Synthesis and catalytic activity of η1-allyl and η3-allyl, ethyl, and hydrido complexes of ruthenium- pentamethyl[60]fullerene

Article abstract of DOI:10.1002/ejic.200700013

η¹-Allyl and η³-allyl, ethyl, and hydrido ruthenium complexes of pentamethyl[60]fullerene, Ru(η⁵-C ₆₀Me₅)R(CO)₂ (R = η¹-allyl, Et, H) and Ru(η⁵-C₆₀Me₅)(η³- allyl)(CO) were synthesized by the reaction of a chlorido complex Ru(η⁵-C₆₀Me₅)Cl(CO)² with an allyl and an ethyl Grignard reagent or lithium aluminum hydride. Conversion of the η¹-allyl complex to the corresponding η³-allyl complex and the catalytic performance of the hydrido and the chlorido complexes in the isomerization reaction of 1-decene to internal decenes are described. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200700013

FULL PAPER
DOI: 10.1002/ejic.200700013
Synthesis and Catalytic Activity of η1-Allyl and η3-Allyl, Ethyl, and Hydrido
Complexes of Ruthenium–Pentamethyl[60]fullerene
Yutaka Matsuo,[a] Takashi Uematsu,[b] and Eiichi Nakamura*[a,b]
Keywords: Ruthenium / Fullerenes / Allyl complexes / Hydrido complexes / Isomerization
η1-Allyl and η3-allyl, ethyl, and hydrido ruthenium com-
plexes of pentamethyl[60]fullerene, Ru(η5-C60Me5)R(CO)2
(R = η1-allyl, Et, H) and Ru(η5-C60Me5)(η3-allyl)(CO) were
synthesized by the reaction of a chlorido complex Ru(η5-
C60Me5)Cl(CO)2 with an allyl and an ethyl Grignard reagent
or lithium aluminum hydride. Conversion of the η1-allyl com-
plex to the corresponding η3-allyl complex and the catalytic
performance of the hydrido and the chlorido complexes in
the isomerization reaction of 1-decene to internal decenes
are described.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
gano[60]fullerene ligands to the d6 metal center with the
octahedral geometry.[6a] Indeed, ruthenium complex Ru(η5-
C60Me5)Cl(CO)2 was obtained in high yield on a large scale
and was used as a useful starting material for the study of
the organometallic chemistry of the metal–fullerene com-
plexes.[6a] As an extension of our work in this area, we have
investigated further derivatization of the ruthenium com-
plex and obtained various ruthenium–pentamethyl[60]ful-
lerene complexes. Herein we report the synthesis and cata-
lytic activity of η1- and η3-allyl, ethyl, and hydrido ruthe-
nium complexes of pentamethyl[60]fullerene (Scheme 1).
Introduction
Cooperative effects of fullerene conjugated systems and
transition metal atoms have attracted the interest of inor-
ganic and organometallic chemists[1] because of the possible
dπ-conjugative synergy that may create new properties un-
available from individual systems.[2] We have employed
pentaorgano[60]fullerenes[3] as η5-fullerene ligands and syn-
thesized various metal–fullerene complexes involving Re,[4]
Fe,[5] Ru,[6] Rh,[7] Ir,[8] Ni,[9] Pd,[9] and Pt[9] atoms. Among
them, many ruthenium(II) complexes are particularly inter-
esting because of stable facial coordination of the pentaor-
Results and Discussion
Synthesis of η1- and η3-Allyl Ruthenium Complexes of
Pentamethyl[60]fullerene
Treatment of a solution of Ru(η5-C60Me5)Cl(CO)2 (1)[6a]
in toluene with a solution of allylmagnesium bromide in thf
at 25 °C led to a ligand exchange reaction to afford η1-allyl
complex 2, Ru(η5-C60Me5)(η1-allyl)(CO)2, in quantitative
yield (Scheme 1). Product 2 was purified by neutral alumina
chromatography to remove magnesium salts. Decomposi-
tion of 2 through loss of the ruthenium metal was observed
upon silica gel column chromatography, which resulted in
the formation of an oxidized compound of pentamethyl-
[60]fullerene, C60Me5O2OH.[10] This product was identified
by MS (APCI–) (m/z = 844 [M]–). Compound 2 was iso-
lated as an orange powder and was stable in air as a solid
for over one month. Characterization of 2 was performed
Scheme 1. Syntheses of allyl, ethyl, and hydrido complexes.
1
by H and 13C NMR, IR, and UV/Vis spectroscopic mea-
[a] Nakamura Functional Carbon Cluster Project, ERATO, Japan
Science and Technology Agency
1
surements, and combustion analysis. In the H NMR spec-
trum, a set of three signals due to the olefinic protons was
observed in lower field at δ = 4.86, 5.14, and 6.51 ppm,
which indicates that the complex is a σ-allyl complex. The
IR spectrum exhibited asymmetric and symmetric stretch-
Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Fax: +81-3-5800-6889
E-mail: nakamura@chem.s.u-tokyo.ac.jp
[b] Department of Chemistry, University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
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Y. Matsuo, T. Uematsu, E. Nakamura
FULL PAPER
ing vibrations of the carbonyl groups at 2016 and Identification of the exo form of 3 was achieved by 1H and
1960 cm–1, which suggests two carbonyl ligands remain on 13C NMR, IR, and UV/Vis spectroscopic measurements,
the ruthenium center.
and combustion analysis as well as an X-ray crystallo-
We next investigated conversion of η1-allyl complex 2 graphic study (Figure 3). The 1H NMR spectrum displayed
into an η3-allyl complex through decarbonylation. Com- a signal pattern typical for an η3-allyl group. Signals due to
pound 2 did not react at all in C6D6 at 25 °C for 24 h. How- the syn and anti protons on the terminal carbon atoms and
ever, when the C6D6 solution of 2 was irradiated by visible one proton on the center carbon atom were observed at δ
light with 60 W incandescent light at 25 °C for 14 h, η3-allyl = 3.38, 1.75, and 4.61, respectively. The IR spectrum
compound 3, Ru(η5-C60Me5)(η3-allyl)(CO), formed. Ac- showed one strong CO absorption at 1943 cm–1. The X-ray
cording to the ligand field theory, such as light-induced de- analysis clearly showed the exo form of the η3-allyl ligand.
carbonylation process involves electron transition to anti- As shown in the top view, the carbonyl ligand are located
bonding orbital of the metal–carbonyl bond. The effect of in the space among two methyl groups of the pentamethyl-
the strongly light-absorbing fullerene part is therefore ap- [60]fullerene ligand and the η3-allyl ligand. The side view
parent. The progress of the reaction was monitored by indicates roughly parallel coordination of the η3-allyl ligand
analysis of the 1H NMR spectra (Figure 1). After three to the η5-cyclopentadienyl part of the pentamethyl[60]-
hours of irradiation, the η1- and η3-allyl complexes were fullerene moiety. The angle between a least-squares plane
observed in a 1:1 ratio. Irradiation for 14 h completed this consisting of the three carbon atoms of the η3-allyl and that
conversion. On heating the reaction mixture to 110 °C in of the five carbon atoms of the η5-cyclopentadienyl part is
C6D6 for 24 h in a sealed tube, instead of the light irradia- 11.24(2)°. Although some ruthenium η3-allyl complexes
tion, η3-allyl compound 3 slowly formed (only with ca. 10% have been used in catalysis,[13] complex 3 was too stable to
conversion). It is known that an η5-cyclopentadienyl-η3-al- show catalytic activity.
lyl metal complex exists in two isomeric forms: exo and
endo isomers (Figure 2).[11] In contrast, the present reaction
produced only an exo isomer (see below). If a pathway of
endo–exo interconversion exists (which may involve pseudo-
rotation of the η3-allyl group about the allyl–metal bond
axis or an equilibrium that goes through an η1-allyl inter-
mediate), the experimental observation would suggest that
the exo isomer is thermodynamically much more stable
than the endo isomer. It must then be the steric bulk of the
pentamethyl[60]fullerene ligand that is responsible for the
exo preference. Such a tendency, though less pronounced,
in the stability of the exo isomer has also been observed in
usual η5-cyclopentadienyl-η3-allyl ruthenium systems.[12]
Figure 3. X-ray crystal structure of 3·CS2. Solvent molecules are
omitted for clarity. (a) ORTEP drawing with 30% probability level
ellipsoids. (b) CPK model, top view. (c) CPK model, side view.
Synthesis of Hydrido Ruthenium Complexes of
Pentamethyl[60]fullerene
Synthesis of hydrido complex 4, Ru(η5-C60Me5)H(CO)2,
was performed next. We used three hydrogenation reagents:
lithium aluminum hydride (LAH), diisobutylaluminum hy-
dride (DIBAL), and sodium borohydride (NaBH4). Target
Figure 1. Conversion of 2 to 3 as monitored with 1H NMR spectro-
compound 4 was obtained in 76% isolated yield by the re-
action of chlorido complex 1 with LAH in thf at 25 °C
(Scheme 1). Treatment of 1 with DIBAL in thf afforded 4
in 42% yield. The reaction of 1 with NaBH4 did not yield
the desired hydrido complex but gave several unidentified
complexes. This may be due to hydroboration taking place
on the fullerene moiety of 1. Characterization of 4 was per-
scopic measurements.
Figure 2. The endo and exo isomers of η5-Cp-η3-allyl ruthenium
carbonyl complex.
1
formed by H, 13C NMR, IR, and UV/Vis spectroscopic
1
measurements and combustion analysis. In the H NMR
η3-Allyl complex 3 was isolated in 49% yield by prepara- spectrum, a proton signal characteristic of the hydride
tive HPLC. Side products were the oxidized penta- group was observed at δ = –10.07 ppm. The IR spectrum
methyl[60]fullerene and unidentified insoluble products. exhibited asymmetric and symmetric vibration absorptions
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Complexes of Ruthenium–Pentamethyl[60]fullerene
Table 1. Isomerization of 1-decene to internal alkenes catalyzed by ruthenium–pentamethyl[60]fullerene complexes.
FULL PAPER
Entry
Catalyst
1-Decene
[equiv.]
Temp.
[°]C
Time
[h]
Conversion
[%]
Yield [%]
Other internal alkenes
2-Decene (E/Z)
1
2
3
4
5
6
4
4
4
3
1
1
10000
2600
2600
2600
2600
2600
140
100
60
100
140
100
6
95
24
0
0
96
12
49 (2.0)
14 (1.8)
–
46
10
–
–
40
ND
16
16
16
18
16
–
56 (1.8)
ND
at 2062 and 2024 cm–1 that are due to the two carbonyl
ligands.
We then examined the catalytic activity of the penta-
methyl[60]fullerene ruthenium complexes in alkene isomer-
ization reactions from terminal alkenes to internal alkenes.
Many active catalysts using transition metal complexes,
such as Fe, Pd, Rh, Pt, Ni, Ir, Ru, Cr, Ti, and Zr complexes,
have been used in isomerization reactions of alkenes.[14] In
general, two reaction pathways have been considered. One
is
a
metal hydride addition/elimination mechanism
(Scheme 2a), and the other is a π-allyl metal hydride mecha-
nism (Scheme 2b). Motivated by the former reaction
mechanism, we used hydrido complex 4 in the isomerization
reaction of 1-octene. Complex 4 was found to be catalyti-
cally active at high temperature. The reaction with the use
of 0.01 mol-% of 4 for 6 h at 140 °C took place with 95%
conversion to give 49% of 2-decene in an E/Z ratio of 2.0
and 46% of other internal alkenes (Table 1, Entry 1). When
the reaction was heated to 100 °C with 0.083 mol-% of 4
for 18 h, only 24% conversion with a similar product distri-
bution (Table 1, Entry 2) was observed, whereas the reac-
tion heated at 25 or 60 °C did not afford any isomerization
products at all (Table 1, Entry 3).
In this reaction, high temperature was essential, which
could be due to the high activation energy for decarbon-
ylation of catalyst precursor 4 to the catalytically active
monocarbonyl complex. We therefore attempted this alkene
isomerization reaction at 25 °C with visible light irradiation
which was effective for the conversion of 2 into 3, but the
isomerized products were not obtained. This may then be
due to decomposition of the intermediates by further loss
of the carbonyl ligand.
Scheme 2. Two possible mechanisms for transition-metal-catalyzed
alkene isomerization.
elimination under light irradiation and under heating. We
considered that the elimination reaction was inhibited be-
cause of either conformational or electronic effects of the
η5-C60Me5 moiety. One may recall the strong stabilization
effect of this fullerene ligand in η3-allylnickel chemistry.[9a]
Allyl complex 3 did not show any catalytic activity in
the alkene isomerization reaction even at 100 °C, whereas
chlorido complex 1 gave the isomerized products in 96%
conversion at 140 °C, and in 12% conversion at 100 °C. The
latter result can be attributed to the formation of 4 from 1
in the presence of alkenes or to a catalytic cycle involving
the π-allyl metal hydride (Scheme 2b).
Conclusion
We have synthesized η1-allyl and η3-allyl, ethyl, and hy-
drido ruthenium complexes of pentamethyl[60]fullerene and
showed that the hydrido complex catalyzes the 1-decene
isomerization reaction. The present set of experiments sug-
gests new opportunities for the exploration of reactivities
of the ruthenium–carbon and –hydrogen bonds, especially
under excitation of the fullerene ligand by light irradiation.
Although ruthenium alkyl complexes having no β-hydro-
gen such as Ru(η5-C60Me5)Me(CO)2 and Ru(η5-C60Me5)-
[6a]
(CH2SiMe3)(CO)2
have been synthesized, syntheses of
ruthenium alkyl complexes having β-hydrogen atoms are
still scarce.[15] In the present fullerene complex series, we
could synthesize a stable ruthenium ethyl complex Ru(η5-
C60Me5)Et(CO)2 (5) by the reaction of 1 with ethylmagne-
sium bromide in thf at 0 °C in 48% yield. This complex was
Experimental Section
General Procedure: All manipulations involving air- and moisture-
sensitive compounds were carried out under an atmosphere of ar-
perfectly stable and did not show any tendency of β-hydride gon by using standard Schlenk techniques. Toluene and thf were
Eur. J. Inorg. Chem. 2007, 2729–2733
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2731

Y. Matsuo, T. Uematsu, E. Nakamura
FULL PAPER
distilled from Na/K alloy and thoroughly degassed by trap-to-trap
distillation before use. Ru(η5-C60Me5)Cl(CO)2 was prepared ac-
cording to the literature.[6a] Solutions of tBuOK in thf and allyl-
magnesium bromide in thf were purchased from Sigma–Aldrich
Co. and used as received. Other commercial reagents were used
without purification. HPLC analyses were performed with a Shim-
adzu LC-10A system equipped with a SPD-M10A diode array de-
tector and a Cosmosil-Buckyprep column (4.6ϫ250 mm, Nacalai
Tesque Co.). Preparative HPLC separations were performed by the
use of a preparative scale Buckyprep column (20 mmϫ250 mm).
The 1H and 13C NMR spectra were recorded with a JEOL EX 400
0.050 mmol) at 25 °C. After stirring for 10 min, the color of the
solution changed from red to brown. After the reaction was
quenched with a small amount of ethanol, the solution was evapo-
rated to dryness. The residue was dissolved in toluene (10 mL), and
the supernatant was separated from the insoluble salts by filtration.
The filtrate was evaporated to dryness and dried under vacuum for
5 h to obtain the title compound (7.2 mg, 0.38 mmol, 76% yield).
M.p. 180–190 °C (dec.). 1H NMR (400 MHz; CDCl3/CS2, 1:1;
25 °C): δ = –10.07 (s, 1 H, Ru-H), 2.30 (s, 15 H, C60Me5) ppm. 13
C
NMR (100 MHz; CDCl3/CS2, 1:1; 25 °C): δ = 32.16 (5 C, C60Me5),
49.88 [5 C, C60(sp3)], 110.70 [5 C, C60(Cp)], 143.41 (10 C, C60),
143.82 (10 C, C60), 146.55 (5 C, C60), 147.63 (10 C, C60), 148.19 (5
C, C60), 152.34 (10 C, C60), 199.73 (2 C, CO) ppm. UV/Vis (tolu-
ene/2-propanol, 7:3): λ = 287, 349 (sh), 396 nm. IR (diamond
1
spectrometer. The H NMR spectra are reported in parts per mil-
lion from internal tetramethylsilane and in the 13C NMR spectra
from 77.0 ppm (CDCl3) or from 128.0 ppm (C6D6). Other spectra
were recorded with the use of the following instruments: IR, Re-
actIR 1000; UV/Vis, JASCO V-570; mass spectra, Waters ZQ2000.
Elemental analyses were performed at organic elemental analysis
laboratory in the Department of Chemistry, University of Tokyo.
probe): ν 1962 (s) (CO), 2024 (s). MS (APCI–): m/z = 954 [M]–.
˜
HPLC (toluene/2-propanol, 7:3; flow rate: 1 mLmin–1): tR
=
8.02 min. C67H16O2Ru (953.93): calcd. C 84.36, H 1.69; found C
84.01, H 1.41.
Ru(η5-C60Me5)(η1-allyl)(CO)2 (2): A solution of allylmagnesium
bromide (0.090 mmol) in thf (0.090 mL) was added to a solution
of 1 (30 mg, 0.030 mmol) in toluene (6 mL) under an atmosphere
of argon at room temperature. After stirring for 10 min, a small
amount of ethanol was added to the resulting brown solution. The
solution was passed through a pad of neutral alumina, and the red-
colored filtrate was dried under vacuum to obtain 2 (30 mg, 99%
yield) as an orange powder. M.p. 215–220 °C (dec.). 1H NMR
Ru(η5-C60Me5)Et(CO)2 (5): A solution of EtMgBr (0.075 mmol) in
thf (0.083 mL) was added to a solution of 1 (50 mg, 0.050 mmol)
in toluene (16 mL)under an atmosphere of argon at 0 °C. After
stirring for 10 min, the resulting brown suspension was quenched
with a small amount of ethanol and passed through a pad of silica
gel. This eluent was purified by HPLC (toluene/2-propanol, 7:3;
flow rate: 20 mLmin–1). The fractions containing the title com-
pound were collected, and the solvents were evaporated to dryness.
The solid was then dissolved again in a small amount of CS2, and
this solution was dried under vacuum to obtain the title compound
(23 mg, 0.025 mmol, 48% yield). M.p. 210–215 °C (dec.). 1H NMR
3
(400 MHz, CDCl3, 25 °C): δ = 6.51 (ddt, JH–H = 16.6 (trans), 9.8
(cis), 8.4 Hz, 1 H, Ru-CH2-CH), 5.14 (dd, 3JH–H = 16.6 Hz (trans),
3
2JH–H = 1.9 Hz (gem), 1 H, Ru-CH2-CH=CH2), 4.86 (dd, JH–H
=
2
3
9.8 Hz (cis), JH–H = 1.9 Hz (gem), 1 H, Ru-CH2-CH=CH2), 3.32
(400 MHz; CDCl3/CS2, 1:1; 25 °C): δ = 2.63 (q, JH–H = 7.6 Hz, 2
(d, JH–H = 8.4, 2 H, Ru-CH2), 2.41 (s, 15 H, C60Me5) ppm. 13C
3
3
H, Ru-CH2CH3), 2.40 (s, 15 H, C60Me5), 1.75 (t, JH–H = 7.6 Hz,
3 H, Ru-CH2CH3) ppm. 13C NMR (100 MHz; CDCl3/CS2, 1:1;
25 °C): δ = –8.31 (1 C, Ru-CH2CH3), 23.19 (1 C, Ru-CH2CH3),
30.07 (5 C, C60Me5), 50.79 [5 C, C60(sp3)], 111.68 [5 C, C60(Cp)],
143.36 (10 C, C60), 143.62 (10 C, C60), 146.46 (5 C, C60), 147.63
(10 C, C60), 148.12 (5 C, C60), 152.34 (10 C, C60), 201.88 (2 C, CO)
ppm. UV/Vis (toluene/2-propanol, 7:3): λ = 285, 355 (sh), 395 nm.
NMR (100 MHz, CDCl3, 25 °C):
δ = 29.79 (1 C, Ru-
CH2CH=CH2), 30.43 (5 C, C60Me5), 51.11 [5 C, C60(sp3)], 108.48
(1 C, Ru-CH2CH=CH2), 111.82 [5 C, C60(Cp)], 143.56 (10 C, C60),
143.85 (10 C, C60), 146.78 (1 C, Ru-CH2CH=CH2), 147.64 (5 C,
C60), 148.02 (10 C, C60), 148.40 (5 C, C60), 152.56 (10 C, C60),
201.50 (2 C, CO) ppm. UV/Vis (toluene/2-propanol, 7:3): λ = 287,
355 (sh), 395 nm. IR (diamond probe): ν1960 (s) (CO), 2016 (s).
˜
IR(diamond probe): ν 2008 (s) (CO), 1950 (s). MS (APCI–): m/z =
˜
MS (APCI–): m/z = 993 [M]–, 952 [M – allyl]–. HPLC (toluene/2-
propanol, 7:3; flow rate: 1 mLmin–1): tR = 8.2 min. C70H20O2Ru
(994.00): calcd. C 84.58, H 2.03; found C 84.38, H 2.00.
981 [M]–. HPLC (toluene/2-propanol, 7:3; flow rate: 1 mLmin–1):
tR = 7.67 min. C69H20O2Ru (981.99): calcd. C 84.40, H 2.05; found
C 84.11, H 1.80.
Ru(η5-C60Me5)(η3-allyl)(CO)
(3):
Compound
2
(30 mg,
NMR-Monitoring of Conversion from 2 to 3: Compound 2 was
placed in an NMR tube connected to a vacuum system and C6D6
(0.6 mL) was transferred into it by trap-to-trap distillation. The
NMR tube was sealed by flame and subjected to the reaction con-
ditions: light irradiation with 60 W incandescent light or heating at
0.030 mmol) was dissolved in toluene (12 mL) under an atmo-
sphere of argon. This solution was stirred vigorously and irradiated
with 60 W incandescent light at room temperature. After 24 h, the
resulting red-colored solution was purified by preparative HPLC
(toluene/2-propanol, 7:3; flow rate: 20 mLmin–1). The fractions
containing 3 were collected, and the solvents were evaporated to
dryness to obtain 3 (14 mg, 49% yield) as orange microcrystals.
M.p. 240–245 °C (dec.). 1H NMR (400 MHz, C6D6, 25 °C): δ =
4.61 (m, 1 H, Hcenter), 3.38 (dt, 3JH(center)–H(syn) = 6.8 Hz, 2 H, Hsyn),
1
110 °C. Conversion of 3 into 2 was monitored by H NMR spec-
troscopy.
Isomerization of 1-Decene: Compound 4 and 10000 equiv. of 1-de-
cene were placed in a Schlenk tube and heated at 140 °C. After
stirring at this temperature for 6 h, the solution was passed through
a cotton plug and subjected to the 1H NMR and GC measurements
to estimate the product distributions. In the 1H NMR spectrum,
terminal and internal olefin protons were observed at δ = 4.9 ppm
and δ = 5.4 ppm, respectively.
3
2.05 (s, 15 H, C60Me5), 1.75 (dt, JH(center)–H(anti) = 11.2 Hz, 2 H,
Hanti) ppm. 13C NMR (100 MHz; CDCl3/CS2, 1:1; 25 °C): δ =
30.45 (5 C, C60Me5), 33.69 (2 C, C3H5), 50.73 [5 C, C60(sp3)], 69.61
(1 C, C3H5), 106.77 [5 C, C60(Cp)], 143.28 (10 C, C60), 143.77 (10
C, C60), 146.65 (5 C, C60), 147.73 (10 C, C60), 148.14 (5 C, C60),
153.05 (10 C, C60), 192.50 (1 C, CO) ppm. UV/Vis (toluene/2-pro-
X-ray Crystallographic Analysis: Single crystals of 3 suitable for X-
ray diffraction studies were grown and subjected to data collection.
The data sets were collected with a MacScience DIP2030 Imaging
Plate diffractometer by using Mo-Kα (graphite monochromated, λ
= 0.71069 Å) radiation. The structure of 3 was solved by direct
panol, 7:3): λ = 291, 348 (sh), 394 nm. IR(diamond probe): ν1943
˜
(s) (CO). MS (APCI–): m/z = 965 [M]–. HPLC (toluene/2-propanol,
7:3; flow rate: 1 mLmin–1): tR = 7.39 min. C69H20ORu (965.99):
calcd. C 85.79, H 2.09; found C 84.68, H 2.01.
Synthesis of Ru(η5-C60Me5)H(CO)2 (4): To a solution of 1 (10 mg, methods (SIR97).[16] The positional and thermal parameters of
0.050 mmol) in thf (1.7 mL) was added powdered LiAlH4 (0.38 mg,
non-hydrogen atoms were refined anisotropically on F2 by the full-
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Complexes of Ruthenium–Pentamethyl[60]fullerene
FULL PAPER
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atoms were placed at calculated positions and refined with riding
mode on their corresponding carbon atoms. In the subsequent re-
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2
2 2
finement, the function Σω(Fo – Fc ) was minimized, where |Fo|
and |Fc| are the observed and calculated structure factor ampli-
tudes, respectively. The agreement indices are defined as R1 = Σ
2
2 2
(||Fo| – |Fc||)/Σ|Fo| and wR2 = [Σω (Fo – Fc ) /Σ (ωFo4)]1/2. CCDC-
632009 contains the supplementary crystallographic information
for 3. This data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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Published Online: April 12, 2007
Eur. J. Inorg. Chem. 2007, 2729–2733
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2733