M. E. Burin, M. V. Smirnova, G. K. Fukin, E. V. Baranov, M. N. Bochkarev
FULL PAPER
(Nizhny Novgorod) and used without additional purification. Va-
nadocene and cobaltocene were prepared according to published
procedures.[17,18] Ferrocene, nickelocene, and chromocene were pur-
chased from Aldrich. The ESR spectra were recorded with a Bruker
200D-SRC instrument. The IR spectra of the samples, prepared
as Nujol mulls, were recorded with a Specord M-75 spectrometer.
Melting points were determined in sealed capillaries.
black pyrophoric powder (1.35 g). IR (nujol, KBr): ν = 1600 (w),
˜
1011 (m), 842 (sh), 800 (s), 677 (w), 619 (w) cm–1.
Reaction of NdI2 (1) with Cp2Cr in Benzene (at 20 °C): A solution
of Cp2Cr (0.34 g, 0.19 mmol) in benzene (10 mL) was added to a
powder of 1 (1.53 g, 0.38 mmol), and the mixture was stirred for
10 h at ambient temperature. The resultant dark-cherry solution
was separated from the precipitate, and the solvent was removed in
vacuo. The waxy residue was extracted with hexane (2×10 mL).
Slow evaporation of hexane from the extract afforded 5 (0.18 g,
39%) as dark cherry-red crystals with m.p. 84–87 °C (dec.).
C10H10Cr2I2 (487.90): calcd. C 24.60, H 2.05, Cr 21.32; found C
Reaction of DyI2 (2) with Cp2V (3) in Benzene: A solution of 3
(0.2 g, 1.10 mmol) in benzene (10 mL) was added to a powder of 2
(1.89 g, 4.54 mmol), and the mixture was stirred at 80 °C for 10 h.
The resultant dark brown solution was separated from the precipi-
tate by decantation, the solvent was removed by evaporation in
vacuo, and the residue was extracted with hexane (2×10 mL). The
extract was placed into an apparatus for sublimation, hexane was
evaporated in vacuo, and the solid residue was heated gradually up
to 110 °C. The sublimed mixture of violet and dark brown crystals
was sublimed again. At 50–60 °C (0.1 Torr) violet crystals of 3
(0.11 g, 54%) were collected and separated [ESR (77 K): gЌ = 4.0,
AЌ (51V) = 2.8 mTs, g = 2.0]. Sublimation of the remaining sub-
stance at 100–110 °C (0.1 Torr) gave dark brown crystals of
(C6H6)2V. Yield 55 mg (24%); m.p. 275–277 °C; ESR (293 K):
Ai(51V) = 6.35 mT, gi = 1.986. The solid residue after extraction
with hexane was recrystallized from THF to give CpDyI2(THF)3
(75 mg, 5%). Decomposition temperature, IR spectrum and results
of elemental analysis of the product were identical to those of the
previously synthesized compound.[19]
25.01, H 2.50, Cr 21.05. IR (nujol, KBr): ν = 3088 (w), 1011 (s),
˜
815 (s), 784 (s), 720 (m), 665 (m), 561 (m) cm–1.
Reaction of DyI2 (2) with Cp2Cr in Benzene (at 20 °C): Under the
conditions of the previous experiment, compound 2 (1.12 g,
2.69 mmol) was treated with Cp2Cr (0.24 g, 1.32 mmol) in benzene
(8 mL). The resultant dark-cherry solution was separated from the
precipitate, the solvent was removed in vacuo, and the residue was
extracted with pentane. Cooling the extract to 0 °C gave 5 (0.142 g,
44%). The residue after pentane extraction was recrystallized from
toluene to give 6 (0.146 g, 26%) as light yellow crystals. C10H10DyI
(739.02): calcd. Dy 38.74; found Dy 38.72. IR (nujol, KBr): ν =
˜
1008 (s), 890 (w), 781 (s), 727 (m), 661 (m) cm–1.
Reaction of DyI2 (2) with Cp2Cr in Benzene (at 80 °C): A mixture
of 2 (0.537 g, 1.29 mmol) and Cp2Cr (0.14 g, 0.77 mmol) in ben-
zene (8 mL) was stirred at 80 °C for 12 h. The initial orange-red
color of the solution gradually turned pale green. The solution was
decanted from the black precipitate, and the solvent was evaporated
in vacuo to leave behind a greenish powder, which was extracted
with toluene. Cooling of the toluene extract in a refrigerator yielded
yellow crystals of 6 (92 mg, 34%). C10H10DyI (739.02): calcd. C
26.61, H 2.38, Dy 38.74; found C26.35, H 2.56, Dy 38.56. The IR
spectrum was identical to that of the compound from the previous
experiment. Among the isolated yellow crystals of 6, a few green-
ish-yellow crystals were found. X-ray diffraction investigation of
one of them revealed the compound to be -ate complex 7. The
amount of isolated 7 was not enough for elemental and spectro-
scopic analyses.
Reaction of NdI2 (1) with Cp2V (3) in Benzene: Compound 1 (3.46 g,
8.69 mmol) reacted with compound 3 (0.35 g, 1.93 mmol), under
the conditions of the previous experiment, to give (C6H6)2V
(42 mg, 10%). The sublimation of the solid products gave unre-
acted 3 (0.24 g, 69%). From the solid residue after hexane extrac-
tion, a few crystals of CpNdI2(THF)3 were isolated by recrystalli-
zation from THF. Characteristics of the product were identical to
those of the complex obtained in the reaction of 1 with cyclopenta-
diene.[19]
Reaction of DyI2 (2) with Cp2V (3) in Isopropylbenzene: A mixture
of 2 (1.01 g, 2.43 mmol), 3 (0.2 g, 1.11 mmol), and isopropylben-
zene (7 mL) was stirred at 90 °C for 20 h. The resultant red-brown
solution was separated from the precipitate by decantation, and
cumene was removed in vacuo. A waxy residue was extracted with
hexane (10 mL), and the extract was transferred into a sublimation
apparatus. After evaporation of hexane, the solid products were
sublimed in vacuo by gradually increasing the temperature from
20 °C to 150 °C. Unreacted 3 (57 mg, 29%), which sublimed at 50–
60 °C, was collected in the top part of the apparatus. At 100–
120 °C, yellow needle crystals of (iPrC6H5)2V (4 mg, 1%) sublimed;
ESR (300 K): αi(51V) = 6.29 mT, gi = 1.988, Ai(H) = 5 G.
Reaction of DyI2 (2) with Cp2Ni in Benzene: A solution of Cp2Ni
(0.12 g, 0.64 mmol) in benzene (15 mL) was added to a powder of
2 (0.56 g, 1.34 mmol), and the mixture was stirred at 70 °C for 12 h.
Formation of a nickel mirror on the walls of the reactor was ob-
served. The resultant wine-colored solution was separated from the
precipitate, and the latter was washed with benzene (15 mL). The
reaction solution and benzene wash were combined, and the sol-
vent was evaporated in vacuo. The solid residue was recrystallized
from benzene to give 6 (0.11 g, 42%).
Reaction of DyI2 (2) with Cp2V (3) in Naphthalene: A mixture of 2 X-ray Diffraction Study: The X-ray diffraction data were collected
(1.6 g, 3.84 mmol), 3 (0.26 g, 1.44 mmol), and naphthalene (2.5 g)
was stirred at 110–120 °C in a sealed ampoule. After 20 h, the re-
sultant black mixture was cooled to room temperature to give a
black solid from which a mixture of naphthalene and unreacted 3
was separated by sublimation in vacuo at 50–60 °C. The black resi-
due was extracted with benzene (3×30 mL), the greenish solution
obtained was concentrated to 8 mL and cooled to 8–10 °C to give
violet crystals of 4. The product was separated by decantation and
dried in vacuo at room temperature. A sample of 4 isolated under
these conditions contained three molecules of benzene. Yield 0.28 g
(5%); m.p. Ͼ240 °C (dec.). C63H63Dy7I15V (3910.94): calcd. C
with a SMART APEX diffractometer (graphite-monochromated,
Mo-Kα-radiation, φ-ω-scan technique, λ = 0.71073 Å). The inten-
sity data were integrated by the SAINT program.[20] SADABS[21]
was used to perform area-detector scaling and absorption correc-
tions. The structures were solved by direct methods and refined on
F2 using all reflections with the SHELXTL package.[22] All non-
hydrogen atoms were refined anisotropically. The H atoms in 5 and
7 [except H(2)] were found from Fourier synthesis and refined iso-
tropically. The H atoms in 4 and the H(2) atom in 5 were placed
in calculated positions and refined in the “riding-model”. In the
unit cell of 4 were found the solvated molecules of benzene. The
details of crystallographic, collection, and refinement data for 4, 5,
and 7 are shown in the Table 1. The selected geometric characteris-
tics for 4, 5, and 7 are given in the captions to Figure 1, Figure 2,
19.20, H 1.81; found C 19.33, H 1.61. IR (nujol, KBr): ν = 1010
˜
(s), 796 (s), 673 (m) cm–1. The black residue after separation of the
benzene extract was dried in vacuo at room temperature to give a
354
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Eur. J. Inorg. Chem. 2006, 351–356
Burin, Mikhail E.
