10.1002/ejic.201701408
European Journal of Inorganic Chemistry
FULL PAPER
Gd4(N3)10(OH)2 · 10 DMSO was found to be a mixture of a triclinic (α) and a
[Ph4P]3[Gd(N3)6] · 2 MeCN were washed with acetonitrile. Drying in vacuum
led to non-stoichiometric loss of solvent (yield: 20–30 %). M.p. 216 °C; 1H
NMR (300 K, [D6]DMSO, 500.13 MHz): δ = 2.17 (s, CH3CN, Δν1/2 = 240 Hz),
7.88 ppm (s, 20 H; Aryl, Δν1/2 = 340 Hz); 13C NMR (300 K, [D6]DMSO,
̅
monoclinic (β) modification (space groups P 1 and P21/c) in varying
compositions
(yield:
20–30 %).
Storage
of
crystalline
Gd4(N3)10(OH)2 · 10 DMSO in DMSO/acetonitrile (excess MeCN) solution for
several months resulted in the slow transformation into crystals of
Gd4(N3)10(OH)2 · 8 DMSO as confirmed by single crystal X-ray diffraction.
125.8 MHz):
δ = 135.79 (s, para), 134.97 (s, ortho), 130.89 (s, meta),
118.10 ppm (d, 1J(13C - 31P) = 87 Hz, PC); 31P NMR (300 K, [D6]DMSO,
202.5 MHz): δ = 22.34 ppm (s); 14N NMR (300 K, [D6]DMSO, 36.1 MHz): δ = -
136 (MeCN, Δν1/2 = 190 Hz), -240 ppm (Nα/γ, Δν1/2 = 750 Hz); IR (ATR,
32 scans): 휈̃ = 3468 (w), 3392 (w), 3168 (w), 3079 (w), 3058 (w), 3022 (w),
2993 (w), 2963 (w), 2690 (w), 2581 (w), 2111 (w), 2052 (s), 1828 (w), 1790
(w), 1585 (m), 1483 (m), 1434 (m), 1357 (m), 1316 (m), 1222 (w), 1186 (w),
1163 (w), 1105 (s), 1079 (sh, m), 1027 (w), 995 (m), 937 (w), 850 (w), 754 (m),
719 (s), 686 (s), 665 (sh, m), 615 cm-1 (m); Raman (473 nm, 0.36 mW, 25 °C,
40 s, 12 acc.): 휈̃ = 3168 (3.4), 3144 (3.4), 3061 (10), 3025 (3.0), 3010 (3.0),
2993 (3.0), 2959 (2.9), 2931 (3.3), 2248 (2.2), 2110 (1.8), 2054 (1.6), 1585
(6.3), 1482 (1.0), 1438 (1.2), 1364 (4.8), 1340 (sh, 1.1), 1274 (0.8), 1223 (0.7),
1188 (1.1), 1163 (1.0), 1106 (sh, 1.9), 1096 (3.2), 1076 (0.7), 1026 (4.1), 999
(7.5), 935 (0.6), 854 (0.4), 749 (0.4), 724 (0.5), 677 (1.5), 614 (1.1), 533 (0.2),
454 (0.2), 394 (0.1), 376 (0.1), 283 (0.6), 254 (1.3), 196 (0.9), 154 cm-1 (1.6);
elemental analysis calcd (%) for C76H66N20GdP3: C 60.47, H 4.41, N 18.56;
found C 58.81, H 4.65, N 17.54.
Gd4(N3)10(OH)2 · 10 DMSO (Mixture of α- and β-phase): M.p. 173 °C
(decomp.); 14N NMR (300 K, [D6]DMSO, 36.1 MHz): δ = -283 ppm (Nα/γ, Δν1/2
=
991 Hz). IR (ATR, 32 scans): 휈̃ = 3581 (w), 3390 (w), 3343 (w), 2997 (w), 2916
(w), 2653 (w), 2092 (m), 2066 (s), 2047 (s), 1413 (m), 1404 (sh, m), 1350 (m),
1315 (m), 1298 (m), 1290 (m), 1233 (w), 1227 (w), 1007 (s), 964 (s), 942 (m),
911 (m), 712 (m), 679 (m), 657 (m), 650 (m), 613 cm-1 (m); Raman (633 nm,
5 mW, 25 °C, 20 s, 10 acc.): 휈̃ = 3583 (0.5), 3002 (1.6), 2918 (4.0), 2109 (0.7),
2073 (0.4), 1416 (0.9), 1357 (3.8), 1320 (0.2), 1299 (0.3), 1291 (0.4), 1030
(0.5), 1013 (0.4), 968 (0.4), 946 (0.1), 717 (2.0), 684 (5.2), 659 (0.3), 615 (0.2),
404 (0.4), 342 (1.0), 318 (1.5), 293 (1.3), 223 (2.3), 174 (2.3), 87 cm-1 (10);
elemental analysis calcd (%) for C20H62N30Gd4O12S10: C 12.88, H 3.35, N
22.54, S 17.20; found C 13.21, H 2.80, N 19.28, S 15.45.
Gd4(N3)10(OH)2 · 8 DMSO: Raman (633 nm, 5 mW, 25 °C, 20 s, 10 acc.): 휈̃ =
2998 (3.3), 2912 (8.6), 2104 (1.0), 2062 (1.0), 1409 (1.1), 1367 (3.4), 1354
(2.3), 1304 (0.8), 1294 (0.9), 1233 (0.4), 1027 (0.5), 1006 (0.6), 970 (0.2), 954
(0.3), 799 (2.6), 739 (1.7), 710 (1.7), 675 (4.6), 635 (0.4), 527 (0.5), 402 (0.5),
328 (2.2), 296 (3.0), 217 (3.1), 203 (3.0), 175 (4.2), 71 cm-1 (10).
[EtPh3P]3[Ce(N3)6]: To
a solution of cerium(III) iodide CeI3 (0.130 g,
0.25 mmol) and silver azide AgN3 (0.114 g, 0.76mmol) in acetonitrile (4 mL), a
suspension of ethyltriphenylphosphonium iodide [EtPh3P]I (0.313 g,
0.75 mmol) and AgN3 (0.114 g, 0.76 mmol) in acetonitrile (4 mL) was added.
After stirring for 30 minutes, the resulting black-brownish solution was
separated from the yellow precipitate by filtration (F4) and concentrated to
about 3 mL in vacuum. Storage at ambient temperature for several hours
resulted in the deposition of colorless crystals of [EtPh3P]3[Ce(N3)6] besides
small amounts of a brownish, amorphous precipitate, which was removed by
washing with acetonitrile (yield: 10–20 %). M.p. 213 °C; 1H NMR (300 K,
[D6]DMSO, 500.13 MHz): δ = 7.73 - 7.90 (m, 15 H, Aryl), 3.61 (dquartett, 2 H,
J(1H - 1H) = 7.4 Hz, J(1H - 31P) = 13.6 Hz, CH2CH3), 1.22 (dtriplett, 3 H, J(1H - 1H)
= 7.4 Hz, 53 J(1H - 31P) = 20.2 Hz, CH2CH3); 13C NMR (300 K, [D6]DMSO,
125.8 MHz): δ = 134.91 (d, 4J(13C - 31P) = 2.8 Hz, para), 133.52 (d, 2J(13C -
31P) = 10.1 Hz, ortho), 130.28 (d, 3J(13C - 31P) = 12.8 Hz, meta), 118.33 (d,
1J(13C - 31P) = 85.2 Hz, PC), 14.41 (d, 1J(13C - 31P) = 51.5 Hz, CH2), 6.27 (d,
2J(13C - 31P) = 5.5 Hz, CH3); 31P NMR (300 K, [D6]DMSO, 202.5 MHz): δ =
26.01 (s, 1J(13C - 31P) = 85.2 Hz); 14N NMR (300 K, [D6]DMSO, 36.1 MHz): δ =
-126 (Nβ, Δ휈1/2 = 100 Hz), -232 (Nα/γ, Δ휈1/2 = 394 Hz); IR (ATR, 32 scans): 휈̃ =
3446 (w), 3376 (w), 3082 (w), 3064 (w), 3053 (w), 2993 (w), 2983 (w), 2936
(w), 2902 (w), 2877 (w), 2648 (w), 2105 (w), 2044 (s), 1824 (w), 1781 (w),
1585 (m), 1573 (w), 1483 (m), 1450 (w), 1434 (m), 1402 (m), 1383 (w), 1347
(m), 1315 (m), 1293 (w), 1279 (w), 1238 (w), 1225 (w), 1186 (w), 1160 (m),
1111 (s), 1073 (m), 1037 (m), 1028 (m), 1013 (w), 996 (m), 978 (w), 929 (w),
848 (w), 770 (sh, w), 746 (m), 737 (s), 721 (s), 690 (s), 665 (m), 617 (m), 530
cm-1 (s). Raman (633 nm, 6 mW, 25 °C, 30 s, 12 acc.): 휈̃ = 3166 (0.7), 3139
(0.7), 3062 (2.5), 3051 (2.1), 3004 (0.7), 2980 (0.7), 2933 (1.3), 2900 (1.0),
2874 (0.8), 2245 (0.6), 2149 (0.6), 2140 (0.5), 2095 (0.6), 2037 (0.5), 1581
(3.3), 1569 (0.9), 1480 (0.4), 1447 (0.4), 1434 (0.4), 1399 (0.4), 1379 (0.4),
1351 (2.1), 1345 (sh, 1.0), 1312 (0.3), 1185 (0.6), 1159 (0.7), 1099 (2.1), 1069
(0.3) 1022 (2.8), 994 (5.5), 922 (0.2), 849 (0.1), 765 (0.1), 733 (0.1), 717 (0.1),
704 (0.1), 686 (0.1), 660 (2.0), 617 (sh, 0.3), 610 (0.8), 524 (0.1), 482 (0.1),
462 (0.1), 449 (0.1), 430 (0.1), 391 (0.1), 374 (0.3), 304 (0.4), 293 (0.2), 275
(0.6), 248 (1.9), 210 (0.9), 196 (0.9), 82 cm-1 (10); elemental analysis calcd
(%) for C60H60N18CeP3: C 56.91, H 4.71, N 19.91; found C 54.72, H 5.00, N
19.46.
[Ph4P]3[Ce(N3)6] · 2 MeCN: To a solution of cerium(III) iodide CeI3 (0.130 g,
0.25 mmol) and tetraphenylphosphonium azide [Ph4P]N3 (0.286 g, 0.75 mmol)
in acetonitrile (7 mL) silver azide AgN3 (0.113 g, 0.75 mmol) was added and
stirred for 45 minutes. After filtration the clear, black-brown solution was slowly
concentrated by evaporation, resulting in the deposition of colorless crystals.
The supernatant was removed by decantation and the colorless crystals of
[Ph4P]3[Ce(N3)6] · 2 MeCN were washed with acetonitrile. According to X-ray
structure determinations, [Ph4P]3[Ce(N3)6] · 2 MeCN was found to be a mixture
̅
of two triclinic modifications (denoted as (α) and (β), space group P1) in
varying compositions. Drying in vacuum led to the non-stoichiometric loss of
solvent (yield: 10–20 %). M.p. 187 °C (heating rate 20 °C/min); 1H NMR
(300 K, [D6]DMSO, 500.13 MHz): δ = 7.95 (m, 4 H, para), 7.81 (m, 8 H, meta),
7.75 (m, 8 H, ortho), 2.04 ppm (s, CH3CN); 13C NMR (300 K, [D6]DMSO,
125.8 MHz): δ = 135.39 (d, 4J(13C - 31P) = 2.75 Hz, para), 134.58 (d, 2J(13C -
31P) = 10.08 Hz, ortho), 130.50 (d, 3J(13C - 31P) = 12.83 Hz, meta), 117.73 ppm
(d, 1J(13C - 31P) = 88.89 Hz, PC); 31P NMR (300 K, [D6]DMSO, 202.5 MHz): δ =
C - =
22.29 ppm (s, 1J(13 31P) 88.89 Hz); 14N NMR (300 K, [D6]DMSO,
36.1 MHz): δ = -126 (Nβ; Δν1/2 = 101 Hz), -228 ppm (Nα/γ, Δν1/2 = 434 Hz); IR
(ATR, 32 scans): 휈̃ = 3453 (w), 3375 (w), 3163 (w), 3079 (w), 3058 (w), 3022
(w), 2993 (w), 2931 (w), 2692 (w), 2584 (w), 2247 (w), 2101 (w), 2040 (s),
1834 (w), 1788 (w), 1585 (m), 1483 (m), 1435 (s), 1350 (m), 1316 (m), 1277
(w), 1226 (w), 1187 (m), 1162 (w), 1105 (s), 1076 (sh, w), 1026 (m), 995 (m),
939 (w), 848 (w), 755 (m), 719 (s), 686 (s), 665 (m), 616 cm-1 (m); Raman
(473 nm, 2 mW, 25 °C, 15 s, 10 acc.): 휈̃ = 3171 (6.0), 3146 (6.0), 3062 (10),
3012 (5.4), 2963 (5.3), 2938 (5.5), 2251 (4.0), 2153 (4.4), 2098 (4.7), 2043
(4.2), 1587 (5.5), 1485 (2.6), 1442 (2.6), 1362 (4.1), 1355 (sh, 3.2), 1347 (sh,
2.7), 1187 (2.2), 1168 (2.2), 1110 (2.6), 1099 (3.8), 1028 (4.1), 1001 (6.8), 932
(1.6), 725 (1.4), 679 (2.2), 615 (2.0), 548 (1.4), 383 (0.9), 288 (1.1), 260 (1.5),
249 (1.6), 198 (1.4), 156 cm-1(1.7); elemental analysis calcd (%) for
C76H66N20CeP3: C 61.16, H 4.46, N 18.77; found C 58.91, H 5.08, N 17.62.
[Ph4P]3[Gd(N3)6] · 2 MeCN: Gadolinium(III) chloride GdCl3 · 2 MeCN (0.086 g,
0.25 mmol) and tetraphenylphosphonium iodide [Ph4P]I (0.351 g, 0,75 mmol)
were dissolved in acetonitrile (10 mL) and silver azide AgN3 (0.229 g,
1.53 mmol) was added. After stirring for one hour, the yellow precipitate was
removed by filtration. Evaporation of the solvent resulted in the deposition of
colorless crystals. For purification the product was recrystallized from
[EtPh3P]3[Gd(N3)6]: To a solution of gadolinium(III) chloride GdCl3 · 2 MeCN
(0.086 g, 0.25 mmol) in acetonitrile (10 mL), ethyltriphenylphosphonium iodide
(0.318 g, 0.76 mmol) followed by silver azide AgN3 (0.225 g, 1.50 mmol) were
added. After stirring for 90 minutes, the resulting yellow precipitate was
removed by filtration (F4). Evaporation of the solvent in vacuum led to the
acetonitrile. After
decantation of supernatant, the crystals
of
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