T. Ryowa et al. / Inorganica Chimica Acta 357 (2004) 3532–3540
3533
well as the corresponding C3S5-complexes, and their
oxidation and electrical conductivities of the oxidized
species. The crystal structures of [NMe4][Au(PPh3)-
(C3S5)], [(PEt3)Au–C3S5–Au(PEt3)] and [(PEt3)Au–
C8H4S8–Au(PEt3)] are also described.
action of C8H4S8(CH2CH2CN)2 (460 mg, 1.0 mmol)
with NMe4OH (900 mg, 9.8 mmol) was reacted with a
methanol (20 cm3) solution of AuCl(PEt3) (350 mg, 1.0
mmol) immediately to yield brown solids of 3 (70%
yield). Anal. Calc. for C18H31AuNPS8: C, 28.98; H, 4.19;
N, 1.88. Found: C, 28.75; H, 4.07; N, 2.05%. H NMR
(in DMSO-d6): d 1.07 (9H, m, CH3), 1.68 (6H, m, CH2),
3.10 (12H, s, NMeþ4 ), 3.25 (4H, s, CH2).
1
2. Experimental
C8H4S8(CH2CH2CN)2 (460 mg, 1.0 mmol) was dis-
solved in an ethanol (30 cm3) solution containing Na
metal (73 mg, 3.1 mmol). To the resulting solution of
Na2[C8H4S8] was added with stirring a dichloromethane
(10 cm3) solution of AuCl(PPh3) (490 mg, 1.0 mmol) and
N-methylpyridinium chloride (155 mg, 1.5 mmol), and
the solution was stirred for 30 min. A brown precipitate
of 4 obtained was collected by filtration, washed with
dichloromethane and methanol, and dried in vacuo (70%
yield). Anal. Calc. for C32H27AuNPS8: C, 42.23; H, 2.99;
N, 1.54. Found: C, 41.12; H, 3.03; N, 1.64%. 1H NMR (in
DMSO-d6): d 3.37 (3H, s, CH3), 7.50 (15H, m, Ph), 8.12
(2H, t, CH), 8.56 (1H, t, CH), 8.98 (2H, d, CH).
2.1. Materials
4,5-Bis(cyanoethylthio)-1,3-dithiole-2-thione, C3S5-
(CH2CH2CN)2 [19], and 4,5-bis-(cyanoethylthio)-1,3-
dithiole-2-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene],
C8H4S8(CH2CH2CN)2 [20–22], as pro-ligand com-
pounds of C3S52ꢀ and C8H4S28ꢀ dithiolates, were pre-
pared according to the literatures. (Triethylphosphine)
chlorogold(I), (triphenylphosphine)chlorogold(I) [AuCl-
(PR3)] (R ¼ Et and Ph), and 7,7,8,8-tetracyano-p-
quinodimethane (TCNQ) were commercially available.
2.2. Preparations of [NMe4][Au(PR3)(C3S5)] [R ¼ Et
(1) and Ph (2)]
2.4. Preparation of [(PEt3)Au–C3S5–Au(PEt3)] (5)
All the following reactions were performed under an
argon atmosphere. To an ethanol (30 cm3) solution of
C3S5(CH2CH2CN)2 (280 mg, 0.90 mmol) was added with
vigorous stirring a methanol (3.6 g, 25 wt%) solution
containing NMe4OH (900 mg, 9.8 mmol) and the solu-
tion was stirred for 15 min. To the solution was added
with stirring a methanol (20 cm3) solution of AuCl(PEt3)
(350 mg, 0.98 mmol) and the solution was stirred for 30
min at room temperature. The resulting red solids of 1
were collected by filtration, washed with methanol, and
dried in vacuo (60% yield). Anal. Calc. for
C13H27AuNPS5: C, 26.66; H, 4.65; N, 2.39. Found: C,
C3S5(CH2CH2CN)2 (300 mg, 1.0 mmol) was dis-
solved in an ethanol (30 cm3) solution containing so-
dium ethanolate (Na, 120 mg, 5.0 mmol). To the
resulting solution of Na2[C3S5] was added with stirring a
methanol (15 cm3) solution of AuCl(PEt3) (700 mg, 2.0
mmol) and the solution was stirred for 30 min. The
orange precipitate of 5 obtained was collected by fil-
tration, washed with dichloromethane and methanol,
and dried in vacuo (60% yield). Anal. Calc. for
C15H30Au2P2S5: C, 21.80; H,3.66. Found: C, 21.81; H,
3.47%. 1H NMR (in CDCl3): d 1.22 (18H, m, CH3), 1.84
(12H, m, CH2). The complex was recrystallized from
dichloromethane to afford brown prisms of 5, which
were suitable for the X-ray analysis.
1
26.19; H, 4.37; N, 2.58%. H NMR (in CDCl3): d 3.21
(12H, s, NMeþ4 ), 1.77 (6H, m, CH2), 1.20 (9H, m, CH3).
Similarly, an ethanol (30 cm3) solution of [NMe4]2-
[C3S5] prepared by the reaction of C3S5(CH2CH2CN)2
(280 mg, 0.90 mmol) with NMe4OH (900 mg, 9.8 mmol)
was reacted with a dichloromethane (20 cm3) solution of
AuCl(PPh3) (490 mg, 1.0 mmol) to yield red solids of 2
(60% yield). Anal. Calc. for C25H27AuNPS5: C, 41.15;
H, 3.73; N, 1.92. Found: C, 40.95; H, 3.73; N, 2.02%. 1H
NMR (in DMSO-d6): d 3.09 (12H, s, NMeþ4 ), 7.52 (15H,
m, Ph). The complex was recrystallized from dichloro-
methane to afford orange plates of [NMe4][Au(PPh3)-
(C3S5)]CH2Cl2, which were suitable for the X-ray crystal
structure analysis.
2.5. Preparations of [(PR3)Au–C8H4S8–Au(PR3)]
(R ¼ Et (6) and Ph (7))
As described for the preparation of 5, an ethanol (30
cm3) solution of Na2[C8H4S8] prepared by the reaction of
C8H4S8(CH2CH2CN)2 (460 mg, 1.0 mmol) with Na metal
(120 mg, 5.0 mmol) was reacted with a methanol (20 cm3)
solution of AuCl(PEt3) (700 mg, 2.0 mmol) to afford or-
ange solids of 6. They were collected by filtration, washed
withmethanol, and dried in vacuo (70% yield). Anal. Calc.
for C20H34Au2P2S8: C, 24.34; H, 3.47. Found: C, 24.18;
1
H, 3.12%. H NMR (in CDCl3): d 1.22 (18H, m, CH3),
2.3. Preparations of [NMe4][Au(PEt3)(C8H4S8)] (3)
and [N-methylpyridinium][Au(PPh3)(C8H4S8)] (4)
1.83 (12H, m, CH2), 3.26 (4H, s, CH2). The complex was
recrystallized from dichloromethane to afford orange
blocks of 6, which were suitable for the X-ray analysis.
Similarly, an ethanol (30 cm3) solution of Na2-
[C8H4S8] prepared by the reaction of C8H4S8
As described for the preparation of 1, an ethanol (30
cm3) solution of [NMe4]2[C8H4S8] prepared by the re-