fill lattice cavities and do not interact with the product). For selected bond distances and
3
angles, see Table 3.
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Figure 2. XRD structures of noniminophosphorane products. Color code: gray, C; light gray, H; green, F; blue, N; red, O; yellow, S; pink, Se. Selected
bond distances (Å) and angles (deg) (for atom numbering, see Chart 1): 5 (averaged over four crystallographically independent molecules,
e.s.d. maximal from refinement or averaging): Se1-N2, 1.851(9); N2-S3, 1.541(7); S3-N4, 1.550(9); N4-C4a, 1.413(15); C4a-C8a, 1.405(11);
C8a-Se1, 1.944(9); C8a-Se1-N2, 100.0(3); Se1-N2-S3, 123.9(6); N2-S3-N4, 120.7(6); S3-N4-C4a, 124.4(7); N4-C4a-C8a, 126.0(8);
C4a-C8a-Se1, 124.6(7). 7: C1-S1, 1.772(4); S1-N2, 1.670(4); N2-S2, 1.528(3); S2-O1, 1.450(4); C2-N1, 1.390(5); C1-S1-N2, 99.8(2);
S1-N2-S2, 123.9(3); N2-S2-O1, 117.8(2). The S1N2S2O1 fragment is planar within (0.005 Å; the dihedral angle between S1N2S2O1 and the
C1 C6 plane is 77.6(1)°. 8 (molecule symmetry Cs): S1-N2, 1.6321(15); S1-N9, 1.6345(16); S7-N8, 1.6357(14); N2-C2a, 1.338(2); N8-C8a,
3 3 3
1.330(2); N9-C9a, 1.336(2); C8a-C9a, 1.455(2); C2a-C9a, 1.424(2); N2-S1-N9, 100.01(7); S1-N2-C2a, 106.23(12); N6-S7-N8, 99.62(8);
S7-N8-C8a, 106.64(10); C9a-N9-S1, 106.19(11). 10 (molecule symmetry Ci): C4a-S5, 1.775(2); S5-S6, 2.0642(11); S6-N7, 1.679(2);
C7a-N7, 1.406(3); C4a-S5-S6, 103.10(9); N7-S6-S5, 107.95(9); N7-C7a-C11a, 120.9(2); C7a-N7-S6, 123.96(18).
single crystals suitable for XRD were prepared by slow evaporation of the
THF solution.
Generation of Herz Radicals.
Scheme 2
a. At 20 °C, 1 mL of a 1 M solution of compound 1a, 2a, or 4a in
CHCl3 was placed into an EPR tube immediately after preparation,
and EPR spectra were measured periodically. The concentration of
radical 1b,19 2b, or 4b19,20 reached its maximum after ∼24 h and
then remained constant for some time, in the case of 2b, up to
∼2 weeks.
b. A total of 1 mL of a 10-3 M squalane solution of compound 1a, 3a, or
4a placed into an EPR tube equipped with a Teflon valve and
degassed by three freeze-pump-thaw cycles was heated at 120 °C
for 5 min and cooled to 20 °C. The measured EPR spectra were
identical to those of radicals 1b,19 3b, and 4b,19,20 respectively.
c. A total of 1 mL of a 10-3 M squalane solution of compound 3,16 5,
or 621 placed into an EPR tube equipped with a Teflon valve and
degassed by three freeze-pump-thaw cycles was heated at 130-
140 °C for 40 min and cooled to 20 °C. The measured EPR spectra
revealed radicals 3b, 5b (with admixture of 3b), and 6b (with
admixture of 4b), respectively.
trace level. The solution was evaporated and the residue sublimed at
140 °C/2 mm and recrystallized from hexane. Compound 14 was
obtained in the form of yellow crystals, yield, 74.1 mg (89%); mp,
138-139 °C. MS, m/z, found (calculated for C12H6F6N280Se2):
451.8767 (451.8766). Found (calculated for C12H6F6N2Se2): C,
31.93 (32.02); H, 1.23 (1.34); N, 6.21 (6.22); F, 25.21 (25.33).
Compounds 9 and 10. A solution of 0.10 g (0.2 mmol) of 4a in
CHCl3 was passed through a silica column (h = 30 cm, d = 1 cm),
evaporated under reduced pressure, and the residue was washed with
toluene. Compound 10 was obtained in the form of white crystals, yield,
6 mg; mp, 205-207 °C. MS, m/z, found: 453.8978 (calculated for
C12H2F8N2S4, 453.8973). IR (KBr), ν, cm-1: 3268 (m), 1632 (m),
1509 (s), 1482 (s), 1402 (m), 1095 (s), 988 (s), 620 (m).
The toluene solution was evaporated. Compound 9 was obtained in
the form of black crystals, yield, 4 mg. The unit cell parameters were
identical to previously reported values.20
Compound 7. A mixture of 0.168 g (1 mmol) of 1 and 0.005 g (1.5 ꢀ
10-2 mmol) of Ph3Sb was exposed to the air. Over 1 min, the deep-blue
crystals turned yellow. The product was recrystallized from hexane.
Compound 7 was obtained in the form of yellow crystals, yield, 0.119 g
(64%); mp, 102-103 °C. MS, m/z, found: 185.9914 (calculated for
C6H6N2OS2, 185.9922).
Hydrolysis of Compound 5. Compound 14. The sample of 5
(0.10 g; 0.4 mmol) for the thermolytic experiments was dissolved in
Et2O (5 mL), and the solution formed was added to the solution of H2O
(0.042 g, 2.3 mmol) and 37% aqueous HCl (0.016 g, 0.16 mmol of HCl
and 0.56 mmol of H2O) in Et2O (10 mL). After 1 day, the blue mixture
became yellow. The solution was washed with 3 mL of H2O and
dried with CaCl2. According to GLC-MS, it contained 2,20-diamino-
3,30,4,40,6,60-hexafluorodiphenyl diselenide (14; product of hydrolysis of
5) as the main product and does not contain 2,20-diamino-3,30,4,40,6,60-
hexafluorodiphenyl disulfide (product of hydrolysis of 3)22 even at a
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Scheme 3
Figure 3. Experimental (left) and simulated (right) EPR spectra of 2b, 3b, 5b, and 6b.
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Table 4. Experimental (Theoretical from DFT/UB3LYP/6-31G(d) Calculations) hfc Constants (ꢀ 10-4 T) and g Values of
Radicals 2b-6b from Thermolytic Experiments
source/radical(s), aX
2/2b
4/4b19
5/5b (93.8%) and 3b (6.2%)
6/6b (93.1%) and 4b (6.9%)
3/3b
aN
8.09 (8.76)
2.11 (-3.77)
2.75 (-3.37)
9.19 (10.36)
1.03 (1.80)
2.0032
8.2
5.7
7.79 (8.00)
7.76 (8.64)
5.33 (7.25)
2.72 (-4.10)
3.69 (-4.54)
3.46 (-4.31)
2.0053
8.00 (8.79)
8.03
6.71
7.79 (8.64)
5.35 (7.25)
2.74 (-4.10)
3.73 (-4.54)
3.46 (-4.31)
2.0060
4
aF(H)
5.49 (6.91)
2.85 (-3.89)
3.88 (-4.27)
3.40 (-4.12)
2.0123
5.89 (7.45)
2.77 (-4.08)
9.58 (10.22)
3.51 (-4.63)
2.0140
5
aF
2.6
2.35
6
aF(H)
10.0
3.5
10.35
3.49
7
aF(H)
g-value
2.0078
2.0095
Scheme 4
’ RESULTS AND DISCUSSION
It was reported that compound 4 interacts with Ph3P in
benzene at 20 °C to give iminophosphorane 4a in an isolated
yield of 12%.3 In this work, the yield of 4a was increased to 60%
by performing the interaction at -70 °C in toluene. Under the
same conditions, derivatives 1a-3a were prepared from com-
pounds 1-3 (Scheme 1) in isolated yields of 16, 20, and 53%,
respectively. The reaction is solvent-dependent and, in hexane
instead of toluene, leads to unidentified insoluble products, likely
of polymeric structure.
The structures of 1a-3a were confirmed by XRD (Tables 2
and 3, Figure 1), in the case of 2a as solvate 2a 0.5C6H6
3
after crystallization from benzene/hexane mixture. Molecules of
1a-3a are chiral. The crystal of 1a was formed by a single enan-
tiomer, whereas those of 2a and 3a were racemic (as in the case of
4a).3 For 1a-3a in the crystal, one of phenyl rings of the Ph3P
fragment is oriented practically parallel to the plane of the
heterocyclic moiety, with interplanar separations of 3.52, 3.49,
and 3.43 Å, respectively (Figure 1). The same structural feature
was previously observed for 4a with an interplanar separation of
3.39 Å.3 For comparison, the sum of the van der Waals radii of
the C atoms is 3.54 Å,23 and the interplanar distance in graphite
is 3.35 Å.24 In the case of 4a, the feature was attributed to
intramolecular π-stacking interactions of the arene-polyfluoroar-
ene type.3 Now one can think that the packing effects might be
the main driving force behind the discussed structural peculiarity;
however, the fact that in the progression 1a-4a the interplanar
separation shortens might indicate a contribution from the
arene-(poly)fluoroarene π-stacking interactions25 in the case of
fluorinated derivatives.
At the same time, compounds 1 and 4 do not interact with Ph3As
and Ph3Sb even under refluxing in toluene for 1 h. It was found in
these experiments, however, that Ph3Sb catalyzes a 1:1 addition of
atmospheric water to 1,3,2,4-benzodithiadiazines,26 and compound
7 (Chart 1) was obtained from compound 1 in an isolated yield of
64% (its fluorinated derivatives were described before).26 The
structure of 7 was confirmed by XRD (Table 2, Figure 2).
Previously, the 1-Se analog of compound 4 (Chart 1, 6) was
prepared by the fluoride-induced intramolecular cyclization of
C6F5-Se-NdSdN-SiMe3, however, in an isolated yield of 7%
only.21 In the present work, it was found that compound 5, the
precursor of iminophosphorane 5a (Chart 1), can be synthesized
in a similar way (Scheme 2) in the isolated yield of 50%. The
hetero ring closure (Scheme 2) was highly regioselective since
only 5, one of two possible isomers, was observed in the reaction
mixture by 19F NMR. The structure of 5 was confirmed by XRD
(Table 2, Figure 2). As minor byproduct, 6-5-5-5 tetracyclic
compound (Chart 1, 818) was identified by XRD (Table 2,
Figure 2).27
The interaction between 5 and Ph3P under the same condi-
tions as above gave iminophosphorane 5a (Scheme 3) in an
isolated yield of 72%. The structure of 5a was confirmed by XRD
(Tables 2 and 3, Figure 1). The racemic crystal of 5a was
isomorphic to that of 3a. The molecular structure of 5a revealed
the same face-to-face orientation of the hetero ring and one of the
hydrocarbon rings that was found for 1a-4a, with an interplanar
separation of 3.45 Å.
Thus, the interaction between Ph3P and 1,3,2,4-benzodithia-
diazines which can be classified as the oxidative imination of the
former covers both hydrocarbon and fluorocarbon series and, in
the later case, 1-Se congeners of the heterocycles as well. As
oxidative imination, the interaction of 1-5 with Ph3P should
involve an electron lone pair of the P atom (nP). However, for
Ph3X (X = P, As, Sb), the ability to react with 1,3,2,4-benzo-
dithiadiazines and their 1-Se congeners does not correlate with
the (nX)-1 vertical ionization energy from HeI UPS, which is
about the same (∼ 7.8 eV) in all cases.28
It should be noted that Ph3PdN-R iminophosporanes have
found a wide application in chemical synthesis.6 Generally, they
can be prepared from Ph3P and R-N3 by performing the
Staudinger reaction via phosphazides6 or from Ph3PCl2 and
R-NH2 by the Kirsanov reaction.6,29 It should be emphasized
that the iminophosporanes synthesized in the present work are
inaccessible by these approaches.
The reactivity of 1,3,2,4-benzodithiadiazines and 3,1,2,
4-benzothiaselenadiazines toward Ph3P can be associated
with RS-N: T RStN nitrenoids (RS = corresponding
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Scheme 5
1,2,3-benzodichalcogenazol-2-yls) detected by matrix isolation
techniques among intermediates of photochemical transforma-
tions of these heterocycles.19 It is very likely that RS-N: T
RStN are also involved in the oxidative imination of SCl2 with
1,3,2,4-benzodithiadiazines, affording 1,2,3-benzodithiazolium
chlorides (Herz salts) after the elimination of NSCl from the
initial imination product.30 A similar intermediate carrying an
exocyclic (N)-StN group was also observed for photochemical
transformations of S4N4,31 which (as well as some other sulfur-
nitrogen rings and cages) readily reacts with Ar3X to give
Ar3XdN-R derivatives (X = P, As).4,5 The properties of RS-
N: T RStN species are not studied in detail. At the same time,
one can think that the properties of these nitrenoids are different
from those of C-bonded nitrenes whose ability to oxidatively
iminate P(III) and As(III) atoms is questionable,6,32,33 whereas
nothing definite is known about Sb(III) atoms.
Earlier, it was shown by EPR spectroscopy that in CHCl3
solution (but not in toluene) and at ambient temperatures
compound 4a spontaneously produced Herz radical 4b. One
can suggest a reversible homolytic splitting of the exocyclic S-N
bond of 4a with the formation of 4b and the Ph3PdN• radical,
following by fast reaction of the latter with CHCl3 solvent to give
Ph3PdNH. This should shift the first stage toward 4b. The final
product isolated from the solution was 5-6-6-6 tetracyclic
compound 9 (Chart 1).20 It was found in this work that
dissolving compounds 1a and 2a in the same solvent leads to
the generation of radicals 1b19 and 2b (Figure 3, Table 4)
detected by EPR. On the other hand, no radicals were detected
in a CHCl3 solution of 3a, which was quantitatively recovered
from the solution after 7 days.
hand, the observed ratios of major and minor radicals do not
reflect the ratio of the major and minor heterocycles in the staring
materials because of a difference in rates of formations and yields
of the radicals. Furthermore, compounds 5 and 6 were analyti-
cally and NMR pure. However, they were not suitable to more
precise GLC-MS analysis. To detect by this method the possible
admixture of 3 in the sample of 5 used in the thermolytic
experiments, the sample was hydrolyzed by analogy with the
hydrolysis of 1,3,2,4-benzodithiadiazines, affording 2,20-diami-
nodiphenyl disulfides.22 No traces of the disulfide corresponding
to 3 were observed with GLC-MS. It is known that the thermal
behavior of 1,3,2,4-benzodithiadiazines (the 6-6 bicyclic system-
s) is extremely complex—in particular, giving rise to various 5-6
and 6-7 bi-, 5-5-6 and 5-6-7 tri-, and 5-6-6-6 tetracyclic sulfur-
nitrogen systems.20 The isolation of compound 8 as a byproduct
of the synthesis of compound 5 (this work) provides an addi-
tional example. Therefore, one can think that precursors of the
discussed minor radicals were not admixtures in the starting
materials but rather compounds formed in the reaction systems
on reaction side routes.
Overall, one can conclude that the discussed iminophosphor-
anes represent a new promising source of Herz radicals on an
EPR scale. A common synthetic approach to these radicals is
based on the reduction of Herz salts8,24 available by the Herz
7
reaction between arylamines and S2Cl2 and the interaction of
ortho-aminothiophenols with SOCl27 or 1,3,2,4-benzodithiadia-
zines with SCl2.30 On an EPR scale, Herz radicals can also be
obtained by the thermolysis or photolysis of various sulfur-
nitrogen derivatives,7 especially 1,3,2,4-benzodithiadiazines19
and, now, their 1-Se congeners. These methods provide radicals
(for example, polyfluorinated)19 which are inaccessible via Herz
salts.34 An advantage of the iminophosphoranes over the parent
1,3,2,4-benzodithiadiazines is the lower temperature of transfor-
mation into Herz radicals since they are better suited structurally
to this reaction.
Thermolysis of dilute solutions of 1a, 3a, and 4a in squalane at
120 °C affords corresponding Herz radicals 1b,19 3b (Figure 3,
Table 4), and 4b19,20 (Scheme 4) identified by EPR. Radical 3b
was also generated by the thermolysis of 3 in squalane at 140 °C
(Scheme 4).
Passing a chloroform solution of 4a through a silica column
unexpectedly gave 5-6-6-6 tetracyclic (9) and 6-10-6 tricyclic
(10) sulfur-nitrogen compounds (Scheme 5). Compound 9
was known before;20 the structure of compound 10 was con-
firmed by XRD (Table 1, Figure 2; cf. structure of the hydro-
carbon congener35).
The behavior of compound 5a was different. Upon either
dissolving 5a in CHCl3 at room temperature or heating it in
decane up to 170 °C, expected radical 5b was not detected by
EPR. In contrast to 3a, compound 5a was not recovered from
CHCl3 solution. Instead, a complex mixture of unidentified
1
compounds was observed by H and 19F NMR. The reasons
for the different behaviors of compounds 1a-5a in CHCl3
solution are not clear.
’ CONCLUSIONS
Meanwhile, previously unknown Herz radicals 5b and 6b
(Scheme 4, Figure 3, Table 4) were obtained by the thermolysis
of compounds 5 and 6 in squalane at 140 °C. In both cases, EPR
spectra also revealed the presence of a minor amount of a
second radical featuring a lesser g value and line widths. The
experimental spectra were fairly well simulated as the super-
position of those of 5b (93.8%) and 3b (6.2%) for the
thermolysis of 5 and those of 6b (93.1%) and 4b (6.9%) for
the thermolysis of 6.
The interaction between Ph3P and 1,3,2,4-benzodithiadia-
zines affording Ph3PdN-R iminophosphoranes (R = 1,2,3-
benzodithiazol-2-yls) readily proceeds in both the hydrocarbon
and fluorocarbon series, in the latter case covering also 1-Se
congeners of the heterocycles. It is the first example of imination
of phosphines with π-heterocycles. The iminophosporanes
obtained are inaccessible by the common procedures based
on the Staudinger reaction or on the Kirsanov reaction.
Therefore, the new reaction of 1,3,2,4-benzodithiadiazines
and their 1-Se congeners described in this work represents
On the one hand, minor products 3b and 4b might arise from
trace admixtures of 3 and 4 in 5 and 6, respectively. On the other
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ARTICLE
the new approach to Ph3PdN-R iminophosphoranes. In the
crystalline state, the synthesized Ph3PdN-R derivatives dis-
play an interesting structural feature; i.e., one of the Ph rings is
oriented face-to-face with the hetero ring R, with the inter-
planar separation being shorter than the sum of van der Waals
radii of two C atoms of 3.54 Å. Overall, they represent a new
structural type of the iminophosphoranes. These derivatives
also reveal interesting heteroatom reactivity. Particularly, they
are a promising new source of 1,2,3-benzodithiazolyls R• (Herz
radicals), as well as of uncommon polycyclic compounds
hardly accessible by other approaches. These Ph3PdN-R
iminophosphoranes can also be of interest as chiral ligands in
coordination compounds.
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’ ASSOCIATED CONTENT
S
Supporting Information. A crystallographic file in CIF
b
format. This material is available free of charge via the Internet at
http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail zibarev@nioch.nsc.ru.
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’ ACKNOWLEDGMENT
The authors are grateful to Prof. Nina P. Gritsan and Prof. Yuri
N. Molin for valuable discussions; to Dr. Mikhail K. Kovalev and
Mr. Stanislav N. Kim for assistance in preliminary experiments;
and to the Russian Foundation for Basic Research (project 09-
03-00361), the Presidium of the Russian Academy of Sciences
(project 18.17), and the Siberian Branch of the Russian Academy
of Sciences (project 105) for financial support. A.G.M. thanks the
Russian Science Support Foundation for a 2010 Postgraduate
Scholarship.
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