Transition Metal Fullerene Complexes
Organometallics, Vol. 22, No. 22, 2003 4597
free C70.17 Finally, it should be noted that one unit cell
of 11 or 12 contains four molecules of 11 or 12 and two
molecules of solvent toluene. There are no appreciable
interactions of the fullerene moiety in 11 or 12 with the
solvent molecule toluene since the nearest distance
between them is ca. 3.7 Å, far beyond the van der Waals
contacts.
After standing overnight, the mixture was filtered and the
brown precipitate was washed with 4 mL of pentane and dried
in vacuo, producing 34 mg (86%) of 7 as a brown-red solid, mp
> 300 °C. Anal. Calcd for C104H28FeP2Pt: C 78.55, H 1.77.
Found: C 78.60, H 1.68. IR (KBr disk): νC 1479 (m), 1432
70
(vs), 1125 (w), 1095 (m), 794 (w), 673 (m), 576 (m), 534 (s) cm-1
.
1H NMR (CDCl3, TMS): δ 4.16 (s, 4H, 2H3, 2H4), 4.34 (s, 4H,
2H2, 2H5), 7.05-8.94 (m, 20H, 4 C6H5) ppm. 31P NMR (CDCl3,
H3PO4): δ 13.28 (s, 2P) ppm. UV-vis (PhCl): λmax (log ꢀ) 289
(4.81), 379 (4.42), 455 (4.40) nm. MS (FAB): m/z 1590 (M+,
195Pt).
Exp er im en ta l Section
Gen er a l Com m en ts. All reactions were carried out under
highly purified nitrogen atmosphere using standard Schlenk
or vacuum-line techniques. Toluene was distilled from Na/
benzophenone ketyl, while chlorobenzene was dried over P2O5
and distilled from CaH2. Other solvents were bubbled with
nitrogen for at least 15 min before use. Pt(PPh3)4,18 Pd(PPh3)4,19
Pt(AsPh3)4,18 Pt(dba)2,20 dppf,20 and dpaf21 were prepared
according to literature methods. C60 (99.9%) and C70 (99.9%)
P r ep a r a tion of (η2-C70)P d (d p p f) (8). Similarly, when 30
mg (0.025 mmol) of Pd(PPh3)4 was used instead of Pt(PPh3)4,
26 mg (69%) of 8 as a brown-red solid was obtained, mp >
300 °C. Anal. Calcd for C104H28FeP2Pd: C 83.19, H 1.88.
Found: C 83.12, H 2.00. IR (KBr disk): νC 1478 (m), 1431
70
(s), 1094 (m), 794 (m), 673 (m), 577 (m), 535 (s), 461 (s) cm-1
.
1H NMR (CDCl3, TMS): δ 4.17 (s, 4H, 2H3, 2H4), 4.37 (s, 4H,
2H2, 2H5), 7.05-8.94 (m, 20H, 4 C6H5) ppm. 31P NMR (CDCl3,
H3PO4): δ 34.06 (s, 2P) ppm. UV-vis (PhCl): λmax (log ꢀ) 288
(4.79), 382 (4.43), 467 (4.40) nm. MS (FAB): m/z 1503 (M+,
108Pd).
1
were available commercially. H NMR spectra were recorded
on a Bruker AC P200 or a Mercury VX (Varian)-300 spectrom-
eter, while UV-vis and IR spectra were taken on Shimadzu
UV 240 and Bio-Rad FTS 135 spectrophotometers, respec-
tively. Elemental analysis was performed on an Elementar
Vario EL analyzer. The Mo¨ssbauer spectra were recorded on
a MS-500 Mo¨ssbauer spectrometer using 57Co diffused in a Pd
matrix as radiation source. The isomeric shifts were recorded
relative to natural iron foil at 293 K. Melting points were
determined on a Yanaco MP-500 apparatus.
P r ep a r a tion of (η2-C60)P t(d p p f) (5). A 100 mL three-
necked flask equipped with a magnetic stir-bar, a rubber
septum, and a nitrogen inlet tube was charged with 54 mg
(0.075 mmol) of C60, 20 mL of toluene, and 94 mg (0.075 mmol)
of Pt(PPh3)4. The mixture was stirred at room temperature
for 0.5 h to give a dark green solution containing (η2-C60)Pt-
(PPh3)2. To this solution was added 42 mg (0.075 mmol) of dppf,
and stirring continued for another 0.5 h. Then, this new
mixture was carefully layered with 60 mL of hexane. After
standing overnight, the mixture was filtered to give a precipi-
tate, which was washed with 15 mL of toluene and 10 mL of
pentane and dried in vacuo, resulting in 72 mg (65%) of 5 as
a dark green solid, mp > 300 °C. Anal. Calcd for C94H28FeP2-
Pt: C 76.80, H 1.92. Found: C 76.65, H 2.05. IR (KBr disk):
νC60 1434 (s), 1185 (m), 577 (m), 525 (vs) cm-1. 1H NMR (CDCl3,
TMS): δ 4.17 (s, 4H, 2H3, 2H4), 4.34 (s, 4H, 2H2, 2H5), 7.24-
7.90 (m, 20H, 4C6H5) ppm. UV-vis (PhCl): λmax (log ꢀ) 286
(4.72), 332 (4.57), 439 (4.10) nm.
P r ep a r a tion of (η2-C60)P t(AsP h 3)2 (9). Meth od (i). The
flask described above was charged with 18 mg (0.025 mmol)
of C60, 10 mL of toluene, and 36 mg (0.025 mmol) of Pt(AsPh3)4.
The mixture was stirred at room temperature for 0.5 h, and
then onto the mixture was carefully placed a layer of 15 mL
of hexane. The system was allowed to stand overnight to give
a dark green precipitate, which was fillered, washed with 15
mL of hexane, and dried in vacuo to afford 31 mg (81%) of 9
as a dark green solid, mp > 300 °C. Anal. Calcd for C96H30
-
As2Pt: C, 75.45; H, 1.98. Found: C, 75.17; H, 1.96. IR (KBr
1
disk): νC 1434 (s), 1184 (s), 579 (m), 526 (vs) cm-1. H NMR
60
(CDCl3): δ 7.11-7.72 (m, 30H, 6 C6H5) ppm. UV-vis (PhCl):
λmax (log ꢀ) 287 (4.76), 333 (4.71), 425 (3.90) nm.
Meth od (ii). The flask described above was charged with
18 mg (0.025 mmol) of C60, 10 mL of toluene, 17 mg (0.025
mmol) of Pt(dba)2, and 24 mg (0.075 mmol) of AsPh3. The
mixture was stirred at room temperature for 0.5 h, and then
onto this solution was carefully placed a layer of 15 mL of
hexane. The two-layer system was allowed to stand overnight
to give a dark green precipitate. The same workup as that in
method (i) afforded 29 mg (76%) of 9.
P r ep a r a tion of (η2-C70)P t(AsP h 3)2 (10). Meth od (i). The
same procedure as method (i) for the preparation of 9 was
followed, but 21 mg (0.025 mmol) of C70 was used instead of
C60 to give 30 mg (73%) of 10 as a brown-red solid, mp > 300
°C. Anal. Calcd for C106H30As2Pt: C, 77.24; H, 1.83. Found:
P r ep a r a tion of (η2-C60)P d (d p p f) (6). Similarly, when 87
mg (0.075 mmol) of Pd(PPh3)4 was utilized instead of Pt(PPh3)4,
71 mg (69%) of 6 as a dark green solid was obtained, mp >
300 °C. Anal. Calcd for C94H28FeP2Pd: C 81.73, H 2.04.
C, 77.35; H, 2.03. IR (KBr disk): νC 1433 (vs), 1414 (w), 1087
70
(m), 1079 (m), 794 (m), 673 (s), 640 (s), 578 (s), 533 (s), 471
60
(s), 457 (s) cm-1 1H NMR (CDCl3): δ 7.13-7.72 (m, 30 H,
.
Found: C 81.99, H 2.25. IR (KBr disk): νC 1434 (s), 1184
1
(m), 578 (m), 526 (s) cm-1. H NMR (CDCl3, TMS): δ 4.20 (s,
6C6H5) ppm. UV-vis (PhCl): λmax (log ꢀ) 287 (4.94), 332 (4.66),
363 (4.54), 382 (4.62), 464 (4.46), 554 (4.16) nm.
4H, 2H3, 2H4), 4.39(s, 4H, 2H2, 2H5), 7.13-7.90 (m, 20H, 4
C6H5) ppm. UV-vis (PhCl): λmax (log ꢀ) 286 (4.72), 333 (4.55),
444 (3.96) nm.
Meth od (ii). The same procedure as method (ii) for the
preparation of 9 was followed, but 21 mg (0.025 mmol) of C70
was utilized instead of C60 to yield 25 mg (61%) of 10.
P r ep a r a tion of (η2-C70)P t(d p p f) (7). The flask described
above was charged with 21 mg (0.025 mmol) of C70, 15 mL of
chlorobenzene, and 32 mg (0.025 mmol) of Pt(PPh3)4. The
reaction mixture was stirred at room temperature for 1 h to
produce a brown-red solution containing (η2-C70)Pt(PPh3)2. To
this solution was added 25 mg (0.045 mmol) of dppf, and
stirring continued for an additional 0.5 h to give a new
mixture, which was layered with 60 mL of petroleum ether.
P r ep a r a tion of (η2-C60)P t(d p a f) (11). Meth od (i). The
flask described above was charged with 18 mg (0.025 mmol)
of C60, 10 mL of toluene, and 36 mg (0.025 mmol) of Pt(AsPh3)4.
The mixture was stirred at room temperature for 0.5 h, and
then 16 mg (0.025 mmol) of dpaf was added. The new mixture
was stirred continuously for 0.5 h to give a dark green solution.
Then, onto this solution was carefully placed a layer of 15 mL
of hexane. The two-layer system was allowed to stand over-
night to give a dark green precipitate. The precipitate was
filtered, washed with 15 mL of toluene and 10 mL of hexane,
and dried in vacuo to afford 27 mg (70%) of 11 as a dark green
solid, mp > 300 °C. Anal. Calcd for C94H28As2FePt: C, 72.47;
H, 1.81. Found: C, 72.23; H, 1.67. IR (KBr disk): νC60 1434 (s),
1184 (s), 577 (s), 548 (s) cm-1. 1H NMR (CDCl3): δ 4.05 (s, 4H,
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