G. B. Deacon, E. E. Delbridge, B. W. Skelton, A. H. White
(40) [(205Tl)Mϩ], 205 (15) [205Tlϩ], 158 (15) [C10H10N2ϩ]. Ϫ ployed to separate the red solution from the deposited grey solids.
FULL PAPER
C10H9N2Tl (361.6): calcd. Tl 56.52; found Tl 56.84.
The THF was removed under vacuum yielding a red solid which
was dissolved in DME (40 mL) and allowed to stand for several
days at room temperature during which time 0.54 g (78%) of large
red crystals formed. Ϫ IR: ν˜ ϭ 1605 cmϪ1 m, 1528 w, 1509 w, 1297
w, 1275 w, 1240 w, 1224 w, 1210 w, 1191 w, 1121 m, 1097 s, 1073
s, 1045 w, 1028 w, 1009 m, 977 m, 954 m, 943 m, 884 m, 855 s, 818
s, 766 vs, 734 m, 716 vs, 686 m, 673 m. Ϫ 1H NMR (300 MHz,
[D8]THF): δ ϭ 2.73 and 2.79 (br. d, overlapping signals, total inte-
gration 4 H, 4-H,5-H), 3.31 (br. s, 12 H, MeO, DME), 3.48 (br. s,
8 H, CH2 DME), 7.00 (br. m, 3 H, 6-H,7-H,9-H), 7.55 (br. s, 1 H,
3-H), 7.85 (br. s, 1 H, 8-H). Integration of the indazolate protons
showed approximately half the expected intensity. Ϫ Visible/near
IR (THF): λmax (ε): 430 (415) nm. Ϫ C30H38N4O4Yb (691.7): calcd.
C 52.09, H 5.54, N 8.10, Yb 25.02; found C 51.91, H 5.66, N 7.27,
Yb 25.14.
(7-Azaindolato)thallium(I) (1c): Thallium(I) ethoxide (2.56 mL, 9.01
g, 36.1 mmol) was added to an ether solution (30 mL) of 7-azain-
dole (4.26 g, 36.1 mmol) giving a white precipitate and a pale yel-
low solution. The white precipitate was filtered from solution and
washed with petroleum ether (2 ϫ 30 mL) giving 1c [11.61 g (65%)].
Ϫ IR: ν˜ ϭ 1582 cmϪ1 w, 1534 w, 1333 w, 1278 m, 1257 w, 1150 m,
1
1092 m, 1044 w, 898 m, 798 s, 766 vs, 746 s, 721 vs, 622 m. Ϫ H
NMR (200 MHz, [D8]THF): δ ϭ 6.39 (s, 1 H, 3-H), 6.90 (dd, 1 H,
5-H) 7.30 (s, 1 H, 2-H), 7.87 (d, 1 H, 4-H), 8.05 (d, 1 H, 7-H). Ϫ
C7H5N2Tl (321.5): calcd. Tl 63.57; found Tl 64.11.
(3,5-Diphenylpyrazolato)thallium(I) (1d): The preparation and
properties have been given in a preliminary report.[8]
(4-Methyl-3,5-diphenylpyrazolato)thallium(I) (1e): Thallium(I)
ethoxide (0.35 mL, 1.25 g, 5.0 mmol) was added to a THF solution
(30 mL) of 4-methyl-3,5-diphenylpyrazole (1.17 g, 5.0 mmol) giving
a deep yellow solution. This was reduced in volume to ca. 5 mL
and petroleum ether was added causing deposition of 1e as a white
solid, which was filtered off and dried under vacuum [1.80 g (82%)].
Ϫ IR: ν˜ ϭ 1601 cmϪ1 m, 1528 w, 1516 w, 1292 w, 1248 w, 1225 w,
1145 w, 1117 s, 1070 s, 1011 s, 994 w, 966 w, 916 m, 847 w, 771 vs,
Bis(1,2-dimethoxyethane)bis(3-methyl-5-phenylpyrazolato)-
ytterbium(II) (3b): A mixture of ytterbium powder (1.73 g, 10.0
mmol), mercury metal (ca. 0.20 mL), and (3-methyl-5-phenylpyr-
azolato)thallium(I) (1.20 g, 2.31 mmol) in THF (30 mL) was sub-
jected to ultrasonication for 48 h. The resulting deep red solution
with grey suspended solids was allowed to stand for several hours
until the suspension settled out. The reaction mixture was then
filtered using a filter cannula. The filtrate was concentrated to dry-
ness under vacuum yielding a red solid which was dissolved in
DME which was subsequently removed under vacuum giving 3b
[0.48 g (62%)]. Ϫ IR: ν˜ ϭ 1602 cmϪ1 m, 1527 w, 1491 m, 1413 m,
1298 w, 1190 w, 1155 w, 1099 m, 1054 s, 1016 m, 964 m, 912 w, 888
m, 858 m, 762 vs, 712 m, 695 vs. Ϫ Visible/near IR (THF): λmax
1
718 s, 700 vs. Ϫ H NMR (300 MHz, [D8]THF): δ ϭ 2.26 (s, 3 H,
CH3), 7.20Ϫ7.26 (m, 2 H, p-H), 7.29Ϫ7.31 (m, 4 H, m-H), 7.44 (t,
4 H, o-H). Ϫ 13C{1H} NMR (400 MHz, [D8]THF): δ ϭ 12.2 (Me),
111.9 (C-4, pz), 127.2 (C-4, Ph), 129.1 (C-2,C-6 and C-3,C-5, Ph),
136.2 (C-1, Ph), 153.1 (C-3,C-5, pz). Ϫ MS (70 eV, EI); m/z (%):
438 (40) [(205Tl)Mϩ], 234 (90) [C16H14N2ϩ], 205 (15) [205Tlϩ], 130
(100) [C9H8Nϩ]. Ϫ C16H13N2Tl (437.7): calcd. C 43.90, H 2.99, N
6.40; found C 44.00, H 3.08, N 6.21.
1
(ε) ϭ 389 nm (586). Ϫ H NMR (300 MHz, [D8]THF): δ ϭ 2.22
(br. s, 6 H, 3-Me), 3.20 (s, 12 H, MeO DME), 3.36 (s, 8 H, CH2
DME), 6.30 (br. s, 2 H, 4-H), 6.96 (br. s, 2 H, p-H), 7.14 (br. s, 4
H, m-H), 7.72 (br. s, 4 H, o-H). Ϫ C28H38N4O4Yb (667.7): calcd.
Yb 25.92; found Yb 25.82.
Bis(3,5-diphenylpyrazolato)mercury(II) (2)
Method A: 3,5-Diphenylpyrazole (1.00 g, 4.5 mmol) was treated
with a THF solution (30 mL) of potassium hydride (0.18 g, 4.5
mmol) at 0°C. Gas evolution was observed and a slightly pale yel-
low solution formed. HgCl2 (0.62 g, 2.3 mmol) was added causing
formation of a white precipitate. The reaction mixture was stirred
for 1 h and then was treated with water. The precipitated mercurial
2 was filtered off, washed with water, ethanol, and ether, and then
dried under vacuum for 30 min giving 1.10 g (76%) of impure 2 as
a white powder. Ϫ IR: ν˜ ϭ 1604 cmϪ1 m, 1542 w, 1400 m, 1236 w,
1321 w, 1296 w, 1274 m, 1236 m, 1157 m, 1128 m, 1074 s, 1026 m,
1001 w, 986 m, 958 w, 914 m, 844 w, 800 w, 758 vs, 696 vs. Ϫ MS
(electrospray); m/z (%): 641 (100) [(202Hg)MHϩ], 549 (100)
Bis(7-azaindolato)bis(1,2-dimethoxyethane)ytterbium(II) (3c):
A
mixture of ytterbium powder (1.73 g, 10.0 mmol), mercury metal
(ca. 0.20 mL), and (7-azaindolato)thallium(I) (0.64 g, 2.0 mmol) in
THF (30 mL) was subjected to ultrasonication for 16 h. The re-
sulting deep red solution with grey suspended solids was allowed
to stand for several hours until the suspension settled out. The
reaction mixture was then filtered using a filter cannula. The filtrate
was concentrated to dryness under vacuum yielding a red solid
which was recrystallised from DME giving 3c [0.41 g (70%)]. Ϫ IR:
ν˜ ϭ 1581 cmϪ1 m, 1542 m, 1402 w, 1335 w, 1321 m, 1295 s, 1258
m, 1193 m, 1153 s, 1118 m, 1060 m, 1020 m, 984 m, 951 w, 907 w,
896 w, 857 vs, 795 s, 771 s, 744 s, 718 vs, 617 m, 598 m. Ϫ Visible/
[
202HgC23H15N4ϩ], 467 (76) [202HgC17H19N3ϩ]. Ϫ C30H22N4Hg
(639.1): calcd. C 56.38, H 3.47, N 8.77; found C 54.57, H 3.77,
N, 8.07.
1
near IR (THF): λmax (ε) ϭ 480 nm (259). Ϫ H NMR (300 MHz,
[D6]benzene): δ ϭ 2.79 (s, 12 H, MeO DME), 2.83 (s, 8 H, CH2
DME), 6.74 (m, 4 H, 2-H,5-H), 7.88 (s, 2 H, 2-H), 7.97 (m, 4 H,
4-H,7-H). Ϫ 171Yb NMR (52.5 MHz, 0.04 in DME): δ ϭ 489
(∆ν1/2 ϭ 54 Hz). Ϫ C22H30N4O4Yb (587.6): calcd. C 44.97, H 5.15,
N 9.54, Yb 29.45; found C 43.85, H 4.82, N 10.01, Yb 29.41.
Method B: HgBr2 (1.80 g, 5.0 mmol) and NaBr (2.05 g, 20 mmol)
were dissolved in tBuOH (80 mL). 3,5-Diphenylpyrazole (2.20 g,
10 mmol) and NaOH (0.80 g, 20 mmol) were added and the reac-
tion mixture was refluxed for 4 h. The cream-coloured solution was
poured into distilled H2O (150 mL) giving bis(3,5-diphenylpyrazol-
ato)mercury as a cream precipitate which was filtered from the
solution and dried under vacuum. The infrared spectrum of this
compound was in good agreement with that of the product from
Method A and a yield of > 90% was obtained.
Bis(1,2-dimethoxyethane)bis(3,5-diphenylpyrazolato)ytterbium(II)
(3d)
Method A: A mixture of ytterbium powder (0.83 g, 4.8 mmol) and
Hg(Ph2pz)2 (1.00 g, 2.4 mmol) in THF (30 mL) was subjected to
ultrasonication for 6 d. The resulting deep red solution with grey
suspended solids was allowed to stand for several hours, and was
Bis(2H-benz[g]-4,5-dihydroindazolato)bis(1,2-dimethoxyethane)-
ytterbium(II) (3a): A mixture of ytterbium powder (0.69 g, 4.0
mmol) and (2H-benz[g]-4,5-dihydroindazolato)thallium(I) (0.74 g, then filtered. The THF was removed under vacuum giving a deep
2.0 mmol) in THF (30 mL) was subjected to ultrasonication for 24
h. The resulting deep red solution with grey suspended solids was
allowed to stand for several hours, when a filter cannula was em-
red sticky solid which was recrystallised from DME affording 1.10
g (58%) of large red crystals. Ϫ IR: identical with that reported.[8]
Ϫ C38H42N4O4Yb (791.8): calcd. Yb 21.85; found Yb 22.28, 22.04.
758
Eur. J. Inorg. Chem. 1999, 751Ϫ761