Transition Metal–Fullerene Complexes Containing Phosphane Ligands
FULL PAPER
ture was stirred at room temperature for 1.5 h. The resulting green
mixture was filtered and the green filtrate was layered with 60 mL
of hexane overnight to give a green precipitate. The precipitate was
washed with hexane (2×5 mL) and diethyl ether (2×5 mL) sequen-
tially, and then was dried in vacuo to afford 0.060 g (35%) of 1
from [Pt(dba)2] or 0.098 g (58%) of 1 from [Pt2(dba)3] as a green
C60 (0.036 g, 0.05 mmol) and [Pt2(dba)3] (0.028 g, 0.025 mmol)
were added to this solution. The new mixture was stirred at room
temperature for 5 h to give a green precipitate. The precipitate was
purified by the same method used for 3 to give 0.085 g (65%) of 5
as a green solid. M.p. Ͼ 300 °C. 1H NMR (300 MHz, CS2/CDCl3):
δ = 7.08–7.60 (m, 44 H, 8 C6H5 + 4 CH) ppm. 31P NMR
(121.48 MHz, CS2/CDCl3, H3PO4): δ = 19.79 (s, 2 P, 2 PPd), 20.12
1
solid. M.p. Ͼ 300 °C. H NMR (300 MHz, CS2/CDCl3): δ = 7.24–
7.60 (m, 44 H, 8 C6H5 + 4 CH) ppm. 31P NMR (121.48 MHz, CS2/
(t, JPt,P = 3848 Hz, 2 P, 2 PPt) ppm. IR (KBr disk): ν = 1434 (s),
˜
CDCl3, H3PO4): δ = –7.24 (s, 2 P, 2 PPh2), 19.88 (t, JPt,P = 3682 Hz, 1183 (m), 579 (m), 523 (vs) (C60), 1571 (m), 967 (m) (C=C) cm–1.
2 P, 2 PPt) ppm. IR (KBr disk): ν = 1434 (s), 1184 (m), 577 (m),
C172H44P4PdPt (2535.6): calcd. C 81.47, H 1.75; found C 81.40, H
˜
524 (vs) (C60), 1571 (m), 967 (m) (C=C) cm–1. C112H44P4Pt 2.00.
(1708.6): calcd. C 78.73, H 2.60; found C 78.75, H 2.41.
Method (ii): A mixture of diphosphane 2 (0.080 g, 0.05 mmol), C60
Preparation of [(η2-C60Pd)(dppet)2] (2): The same procedure as that (0.036 g, 0.05 mmol), and [Pt(dba)2] (0.034 g, 0.05 mmol) in tolu-
for the preparation of 1 was followed, but [Pd(dba)2] (0.057 g,
0.10 mmol) was used instead of [Pt(dba)2] or [Pt2(dba)3] to give
0.123 g (75%) of 2 as a green solid. M.p. Ͼ 300 °C. 1H NMR
(300 MHz, CS2/CDCl3): δ = 7.09–7.63 (m, 44 H, 8 C6H5 + 4 CH)
ppm. 31P NMR (121.48 MHz, CS2/CDCl3, H3PO4): δ = –7.48 (s, 2
ene (20 mL) was stirred at room temperature for 5 h to give a pre-
cipitate. The same workup as that in method (i) afforded 0.070 g
(55%) of 5.
Preparation of [(η2-C60Pd)(η2-C70Pd)(dppet)2] (6). Method (i): A
mixture of C60 (0.036 g, 0.05 mmol), [Pd(dba)2] (0.029 g,
0.05 mmol), and trans-dppet (0.039 g, 0.10 mmol) in toluene
(25 mL) was stirred at room temperature for 1 h to give a green
solution. C70 (0.042 g, 0.05 mmol) and [Pd(dba)2] (0.029 g,
0.05 mmol) were then added to this solution. The new mixture was
stirred at room temperature for 5 h to give a green precipitate. The
precipitate was purified by the same method as that utilized for 3
P, 2 PPh ), 20.21 (s, 2 P, 2 PPd) ppm. IR (KBr disk): ν = 1434 (s),
˜
2
1183 (m), 578 (m), 513 (vs) (C60), 1570 (m), 966 (m) (C=C) cm–1.
C112H44P4Pd (1619.9): calcd. C 83.04, H 2.74; found C 82.87, H
2.75.
Preparation of [(η2-C60Pt)(dppet)]2 (3). Method (i): The flask de-
scribed above was charged with C60 (0.072 g, 0.10 mmol), [Pt(dba)2]
(0.066 g, 0.10 mmol), trans-dppet (0.078 g, 0.20 mmol), and toluene to give 0.048 g (37%) of 6 as a brown solid. M.p. Ͼ 300 °C. 1H
(50 mL). The mixture was stirred at room temperature for 5 h to
give a green precipitate. The precipitate was washed with toluene
(2×10 mL), hexane (2×10 mL), and diethyl ether (2×10 mL), and
finally dried in vacuo to afford 0.108 g (82%) of 3 as a dark-green
NMR (300 MHz, CS2/CDCl3): δ = 7.09–7.54 (m, 44 H, 8 C6H5 +
4 CH) ppm. 31P NMR (121.48 MHz, CS2/CDCl3, H3PO4): δ =
25.64–27.50 (m, 4 P) ppm. IR (KBr disk): ν = 1433 (s), 1183 (m),
˜
576 (m), 510 (vs) (C60), 1130 (w), 1097 (m), 793 (m), 673 (m), 640
(w), 456 (s) (C70), 1569 (w), 967 (m) (C=C) cm–1. C182H44P4Pd2
(2567.09): calcd. C 85.15, H 1.72; found C 84.95, H 1.88.
1
solid. M.p. Ͼ 300 °C. H NMR (300 MHz, CS2/CDCl3): δ = 6.90–
7.60 (m, 44 H, 8 C6H5 + 4 CH) ppm. 31P NMR (121.48 MHz, CS2/
CDCl3, H3PO4): δ = 19.71 (t, JPt,P = 3794 Hz, 4 P) ppm. IR (KBr
Method (ii): A mixture of diphosphane 2 (0.080 g, 0.05 mmol), C70
(0.042 g, 0.05 mmol), and [Pd(dba)2] (0.029 g, 0.05 mmol) in tolu-
ene (20 mL) was stirred at room temperature for 5 h. The same
workup as that in method (i) afforded 0.049 g (38%) of 6.
disk): ν = 1434 (s), 1183 (m), 577 (m), 524 (vs) (C ), 1571 (m), 969
˜
60
(m) (C=C) cm–1. C172H44P4Pt2 (2624.3): calcd. C 78.72, H 1.69;
found C 78.71, H 1.70.
Method (ii): A mixture of diphosphane 1 (0.086 g, 0.05 mmol), C60
(0.036 g, 0.05 mmol), and [Pt(dba)2] (0.034 g, 0.05 mmol) in tolu-
ene (20 mL) was stirred at room temperature for 5 h to give a pre-
cipitate. The same workup as that in method (i) gave 0.078 g (59%)
of 3.
Preparation of [(η2-C70Pd)(dppet)]2 (7): A mixture of C70 (0.042 g,
0.05 mmol), [Pd(dba)2] (0.029 g, 0.05 mmol), and trans-dppet
(0.039 g, 0.10 mmol) in toluene (25 mL) was stirred at room tem-
perature for 1.5 h. The resulting mixture was filtered to give a
brown precipitate, which was purified by the method used for puri-
fication of 3 to afford 0.023 g (44%) of 7 as a dark-green solid.
M.p. Ͼ 300 °C. 1H NMR (300 MHz, CS2/CDCl3): δ = 7.15–7.67
(m, 44 H, 8 C6H5 + 4 CH) ppm. 31P NMR (121.48 MHz, CS2/
Preparation of [(η2-C60Pd)(dppet)]2 (4). Method (i): The flask de-
scribed above was charged with C60 (0.072 g, 0.10 mmol), [Pd-
(dba)2] (0.114 g, 0.20 mmol), trans-dppet (0.039 g, 0.10 mmol), and
toluene (50 mL). The mixture was stirred at room temperature for
5 h. The resulting mixture was filtered to give a green precipitate,
which was purified by the same method used above for 3 to afford
0.112 g (92%) of 4 as a dark-green solid. M.p. Ͼ 300 °C. 1H NMR
(300 MHz, CS2/CDCl3): δ = 7.20–7.66 (m, 44 H, 8 C6H5 + 4 CH)
ppm. 31P NMR (121.48 MHz, CS2/CDCl3, H3PO4): δ = 20.22 (s, 4
CDCl , H PO ): δ = 21.15, 22.77 (2s, 4 P) ppm. IR (KBr disk): ν
˜
3
3
4
= 1432 (vs), 1129 (w), 1097 (m), 794 (m), 673 (s), 641 (w), 577 (m),
534 (s), 457 (s) (C70), 1567 (m), 967 (m) (C=C) cm–1. C192H44P4Pd2
(2687.2): calcd. C 85.82, H 1.65; found C 85.60, H 1.73.
Preparation of [(η2-C60Pt)(dppeda)] (8) and [(η2-C60Pt)2(dppeda)]
(10): A brown mixture of C60 (0.036 g, 0.05 mmol) and [Pt2(dba)3]
(0.028 g, 0.05 mmol) in toluene (25 mL) was stirred at room tem-
perature for 15 min, and then dppeda (0.043 g, 0.05 mmol) was
added to cause an immediate color change from brown to green.
The green mixture was stirred at room temperature for 5 h and was
then filtered to give a green filtrate and a green precipitate. Whereas
the green filtrate was treated by a procedure similar to that used in
the preparation of 1 to afford 0.025 g (28%) of 8, the precipitate
was purified by the method used for purification of 3 to afford
0.033 g (49%) of 10.
P) ppm. IR (KBr disk): ν = 1432 (m), 1183 (m), 577 (m), 524 (vs)
˜
(C60), 1571 (m), 964 (m) (C=C) cm–1. C172H44P4Pd2 (2447.0): calcd.
C 84.43, H 1.81; found C 84.16, H 2.00.
Method (ii): A mixture of diphosphane 2 (0.080 g, 0.05 mmol), C60
(0.036 g, 0.05 mmol), and [Pd(dba)2] (0.029 g, 0.05 mmol) in tolu-
ene (20 mL) was stirred at room temperature for 5 h to give a pre-
cipitate. The same workup as that in method (i) produced 0.064 g
(53%) of 4.
Preparation of [(η2-C60Pd)(η2-C60Pt)(dppet)2] (5). Method (i): A
mixture of C60 (0.036 g, 0.05 mmol), [Pd(dba)2] (0.029 g,
0.05 mmol), trans-dppet (0.039 g, 0.10 mmol), and toluene (25 mL)
was stirred at room temperature for 1 h to give a green solution.
8: Green solid. M.p. 300 °C (dec.). 1H NMR (300 MHz, CS2/
CDCl3): δ = 2.37–2.45 (m, 4 H, NCH2CH2N), 3.35–3.47, 3.70–3.75
(2m, 8 H, 4 CH2P), 7.27–7.74 (m, 40 H, 8 C6H5) ppm. 31P NMR
Eur. J. Inorg. Chem. 2006, 422–429
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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