Naphthalenehydrides of NdIII and DyIII
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
1593
the dianion (C10H8)2– distant from the lutetium atoms
is not shown).
Hydrolysis of complex 1. A mixture of H2O (0.2 mL, 11.11
mmol) and DME (2 mL) was added to a suspension of complex 1
(0.28 g, 0.24 mmol) in DME (1 mL) at –10 °C, which was acꢀ
companied by vigorous evolution of a gas and formation of a pale
violet flocculent precipitate. The reaction was completed within
10 s, the amount of liberated hydrogen was 64 mL (s.c., 2.86
mmol, 84%), that corresponds to the ratio H2 : Nd = 2.38 : 1.00.
The mixture was centrifuged and the solution was separated from
the precipitate of Nd(OH)3 (identified as Nd2O3 after washing
with water and calcination in air at 200 °C; the yield was 0.23 g
(98%)). A mixture of C10H8, 1,4ꢀC10H10, 1,2ꢀC10H10, and
C10H12 (80 mg, 86%, 4 : 7 : 4 : 1) was also found in the DME
solution.
Hydrolysis of complex 2. Hydrogen (83 mL, 3.70 mmol, 82%)
(H2 : Dy = 2.31 : 1.00), Dy(OH)3 (0.32 g, 94%), and a mixture
of C10H8, 1,4ꢀC10H10, 1,2ꢀC10H10 and C10H12 (0.10 g, 81%)
were obtained from complex 2 (0.40 g, 0.32 mmol) under condiꢀ
tions of the preceding experiment.
Reaction of complex 1 with hexamethyldisilazane. A mixture
of HN(SiMe3)2 (2.28 g) and THF (3 mL) was added to a suspenꢀ
sion of complex 1 (0.50 g, 0.43 mmol) in THF (15 mL). The
reaction mixture was stirred for 48 h at 70 °C, which was accomꢀ
panied by evolution of hydrogen (43 mL, s.c., 90%). A black
precipitate was separated from a colorless solution by decantaꢀ
tion, washed with THF (2×5 mL), and dried in vacuo for 5 h at
40 °C to yield complex 3 (0.45 g, 93%) as a black pyrophoric
powder. Found (%): Nd, 65.0. C30H33Nd5. Calculated (%): Nd,
64.42. IR (Nujol, ν/cm–1): 1270, 840. The colorless solution was
combined with the tetrahydrofuran extract. Recrystallization
Experimental
Syntheses were carried out under conditions excluding exposure
of reagents to atmospheric oxygen and moisture using standard
Schlenk technique. Tetrahydrofuran was distilled over NaOH,
degassed, dried with NdI2 (500 mL of THF, 2 g of NdI2, 20 °C,
30 min), and condensed into the reaction tube just before use.
Diiodides NdI2 and DyI2 were prepared according to the procedure
developed earlier.16 IR spectra were recorded on a FSMꢀ1201
Fourierꢀtransform infrared spectrometer in the range of
4000—400 cm–1. Samples were prepared as suspensions in Nujol.
The content of lanthanide in the compounds obtained was deꢀ
termined by complexometric titration, the content of iodine, by
back titration. Magnetic measurements were carried out using
the known procedure.17 Organic hydrolysis products were anaꢀ
lyzed on a Polaris Q GLCꢀMS instrument.
Reaction of NdI2H with lithium naphthalenide. A solution of
C10H8Li (obtained in situ from Li (0.13 g, 18.6 mmol) and naphꢀ
thalene (4.76 g, 37.2 mmol)) in THF (15 mL) was added to
a suspension of NdI2H (1.82 g, 4.6 mmol) in THF (5 mL). The
solution turned its color from dark green to light brown. The
mixture was vigorously stirred for 24 h at ∼20 °C. The brown
solution was decanted from the black jellyꢀlike precipitate that
formed. The precipitate was washed with fresh THF (6×10 mL)
and dried in vacuo for 4 h at 20 °C to yield complex 1 (0.92 g,
88%) as a black pyrophoric powder. Found (%): Nd, 62.13.
C30H38Li5Nd5. Calculated (%): Nd, 62.48. IR (Nujol, ν/cm–1):
7
from hexane gave LiN(SiMe3)2(THF) (0.47 g, 90%). Li NMR
1
(200 MHz, C6D6, 20 °C), δ: 2.954 (Li). H NMR (200 MHz,
C6D6, 20 °C), δ: 0.10 (3 H, SiMe3); 0.38 (15 H, SiMe3); 1.30 (4 H,
βꢀCH2, THF); 3.64 (4 H, αꢀCH2, THF). IR (Nujol, ν/cm–1):
1251, 1238, 1180, 1046, 1016, 893, 875, 828, 761, 686, 660, 604, 448.
Reaction of complex 2 with hexamethyldisilazane. The reꢀ
action of complex 2 with HN(SiMe3)2 was carried out similarꢀ
ly to that described above for complex 1. The compound
LiN(SiMe3)2(THF) (0.49 g, 89%) was obtained from complex 2
(0.45 g, 0.35 mmol) and (Me3Si)2NH (2.30 g). 7Li NMR
1
(200 MHz, C6D6, 20 °C), δ: 2.954 (Li). H NMR (200 MHz,
C6D6, 20 °C), δ: 0.10 (3 H, SiMe3); 0.38 (15 H, SiMe3); 1.300 (4 H,
βꢀCH2, THF); 3.64 (4 H, αꢀCH2, THF). IR (Nujol, ν/cm–1):
1251, 1238, 1180, 1046, 1016, 893, 875, 828, 761, 686, 660, 604,
448. Amount of liberated hydrogen was 33 mL (s.c., 85%). Comꢀ
plex 4 (0.41 g, 96%) was obtained as a black powder. Found (%):
Dy, 66.70. C30H33Dy5. Calculated (%): Dy, 67.10. IR (Nujol,
ν/cm–1): 1250, 870, 835.
Hydrolysis of complex 3. A mixture of H2O (0.2 mL) and
DME (2 mL) was added to a suspension of complex 3 (0.35 g,
0.31 mmol) in DME (1 mL) at –10 °C, which was accompanied
by vigorous evolution of a gas and formation of a flocculent
precipitate. The amount of liberated hydrogen was 54 mL (s.c.,
2.41 mmol, 86%) (H2 : Nd = 1.55 : 1.00). The precipitate was
separated from the solution and washed with DME (2×1 mL) to
yield Nd(OH)3 (0.29 g, 97%).
1598, 1026, 782, 475. μeff (293 K) = 5.6 μ .
B
Reaction of DyI2H with lithium naphthalenide. The reaction
was carried out similarly to the synthesis of compound 1. Comꢀ
plex 2 (0.62 g, 94%) was obtained as a black powder from DyI2H
(1.10 g, 2.6 mmol), Li (0.055 g, 7.6 mmol), and naphthalene
(1.35 g, 10.5 mmol). Found (%): Dy, 64.90. C30H38Dy5Li5. Calꢀ
culated (%): Dy, 65.23. IR (Nujol, ν/cm–1): 1595, 1509, 1271,
1038, 782, 475.
Hydrolysis of complex 4. Hydrogen (53 mL, s.c., 2.37 mmol,
88%) (H2 : Dy = 1.58 : 1.00) and Dy(OH)3 (0.30 g, 94%) were
obtained from complex 4 (0.36 g, 0.30 mmol) under conditions
of the preceding experiment.
Reaction of complex 1 with cyclopentadiene. A solution of
cyclopentadiene (0.5 g, 7.57 mmol) in THF (10 mL) was added