Inorganic Chemistry
Article
elimination producing volatile byproducts that should be
removed at the reaction temperature.
2-ethoxyethanol. (22.2 g, 0.108 mol, 54.3% yield). mp = 201−204 °C.
33−36
Calc. for C H KO S (%): C 29.4, H 4.44, S 31.3, K 19.2; found: C
5
9
2 2
−1
2
9.4, H 4.38, S 30.9, K 19.6. FT-IR (cm ): 2972 (w), 2859 (w), 1443
(
m), 1421(w), 1290 (w), 1246 (w), 1107(m), 1053 (s), 934 (w), 826
2
. EXPERIMENTAL SECTION
1
(w), 795 (w). H NMR (400 MHz, D O) δ (ppm) = 1.13 (t, 3H,
2
CH CH ), 3.57 (q, 2H, CH CH ), 3.76 (t, 2H, CH CH O), 4.49 (t,
2
.1. General. All chemicals were purchased from Sigma-Aldrich
2
3
2
3
2
2
2
H, CH CH O).
and were used as received. Elemental analysis (EA) and thermogravi-
metric analysis (TGA) were performed by the Microelemental
Analysis service at the University of Manchester. EA was performed
using a Flash 2000 Thermo Scientific elemental analyzer, and TGA
data were obtained with Mettler Toledo TGA/DSC1 star system in
the range of 30−600 °C at a heating rate of 10 °C min under
nitrogen flow. NMR spectra were recorded in CDCl3 and D O
solutions on a Bruker Ascend spectrometer operating at 400 MHz.
Single-crystal X-ray diffraction (XRD) was performed using a Bruker
diffractometer with a Cu Kα source (λ = 1.5418 Å) at 100 K and
2 2
Synthesis of Potassium 1-Methoxy-2-propylxanthate (5). [K-
(
S COC(H)(Me)CH OMe)] was prepared via the same method,
2
2
using 1-methoxy-2-propanol (75 mL). The product was recrystallized
from 1-methoxy-2-propanol to give 5 (27.1 g, 0.132 mol, 66.3% yield).
e
−1
mp = 221−226 °C. Calc. for C H KO S (%): C 29.4, H 4.44, S 31.3,
5 9 2 2
−1
K 19.2; found: C 29.7, H 4.38, S 31.5, K 19.5. FT-IR (cm ): 2974
(w), 2935(w), 2897 (w), 1442 (m), 1474(w), 1445 (w), 1247 (m),
2
1172 (m), 1108(m), 1045 (s), 949.6 (w), 938.7 (m), 628.2 (w), 572
1
(w). H NMR (400 MHz, D
O) δ (ppm) = 1.2 (d, 3H, CHCH
), 3.58 (m, 2H, CH O), 5.59 (m, 1H, CHCH ).
Synthesis of Potassium 3-Methoxy-1-butylxanthate (6). [K-
CO(CH C(H)(OMe)Me)] was prepared via the same method,
), 3.33
2
3
(s, 3H, OCH
3
2
3
(S
)
2 2
2
550291−550300. Transmission electron microscope (TEM) images
using 3-methoxy-1-butanol (75 mL). The product was recrystallized
from 3-methoxy-1-butanol to give 6 (30.7 g, 0.14 mol, 70.3% yield).
were collected at 300 keV using an FEI Tecnai TF30 equipped with a
field emission gun. Energy-dispersive X-ray spectroscopy (EDS)
measurements were performed using an FEI Quanta 200 SEM
equipped with an EDAX Genesis spectrometer. Grazing incidence X-
ray diffraction (XRD) patterns were obtained with a Bruker D8
Advance diffractometer using a Cu Kα source (λ = 1.5418 Å). UV−vis
spectra were collected on a Shimadzu UV-1800, using 1.57 mM
solution of nanorods in toluene.
mp = 202−206 °C. Calc. for C H11KO S (%): C 33.0, H 5.08, S 29.3,
6 2 2
−1
K 17.9; found: C 33.3, H 5.06, S 29.2, K 18.0. FT-IR (cm ): 2963
(w), 2924(w), 2820 (w), 1449 (m), 1372(w), 1171 (m), 1131 (s),
1100 (s), 1060(s), 958.4 (w), 935.6 (w), 916.1 (w), 830.8(m), 780.4
1
(w), 559.2 (w). H NMR (400 MHz, D
O) δ (ppm) = 1.13 (d, 3H,
), 3.28 (s, 3H, CH CHOCH ),
), 4.42 (m, 2H, CH CH CHOCH ).
2
CHCH
), 1.87 (m, 2H,CH
CHOCH
CHOCH
3
2
3
2
3
3.56 (s, 1H, CH
2
3
2
2
3
2
.2. Synthesis of Precursors. Synthesis of Potassium n-
Synthesis of Potassium 3-Methoxy-3-methyl-1-butylxanthate (7).
Butylxanthate (1). Potassium n-butylxanthate was prepared following
[K(S CO(CH ) C(OMe)(Me) )] was prepared via the same method,
2
2
2
2
37
a literature procedure. Potassium hydroxide (5.64 g, 0.10 mol) and
n-butyl alcohol (50 mL) were stirred for 2 h at room temperature, and
then CS (7.73 g, 6.11 mL, 0.10 mol) was added dropwise to the
reaction, resulting in an orange solution. The unreacted alcohol was
removed in vacuo, and the yellow solid product was dried and
recrystallized from n-butyl alcohol to give [K(S CO Bu)] (13.5 g,
.0717 mol, 71.7% yield). mp = 232−235 °C. Calc. for C H KOS
%): C 31.9, H 4.82, S 34.0, K 20.8; found: C 32.2, H 4.83, S 33.8, K
0.4. Fourier transform infrared (FT-IR) (cm ): 2958 (m), 2869 (w),
461 (m), 1445 (w), 1261 (s), 1149 (m), 1173 (m), 1062 (m), 1014
m), 747.3 (m), 669.0 (s), 566.2 (s). H NMR (400 MHz, D O) δ
ppm) = 0.85 (t, 3H, CH ), 1.35 (s, 2H, CH CH CH ), 1.65 (p, 2H,
using 3-methoxy-3-methyl-1-butanol (75 mL). The product was
recrystallized from 3-methoxy-3-methyl-1-butanol to give 7. (29.2 g,
0.125 mol, 62.8% yield). mp = 237−240 °C. Calc. for C H KO S
2
7
13
2 2
(%): C 36.2, H 5.65, S 27.6, K 16.8; found: C 36.5, H 5.75, S 27.6, K
17.0. FT-IR (cm-1): 2973 (w), 2955 (w), 1463 (w), 1385 (w), 1366
n
2
(w), 1293 (w), 1157 (m), 1087 (s), 1050 (s), 988.4 (w), 945.7 (w),
1
0
(
2
1
(
(
870.3 (m), 779.4 (w), 754.6 (m). H NMR (400 MHz, D O) δ (ppm)
5
9
2
2
= 1.17 (s, 6H, CH C(CH ) OCH ), 1.95 (t, 2H, CH C-
2
3
2
3
2
−1
(CH ) OCH ), 3.16 (s, 3H, CH C(CH ) OCH ), 4.44 (t,
3 2 3 2 3 2 3
2H,CH CH C(CH ) OCH ).
2 2 3 2 3
Synthesis of Triphenylphosphine Copper Chloride (8).
1
2
3
2
2
3
[(Ph P) CuCl] ·2CHCl was prepared through a modified literature
3
2
2
3
3
8
CH CH CH ), 4.37 (t, 2H, OCH CH ).
method. PPh (21.5 g, 0.082 mol) and copper(I) chloride (3.96 g,
2
2
2
2
2
3
i
Synthesis of Potassium iso-Butylxanthate (2). [K(S CO Bu)] was
prepared via the same method, using isobutanol (50 mL). The product
was recrystallized from isobutanol. (9.66 g, 65% yield). mp = 241−243
C. Calc. for C H KOS (%): C 31.9, H 4.82, S 34.0, K 20.8; found: C
1.7, H 4.72, S 34.0, K 21.0. FT-IR (cm ): 2958 (m), 2927 (w), 2870
w), 1463 (w), 1386 (w), 1366 (w), 1179 (w), 1165 (w), 1141 (m),
0.04 mol) were heated to reflux for 12 h in chloroform (150 mL)
2
under N . After filtration the product was allowed to cool to give
2
crystalline [(Ph P) CuCl] . White crystals suitable for diffraction were
3
2
2
°
3
(
1
5
obtained from a chloroform solution at −20 °C. (17.6 g, 0.011 mol,
5
9
2
−1
61.0% yield). mp = 214−217 °C. Calc. for C H Cl Cu P (%): C
7
4
62
8
2 4
−1
59.8, H 4.21, P 8.34; found: C 59.4, H 4.21, P 8.05. FT-IR (cm ):
3052 (w), 2969 (w), 1479 (w), 1432 (m), 1234 (w), 1183 (w), 1092
092 (s), 968.8 (m), 937.6 (w), 912.7 (w), 802.1 (w), 653.3(w),
71.9(w). 1H NMR (400 MHz, D O) δ (ppm) = 0.89 (d, 6H,
2
(m), 1069 (w), 1026 (w), 997.5 (w), 741.7 (s), 691.3 (s), 665.8 (w),
1
CH(CH ) ), 1.99 (s, 1H, CH(CH ) ), 4.16 (d, 2H, OCH CH).
Synthesis of Potassium 2-Methoxyethylxanthate (3). [KS CO-
CH ) OMe] was synthesized by dissolving KOH (11.2 g, 0.20 mol)
in (75 mL) of 2-methoxyethanol. The reactors were stirred for 6 h at 0
C, and then a solution of CS (15.2 g, 12 mL, 0.20 mol) in 2-
methoxyethanol (25 mL) was added dropwise, resulting in a clear
yellow solution. [KS CO(CH ) OMe] was isolated from solution by
adding tetrahydrofuran (THF; 100 mL) and shaking the mixture for
5 min. The yellow solid product was dried in vacuo and recrystallized
from 2-methoxyethanol to give [K(S CO(CH ) OMe)] (19.8 g, 0.104
mol, 52.1% yield). mp = 216−219 °C. Calc. for C H KO S (%): C
5.3, H 3.71, S 33.6, K 20.6; found: C 25.5, H 3.79, S 33.5, K 20.8. FT-
618.2 (w). H NMR (400 MHz, CDCl ) δ (ppm) = 7.13−7.35 (m,
3
2
3
2
2
3
30H, Ph). 31P NMR (400 MHz, CDCl ) δ (ppm) = −4.2.
2
3
(
2.3. Synthesis of Copper Xanthates. Synthesis of Triphenyl-
phosphine Copper(I) Ethylxanthate (9). A solution of potassium
ethylxanthate (0.641 g, 0.0040 mol) in chloroform (40 mL) was added
to a solution of triphenylphosphine (2.09 g, 0.008 mol) and CuCl
(0.40 g, 0.0040 mol) in the same amount of chloroform. A white
precipitate was obtained after continuous stirring for 1 h at room
temperature. The solution was filtered to obtain a clear yellow
solution. Cooling the yellow solution to −20 °C gave yellow crystals of
triphenylphosphine copper(I) ethylxanthate (2.40 g, 0.0033 mol,
82.5% yield). mp = 185−191 °C. Calc. for C H CuOP S (%): C
2
2
°
2
2
2 2
1
2
2 2
4
7
2 2
2
39
35
2 2
−1
IR (cm ): 2935 (w), 2888 (w), 1442 (m). 1445 (w), 1230 (m), 1134
m), 1099 (m), 1066 (s), 1018 (m), 844.3 (w), 676.7 (m), 532.5 (m).
H NMR (400 MHz, D O) δ (ppm) = 3.35 (s, 3H, OCH ), 3.72 (t,
66.1, H 4.97, S 9.02, P 8.74, Cu 8.96; found: C 65.7, H 5.08, S 8.77, P
−1
(
8.44, Cu 8.74. FT-IR (cm ): 3048 (w), 2992 (w), 1478 (m) 1433
1
2
3
(m), 1290 (s), 1142 (m), 1041 (m), 1009 (s), 849.5 (s), 740.8 (m),
1
2
H, CH CH O), 4.50 (t, 2H, CH CH O).
617.7 (s), 559.2 (s). H NMR (400 MHz, CDCl ) δ (ppm) = 1.27 (t,
2
2
2
2
3
Synthesis of Potassium 2-Ethoxyethylxanthate (4). [K(S CO-
3H,CH CH ), 4.34 (q, 2H, OCH CH ), 7.02−7.37 (m, 30H, Ph).
2
2
3
2
3
(
CH ) OEt)] was prepared via the same method, using 2-
Synthesis Triphenylphosphine Copper(I) n-Butylxanthate (10).
2
2
ethoxyethanol alcohol (75 mL). The product was recrystallized from
[(Ph P) Cu(S COBu)] was also synthesized by the same method
3
2
2
B
Inorg. Chem. XXXX, XXX, XXX−XXX