European Journal of Inorganic Chemistry
10.1002/ejic.202000258
FULL PAPER
=
3
192.63 g mol–1): C 12.47, H 1.57, S 33.29 %; found: C 12.42, H 1.59, S
3.26 %. 1H NMR: δ 3.95 (s) ppm. 13C NMR: δ 61.8 (s; CH
), 235.1 (s;
840(w), 829(m), 804(w), 574(w), 553(w), 542(w), 524(m), 473(s), 330(sh),
320(m br), 306(sh), 238(s br), 201(s br) cm–1
.
3
CSS) ppm. IR: ν 2999(w), 2940(w), 2812(w), 1443(w), 1420(m), 1414(sh),
1
8
240(w), 1178(s), 1112(sh), 1097(m), 1076(s), 1040(s), 1003(sh), 936(m),
33(w), 701(w), 577(m), 468(s), 329(m), 297(m br) cm–1
3
·18c6: Yield: 3.65 g (89%). Pale yellow, odorless, air-stable crystalline
.
solid, Dec. 160 °C. Very soluble in water and methanol, soluble in THF and
acetone, poorly soluble in diethyl ether as well as in chlorinated and non-
chlorinated hydrocarbons. Single crystals of 3·18c8 suitable for X-ray
structure determination were obtained by slow evaporation of a methanol
Cs(SSC-OMe) (5): Yield: 5.04 g (70%). Pale yellow, odorless, air-stable
crystalline solid, Dec. 160 °C. Very soluble in water and methanol, soluble
in THF and acetone, poorly soluble in diethyl ether. Anal. calcd. for
solution at room temperature. Anal. calcd. for C12
H
27KO
7
S
2
(M = 410.58 g
(M = 240.07 g mol 1): C 10.01, H 1.26, S 26.71 %; found: C
–
mol–1): C 40.96, H 6.63, S 15.62 %; found: C 40.97, H 6.62, S 15.60 %. H
1
C
9
2
H
3
CsOS
2
.94, H 1.31, S 26.62 %. H NMR: δ 3.88 (s) ppm. 13C NMR: δ 60.3 (s;
1
NMR: δ 3.59 (s, 24H; CH
CH ), 69.7 (s; CH ), 233.5 (s; CSS) ppm. IR: ν 2965(w), 2930(sh), 2901(m),
2 3
), 3.91 (s, 3H; CH
) ppm. 13C NMR: δ 60.3 (s;
CH
3
), 233.6 (s; CSS) ppm. 133Cs NMR: δ 2.6 (s) ppm. IR: ν 2992(w),
3
2
2
1
8
2
936(w), 2810(w), 1443(w), 1417(m), 1391(sh), 1351(w br), 1238(w),
176(s), 1106(sh), 1095(sh), 1078(s), 1040(s), 1024(sh), 992(sh), 935(m),
30(m), 694(m), 661(w), 576(m), 467(s), 326(m), 288(m br), 250(w br),
2966(w), 2926(w), 1472(m), 1455(m), 1436(w), 1428(w), 1370(w),
1350(m), 1285(m), 1251(m), 1236(w), 1182(m), 1135(w), 1096(s),
1082(sh), 1044(s), 1009(w), 960(s), 835(s), 531(w), 474(m), 255(m br),
43(sh) cm–1
.
228(m br) cm–1
.
Synthesis of K(SSC-OMe) (3): Procedure B) Anhydrous solutions of 3 in
methanol or THF were prepared similarly as described for 2, using
potassium hydride (1.20 g, 30 mmol) instead of metallic sodium (13C NMR:
4·18c6: Yield: 3.56 g (78%). Pale yellow, odorless, air-stable crystalline
solid, Dec. 180 °C. Very soluble in water and methanol, soluble in THF and
acetone, poorly soluble in diethyl ether as well as in chlorinated and non-
chlorinated hydrocarbons. Single crystals of 4·18c8 suitable for X-ray
structure determination were obtained by slow evaporation of a methanol
(
δ 234.1 ppm in MeOH, 234.1 ppm in THF; MeOCSSK).
solution at room temperature. Anal. calcd. for C12
H
27
O
7
RbS
g mol ): C 36.80, H 5.96, S 14.03 %; found: C 36.72, H 6.08, S 13.95 %.
1H NMR: δ 3.60 (s, 24H; CH ) ppm. 13C NMR: δ 60.3 (s;
), 3.91 (s, 3H; CH
CH ), 69.5 (s; CH ), 233.5 (s; CSS) ppm. IR: ν 2966(w), 2930(w), 2902(m),
2
(M = 456.95
Synthesis of 1·12c4: A solution of compound 1 (10 mmol) in dry methanol
20 mL) was prepared in situ under an inert atmosphere of nitrogen as
–1
(
2
3
described above, followed by addition of dry [12]crown-4 (1.62 mL, 10
mmol). Stirring was continued for 30 min and the solution was
subsequently evaporated to dryness in vacuo. The rosiny residue was
washed with dry diethyl ether (3 × 10 mL) and then dried in vacuo, upon
which the product solidified. The product was stored under exclusion of air
and moisture. Yield: 2.71 g (93%). Pale yellow, hygroscopic, crystalline
solid, M.p. 78 °C. A characteristic malodor of the product indicated the
presence of small amounts of sulfur-containing decomposition products.
Very soluble in water and methanol, soluble in THF and acetone, poorly
soluble in diethyl ether. Single crystals of 1·12c4 suitable for X-ray
structure determination were obtained from a concentrated THF solution
3
2
2
1
1
2
869(w), 2856(sh), 2822(w), 1474(m), 1455(m), 1430(w), 1349(m),
285(m), 1249(m), 1233(w), 1182(m), 1135(m), 1094(s), 1077(sh),
041(s), 1017(sh), 955(s), 834(s), 527(w br), 473(m), 295(w), 254(m),
30(m) cm–1
.
5·18c6: Yield: 3.38 g (67%). Pale yellow, odorless, air-stable crystalline
solid, M.p. 144 °C. Very soluble in water and methanol, soluble in THF and
acetone, poorly soluble in diethyl ether as well as in chlorinated and non-
chlorinated hydrocarbons. Single crystals of 5·18c8 suitable for X-ray
structure determination were obtained by slow evaporation of a methanol
at 5 °C. Anal. calcd. for C10
H
19LiO
5
S
2
(M = 290.32 g mol–1): C 41.37, H
1
6
1
2
1
1
1
8
3
.60, S 22.09 %; found: C 41.50, H 6.61, S 22.08 %. H NMR: δ 3.62 (s,
7 2
solution at room temperature. Anal. calcd. for C12H27CsO S (M = 504.39
6H; CH
2
), 3.89 (s, 3H; CH
3
) ppm. 13C NMR: δ 60.2 (s; CH
3
), 69.5 (s; CH
2
),
g mol ): C 33.34, H 5.40, S 12.71 %; found: C 33.29, H 5.50, S 12.67 %.
–1
2 3
), 3.87 (s, 3H; CH
) ppm. 13C NMR: δ 60.4 (s;
33.4 (s; CSS) ppm. IR: ν 2963(w), 2931(m), 2918(sh), 2874(m), 1491(w),
474(w), 1448(m), 1440(sh), 1417(w), 1359(m), 1344(sh), 1308(sh),
284(m), 1258(sh), 1244(m), 1233(sh), 1180(m), 1132(s), 1100(sh),
083(s), 1067(sh), 1054(sh), 1041(s), 1016(s), 932(sh), 921(s), 858(s),
15(w), 779(w), 565(m), 555(w), 537(w), 507(w), 478(m), 372(s br), 330(s),
1H NMR: δ 3.56 (s, 24H; CH
CH ), 61.6 (s; CH
3
2
), 235.7 (s; CSS) ppm. 133Cs NMR: δ 4.0 (s) ppm. IR: ν
2969(w), 2931(w), 2900(m), 2877(w), 2863(sh), 2851(sh), 2819(w),
1475(m), 1454(m), 1430(w), 1348(m), 1283(m), 1247(m), 1233(w),
1182(m), 1132(m), 1093(s), 1041(s), 1017(sh), 953(s), 940(sh), 925(sh),
07(m br), 287(w), 275(w), 242(sh), 205(sh) cm–1
.
864(w), 831(s), 523(w), 475(m), 296(w br), 247(m br), 230(sh) cm–1
.
Synthesis of 2·15c5, 3·18c6, 4·18c6, and 5·18c6: The respective crown
ether (10 mmol) was added to a solution of the respective xanthate salt 2–
Reaction with CO
decomposed within several hours under precipitation of Li
2
: In contact with atmospheric CO
2
, solutions of 1 and 2
2
CO or NaHCO ,
3
3
5
(10 mmol)* in methanol (30 mL), and the mixture was stirred for 30 min
respectively. For 3–5, this reaction proceeded significantly slower.
However, samples of 3–5, which were isolated from solutions that were
exposed to air for a prolonged period of time, were always contaminated
at room temperature. The solution was then reduced in vacuo until the
product began to crystallize, and subsequently diethyl ether (100 mL) was
added. The precipitate was isolated by vacuum filtration, washed with
diethyl ether (3 × 20 mL) and dried in vacuum. *In-situ preparation of 2–5
instead of using the isolated solids led to comparable results.
3
with significant amounts of MHCO (M = K, Rb, Cs). In a representative
series of test reactions, excess dry ice was added to solutions of 1, 2, or 3
in methanol. 13C NMR spectroscopy indicated immediate formation of
carbonate (δ 161.2 ppm), together with gradual decrease of the MeO-
–
CSS signal intensity.
2·15c5: Yield: 2.21 g (63%). Pale yellow, odorless, air-stable crystalline
solid, M.p. 120 °C. Very soluble in water and methanol, soluble in THF and
acetone, poorly soluble in diethyl ether as well as in chlorinated and non-
chlorinated hydrocarbons. Single crystals of 2·15c5 suitable for X-ray
Acknowledgements
structure determination were obtained by layering
a concentrated
methanol solution with excess diethyl ether within several days at room
(M = 350.42 g mol–1): C 41.13,
General financial support by Otto von Guericke Universität
Magdeburg is gratefully acknowledged.
temperature. Anal. calcd. for C10
H 6.62, S 18.30 %; found: C 41.08, H 6.68, S 18.26 %. H NMR: δ 3.70 (s,
H
23NaO
6
S
2
1
2 3 3 2
0H; CH ), 4.00 (s, 3H; CH ), 69.2 (s; CH ),
) ppm. 13C NMR: δ 60.3 (s; CH
2
2
2
1
1
1
33.6 (s; CSS) ppm. 23Na NMR: δ –1.2 (s) ppm. IR: ν 2991(w), 2971(w),
961(w), 2928(sh), 2912(m), 2894(w), 2873(m), 2864(sh), 2818(w),
472(m), 1453(w), 1425(m), 1348(m), 1288(m), 1276(sh), 1252(m),
239(w), 1229(sh), 1180(m), 1142(w), 1119(sh), 1112(s), 1093(sh),
084(s), 1071(sh), 1045(s), 1036(s), 952(sh), 946(s), 926(sh), 861(m),
Keywords: xanthate • dithiocarbonate • crown ether • alkali
metal • crystal structure elucidation
[1]
R. J. Magee, Rev. Anal. Chem. 1973, 1, 335–377.
6
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