2744
A. Alberola et al. / Journal of Organometallic Chemistry 692 (2007) 2743–2749
properties of radicals 2Å and 3Å have been reported recently
elsewhere [5f,9]. The crystal and electronic structure of 1Å is
described in the current contribution.
bined and washed with water and brine, and the solvent
removed in vacuo. The product was recrystallised from
diethylether to afford pure C6H3(CN)(StBu)2. Yield: 1.9 g,
57%. Analysis found: C, 67.43; H, 7.58; N, 5.04.
C15H21S2N requires: C, 64.47; H, 7.57; N, 5.01%. dH
(CDCl3) 1.32 (s, 18H), 7.41 (t, 1H), 7.70 (dd, 1H), 7.95
(dd, 1H). m/z (EI) 279.1 (M+, 100%).
S
S
S
S
.
N
.
N
Chlorination of C6H3(CN)(StBu)2 (1.0 g, 3.5 mmol) with
Cl2 (g) in CCl4 (20 ml) under ambient conditions yielded an
orange solution of C6H3(CN)(SCl)2 . The solvent was
removed in vacuo and the oily residue redissolved in
CH2Cl2.This was treated with Me3SiN3 (0.4 ml, 5 mmol)
to yield the salt [C6H3(CN)S2N]Cl, [2]Cl. Reduction of
[2]Cl with Ag powder in acetonitrile yielded 2 which was
purified by vacuum sublimation. Yield: 0.236 g, 35%. Anal-
ysis found: C, 49.46; H, 1.73; N, 15.24. C7H3S2N2 requires:
C, 49.91; H, 1.68; N, 15.63%.
CN
1
2
S
S
.
N
.
N
S
S
N
NC
3
4
2.3. 40-Cyano-benzo-1,3,2-dithiazolyl (3)
2. Experimental
To 2 g (11.6 mmol) of 3,4-dichlorobenzonitrile dissolved
in 20 ml of 1,3-dimethyl-2-imidazolidinone, sodium butyl-
thiolate 4.7 g (43 mmol) was added and the reaction mix-
ture was heated to 60 ꢁC for 24 h. After allowing the
reaction mixture to cool down to room temperature, water
(100 ml) was poured in and the mixture extracted with
diethyl ether (3 · 75 ml). The organic extracts were com-
bined and washed with water and brine, and the solvent
removed in vacuo. The product was recrystallised from
diethylether to afford pure C6H3(CN)(StBu)2. Yield: 2 g,
61%. Analysis found: C, 64.81; H, 7.63; N, 4.98.
C15H21S2N requires: C, 64.47; H, 7.57; N, 5.01%. dH
(CDCl3) 1.41 (s, 18H), 7.47 (dd, 1H), 7.68 (d, 1H), 7.85
(d, 1H). m/z (EI) 279.1 (M+, 100%).
2.1. 30-Methyl-benzo-1,3,2-dithiazolyl (1)
To 1.44 g (8.9 mmol) of 2,3-dichlorotoluene dissolved in
30 ml of 1,3-dimethyl-2-imidazolidinone, sodium butylthi-
olate, 5 g (45 mmol) was added and the reaction mixture
heated to 100 ꢁC for a week. After allowing the reaction
mixture to cool down to room temperature, water
(100 ml) was poured in and the mixture extracted with
diethyl ether (3 · 75 ml). The organic extracts were com-
bined and washed with water and brine, and the solvent
removed in vacuo. The product was purified via column
chromatography (Silica, hexane) to afford pure
C6H3(CH3)(StBu)2. Yield: 1.85 g, 78%. Analysis found: C,
67.59; H, 9.26; C15H24S2 requires: C, 67.10; H, 9.01%. dH
(CDCl3) 1.26 (s, 18H), 2.50 (s, 3H), 6.9 (dq, 1H), 7.06
(d,1H), 7.13 (d, 1H). m/z (EI) 268.1 (M+, 100%).
Chlorination of C6H3(CN)(StBu)2 (1.0 g, 3.5 mmol) with
Cl2 (g) in CCl4 (20 ml) under ambient conditions yielded an
orange solution of C6H3(CN)(SCl)2. The solvent was
removed in vacuo and the oily residue redissolved in
CH2Cl2.This was treated with Me3SiN3 (0.4 ml, 5 mmol)
to yield the salt [C6H3(CN)S2N]Cl, [3]Cl. Reduction of
[3]Cl with Ag powder in acetonitrile yielded 3 which was
purified by vacuum sublimation. Yield: 0.314 g, 46%. Anal-
ysis found: C, 46.91; H, 1.70; N, 15.62. C7H3S2N2 requires:
C, 49.91; H, 1.68; N, 15.63%.
Chlorination of C6H3(CH3)(StBu)2 (1.3 g, 3.5 mmol)
with Cl2 (g) in CCl4 (20 ml) under ambient conditions
yielded an orange solution of C6H3(CH3)(SCl)2. The sol-
vent was removed in vacuo and the oily residue redissolved
in CH2Cl2. This was treated with Me3SiN3 (0.4 ml,
5 mmol) to yield the salt [C6H3(CH3)S2N]Cl, [1]Cl. Reduc-
tion of [1]Cl with Ag powder in acetonitrile yielded 1 which
was purified by vacuum sublimation. Yield: 0.36 g, 45%.
Analysis found: C, 49.32; H, 3.12; N, 8.21; C7H6S2N
requires: C, 49.97; H, 3.59; N, 8.324%.
2.4. Pyridine-1,3,2-dithiazolyl (4)
To 1.5 g (11 mmol) of 2,3-dichloropyridine dissolved in
20 ml of 1,3-dimethyl-2-imidazolidinone, sodium butylthi-
olate 4.7 g (43 mmol) was added and the reaction mixture
heated to 75 ꢁC for 24 h. After allowing the reaction mix-
ture to cool down to room temperature, water (100 ml)
was poured in and the mixture extracted with diethyl ether
(3 · 75 ml). The organic extracts were combined and
washed with water and brine, and the solvent removed in
vacuo. The product was recrystallised from diethylether
to afford pure C5H3N(StBu)2. Yield: 2.3 g, 82%. Analysis
2.2. 30-Cyano-benzo-1,3,2-dithiazolyl (2)
To 2 g (11.6 mmol) of 2,3-dichlorobenzonitrile dissolved
in 20 ml of 1,3-dimethyl-2-imidazolidinone, sodium butyl-
thiolate 4.7 g (43 mmol) was added and the reaction mix-
ture was heated to 60 ꢁC for 24 h. After allowing the
reaction mixture to cool down to room temperature, water
(100 ml) was poured in and the mixture extracted with
diethyl ether (3 · 75 ml). The organic extracts were com-