Synthesis, characterization and properties of transition metal Pd/Pt [60]fullerene complexes containing phosphane ligands - Crystal structure of [Pd(η2-C60){Ph2PCH2(CH 2OCH2)2CH2PPh2}]

Article abstract of DOI:10.1002/ejic.200300513

A solution of C₆₀ in toluene reacts with Pd(dba)₂ or Pd₂(dba)₃ (dba = dibenzylideneacetone) and monophosphanes in a 1:1:2 molar ratio to give the corresponding Pd monophosphane fullerene derivatives [Pd(η²-C₆₀)L₂] [L = P(2-Fu)₃ (Fu = furyl) 1; L = P(2-Fu)Ph₂ 2; L = PPh ₂H 3; L = P(Fc)Ph₂ (Fc = ferrocenyl) 4; L = P(Fc) ₂Ph 5], whereas reaction with M(dba)₂ (M = Pd, Pt) and subsequent treatment with diphosphanes in 1:1:1 molar ratio afforded the corresponding Pd/Pt diphosphane fullerene complexes [Pd(η²-C ₆₀){Ph₂PCH₂(CH₂-OCH ₂)_nCH₂PPh₂}] (n = 1 6; n = 2 7; n = 3 8) and [Pt(η²-C₆₀)-{Ph₂PCH ₂(CH₂OCH₂)_nCH₂PPh ₂}] (n = 1 9; n = 2 10; n = 3 11). All the new fullerene complexes 1-11 were characterized by elemental analysis, IR, ¹H NMR and ³¹P NMR spectroscopy, as well as by X-ray diffraction analysis (for 7). The optical limiting properties of 3-5 were determined and the possible pathways for the one pot reactions leading to 1-11 are briefly discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300513

FULL PAPER
Synthesis, Characterization and Properties of Transition Metal Pd/Pt
[60]Fullerene Complexes Containing Phosphane Ligands ؊ Crystal Structure
of [Pd(η2-C60){Ph2PCH2(CH2OCH2)2CH2PPh2}]
Li-Cheng Song,*[a] Guang-Ao Yu,[a] Hu-Ting Wang,[a] Fu-Hai Su,[a] Qing-Mei Hu,[a]
Ying-Lin Song,[b] and Ya-Chen Gao[b]
Keywords: Fullerenes / Palladium / Phosphanes / Platinum
A solution of C60 in toluene reacts with Pd(dba)2 or Pd2(dba)3
{Ph2PCH2(CH2OCH2)nCH2PPh2}] (n = 1 9; n = 2 10; n =3 11).
(dba = dibenzylideneacetone) and monophosphanes in a All the new fullerene complexes 1−11 were characterized by
1:1:2 molar ratio to give the corresponding Pd monophos- elemental analysis, IR, 1H NMR and 31P NMR spectroscopy,
phane fullerene derivatives [Pd(η2-C60)L2] [L = P(2-Fu)3 (Fu =
furyl) 1; L = P(2-Fu)Ph2 2; L = PPh2H 3; L = P(Fc)Ph2 (Fc =
ferrocenyl) 4; L = P(Fc)2Ph 5], whereas reaction with M(dba)2
(M = Pd, Pt) and subsequent treatment with diphosphanes in
1:1:1 molar ratio afforded the corresponding Pd/Pt diphos-
as well as by X-ray diffraction analysis (for 7). The optical
limiting properties of 3−5 were determined and the possible
pathways for the ‘‘one pot’’ reactions leading to 1−11 are bri-
efly discussed.
phane fullerene complexes [Pd(η2-C60){Ph2PCH2(CH2- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
OCH2)nCH2PPh2}] (n = 1 6; n = 2 7; n = 3 8) and [Pt(η2-C60)-
Germany, 2004)
Introduction
C60){Ph2PCH2(CH2OCH2)2CH2PPh2}]
ported.
— are also re-
The synthesis, structural characterization, and properties
of transition metal fullerene complexes have attracted great
attention,[1] since the discovery of [60]fullerene[2] and its Results and Discussion
synthesis in macroscopic quantities.[3] These complexes may
Synthesis and Characterization of [Pd(η2-C60)L2]
be classified into two major categories: exohedral metal
complexes in which the fullerene behaves mainly as an elec-
tron-deficient alkene ligand directly π-bonded to transition
metal center,[1] and endohedral compounds in which the
metal atom is encapsulated by the fullerene cage.[4] We are
interested in exohedral transition metal fullerene com-
plexes[5] because it can be expected that the exohedral modi-
fication of the fullerene core using different metals with an-
cillary ligands may change the structure and properties of
the fullerene itself and allow us to obtain new transition
metal fullerene derivatives, possibly with novel structures
and unique properties. In this article we will describe the
synthesis and spectroscopic characterization of a series of
new transition metal Pd/Pt [60]fullerene complexes contain-
ing mono- and diphosphane ligands. The nonlinear optical
properties of some of the new derivatives and the crystal
structure of one representative fullerene complex — [Pd(η2-
A toluene solution of C60 reacts with the mononuclear
Pd complex Pd(dba)2 (dba ϭ dibenzylideneacetone) and the
monophosphanes P(2-Fu)3 (Fu ϭ furyl), P(2-Fu)2Ph,
PPh2H or P(Fc)Ph2 in a 1:1:2 molar ratio at room tempera-
ture to give the corresponding monophosphane fullerene
complexes 1Ϫ4, respectively, in 63Ϫ93% yields, whereas it
reacts with the dinuclear Pd complex Pd2(dba)3 and the
monophosphane P(Fc)2Ph (Fc ϭ ferrocenyl) under similar
conditions to afford complex 5 in 76% yield (Scheme 1).
Our attempts to prepare [Pd(η2-C60){P(Fc)3}2] by the reac-
[a]
Department of Chemistry, State Key Laboratory of Elemento-
Organic Chemistry, Nankai University,
Tianjin 300071, China
Fax: (internat.) ϩ86-22-2350-4853
E-mail: lcsong@public.tpt.tj.cn
[b]
Department of Physics, Harbin Institute of Technology,
Harbin 150001, China
Scheme 1
866
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200300513
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Synthesis, Characterization and Properties of Pd/Pt [60]Fullerene Complexes
FULL PAPER
tion of a toluene solution of C60 with Pd(dba)2 or Pd2(dba)3
followed by treatment with the monophosphane P(Fc)3 un-
der similar conditions were unsuccessful, probably due to
the very low nucleophilicity of P(Fc)3 caused by the three
bulky ferrocenyl groups attached to the phosphorus atom.
It is believed that the sequential ‘‘one-pot’’ reactions
leading to 1Ϫ5 include an intermediate fullerene complex
(C60Pd)n generated from C60 and Pd(dba)2 or Pd2(dba)3,
which reacts further with the monophosphanes to yield
1Ϫ5. This pathway is suggested as C60 is known to react
with Pd2(dba)3 to produce a black, insoluble polymer
(C60Pd)n (n ഠ 1),[6] which can be depolymerized by mono-
phosphanes to give the fullerene derivatives [PdC60L2] (L ϭ
PPh3, PEt3).[7] This pathway is consistent with our obser-
Figure 1. Optical limiting of 3Ϫ5 determined in toluene solution:
3 (6.26 ϫ 10Ϫ5 mol/L); 4 (3.74 ϫ 10Ϫ5 mol/L); 5 (5.10 ϫ 10Ϫ5
mol/L)
vation that C60 reacts with Pd(dba)2 or Pd2(dba)3 in toluene
to give black suspensions.
Complexes 1Ϫ5 are air-stable solids that dissolve in polar
solvents such as toluene, chlorobenzene, THF and CS2, but
do not dissolve in nonpolar solvents such as petroleum
ether and hexane. In solution, 1Ϫ5 are air sensitive, and
can release C60 completely within 1Ϫ2 days.
The IR spectra of 1Ϫ5 display four absorption bands in
the range ν˜ ϭ 1435Ϫ521 cmϪ1 for their C60 cores,[8] while
the 31P NMR spectra of 1Ϫ5 each exhibit one singlet in the
region δ ϭ 7Ϫ30 ppm for the two identical P atoms. The
1H NMR spectra of 1Ϫ5 show the corresponding signals
for their respective hydrogen-containing groups. The UV/
Vis spectra of 1Ϫ5 display two intense bands between 200
and 400 nm; the new weak broad band appearing at ca.
440 nm suggests that the C60 ligand is coordinated to pal-
ladium in an η2-fashion in each of the compounds.[9]
The nonlinear optical properties of [60]fullerene and its
derivatives are of considerable interest, largely because of
their potential applications as optical limiting
Scheme 2
materials.[10Ϫ13] We recently studied the optical limiting diphosphanes affords 6Ϫ11. C60 is known to react with
properties of the fullerene derivatives 3Ϫ5. Figure 1 shows Pt(dba)2 to give a black, insoluble polymer (C60Pt)n (n ഠ
the optical limiting curves of 3Ϫ5, from which it can be 1), and treatment of (C60Pt)n with monophosphanes affords
seen that the optical limiting properties of 4 and 5 are vir- [PtC60L2] (L ϭ PPh3, PEt3).[15] Similarly, reaction of C60
tually the same within the experimental accuracy. They dis- with Pd2(dba)3 produces the polymer (C60Pd)n (n ഠ 1),[6]
play better optical limiting characteristics than 3, probably which reacts with dppe to yield [PdC60(dppe)].[7] We also
due to both phenyl and ferrocenyl groups having stronger observed the formation of black suspensions when C60 was
electron-donating ability than that of a hydrogen atom.[14]
reacted with M(dba)2 (M ϭ Pd, Pt) in toluene.
Similar to 1Ϫ5, complexes 6Ϫ11 are air-stable solids,
which are soluble in polar solvents, but insoluble in nonpo-
lar solvents. In solution, 6Ϫ11 are air sensitive, but less so
than 1Ϫ5; they release C60 completely after two or three
Synthesis and Characterization of [Pd(η2-
C60){Ph2PCH2(CH2OCH2)nCH2PPh2}] and [Pt(η2-
C60){Ph2PCH2(CH2OCH2)nCH2PPh2}]
Similarly, C60 reacted with mononuclear complexes days. Compounds 6Ϫ11 were fully characterized by elemen-
M(dba)2 (M ϭ Pd, Pt) in toluene, followed by in situ treat- tal analysis and spectroscopy, and 7 by X-ray crystallogra-
ment with diphosphanes Ph2PCH2(CH2OCH2)nCH2PPh2 phy. For instance, the IR spectra of 6Ϫ11 show four bands
(n ϭ 1Ϫ3) in 1:1:1 molar ratio at room temperature to af- in the range ν˜ ϭ 1434Ϫ525 cmϪ1 for their C60 spheres,[8]
ford the first examples of the ether-chain-bridged diphos- whereas the UV/Vis spectra of 6Ϫ11 display two intense
phane fullerene complexes 6Ϫ11 (M ϭ Pd: n ϭ 1 6, n ϭ 2 bands in the 200Ϫ400 nm range and one weak broad band
7, n ϭ 3 8; M ϭ Pt: n ϭ 1 9, n ϭ 2 10, n ϭ 3 11) in 61Ϫ94% at ca. 440 nm, indicating that the C60 ligand is coordinated
yield (Scheme 2).
to Pd or Pt in an η2-mode in each of these complexes.[9] In
Presumably, these ‘‘one-pot’’ reactions for production of addition, the 31P NMR spectra of 6Ϫ8 show a singlet at
6Ϫ11 also involve an intermediate polymer, either (C60Pd)n about δ ϭ 16 ppm for the two identical P atoms in each of
or (C60Pt)n, generated from C60 and M(dba)2 (M ϭ Pd, 6Ϫ8, whereas the spectra of 9Ϫ11 exhibit a singlet at about
Pt); the in situ reaction of (C60Pd)n or (C60Pt)n with the δ ϭ 18 ppm, along with two satellite singlets due to 195Pt-
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FULL PAPER
31P coupling, attributed to the two identical P atoms in each
of 9Ϫ11.
Crystal Structure of 7
The molecular structure of 7 has been unequivocally con-
firmed by single-crystal X-ray diffraction techniques (Fig-
ure 2). Figure 3 displays its cell packing. Selected bond
lengths and angles are listed in Table 1. As can be seen from
Figure 2, complex 7 indeed consists of a C60 ligand bound
to the Pd atom in an η2-fashion by the C(1)ϪC(2) 6:6 bond,
and a diphosphane ligand Ph2PCH2(CH2OCH2)2CH2PPh2
chelated to the Pd atom through the P(1) and P(2) atoms.
In addition, from Figure 3 it can be seen that each crystal
cell contains two molecules of 7 and two molecules of
MeOH. The closest contact between solvent MeOH and 7
˚
[2.467 A, from the oxygen atom of MeOH to C(10) of the
Figure 3. Cell packing of 7
C60 ligand] is less than the sum of the van der Waals radii
of C and O (3.22 A),
[16]
˚
which might be due to disorder
of the MeOH molecule. In addition, the disordered MeOH
molecule could also give rise to the relatively high R value
(0.1426) for the structure of 7.
˚
Table 1. Selected bond lengths (A) and angles (°) for 7
Pd(1)ϪC(1)
Pd(1)ϪC(2)
Pd(1)ϪP(1)
Pd(1)ϪP(2)
P(1)ϪC(61)
2.060(18) P(1)ϪC(73)
2.119(17) P(1)ϪC(67)
1.80(2)
1.83(2)
1.77(2)
1.81(2)
1.43(3)
To the best of our knowledge, 7 is the first crystallograph-
ically characterized transition metal fullerene complex con-
taining an ether-chain-bridged diphosphane ligand. The Pd
coordination geometry of 7 is similar to that of its mono-
2.297(5)
2.344(6)
1.76(2)
P(2)ϪC(79)
P(2)ϪC(85)
C(1)ϪC(2)
phosphane
PPh3-containing
analogue
[Pd(η2-
C(1)ϪPd(1)ϪC(2)
40.1(7)
103.2(5)
143.2(5)
150.5(5)
110.4(5)
106.27(19)
C(61)ϪP(1)ϪC(67) 102.8(9)
C(73)ϪP(1)ϪC(67) 100.7(9)
C(61)ϪP(1)ϪPd(1) 117.9(6)
C(79)ϪP(2)ϪC(85) 102.1(9)
C(79)ϪP(2)ϪC(78) 101.7(10)
C(85)ϪP(2)ϪC(78) 106.9(10)
C(79)ϪP(2)ϪPd(1) 113.7(6)
C60)(PPh3)2].[17] Figure 4 shows that the corresponding C(1)ϪPd(1)ϪP(1)
C(2)ϪPd(1)ϪP(1)
bond lengths and angles within the coordination spheres of
C(1)ϪPd(1)ϪP(2)
the Pd atoms of these two complexes are very similar.
C(2)ϪPd(1)ϪP(2)
It is noteworthy that the C(1)ϪC(2) bond lengths of 7
P(1)ϪPd(1)ϪP(2)
and [Pd(η2-C60)(PPh3)2][17] are slightly longer than the 6:6
C(61)ϪP(1)ϪC(73) 103.5(10)
bond length in free C60,[1a] due to the metal-to-C60 π-back-
Figure 2. ORTEP diagram of 7
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Synthesis, Characterization and Properties of Pd/Pt [60]Fullerene Complexes
FULL PAPER
solution was carefully layered with hexane (40 mL). After standing
overnight, the mixture was filtered to give a precipitate, which was
washed with (10 ϫ 2 mL) of toluene and dried in vacuo. 0.054 g
(84%) of 1 was obtained as a black solid. M.p. Ͼ 300 °C. 1H NMR
(200 MHz, CDCl3, TMS): δ ϭ 6.39 (s, 6 H, 6 H4 of furan ring),
6.78 (s, 6 H, 6 H3 of furan ring), 7.64 (s, 6 H, 6 H5 of furan ring)
ppm. 31P NMR (81.0 MHz, CDCl3, H3PO4): δ ϭ 30.04 (s, 2 P)
ppm. IR (KBr disk): ν˜ ϭ 2327 (m), 1458 (m), 1427 (m) (C60), 1364
(m), 1213(m), 1183 (m) (C60), 1159 (m), 1122(m), 1009 (s), 906 (m),
745 (s), 592 (m), 577(m) (C60), 524 (s) (C60), 490 (s), 438 (m) cmϪ1
.
UV/Vis (PhCl): λmax (log ε) ϭ 285.0 (4.93), 333.3 (5.11), 406.7
(3.85), 435.5 (3.84) nm. C84H18O6P2Pd (1291.43): calcd. C 78.12,
H 1.40; found C 77.95, H 1.50.
Preparation of [Pd(η2-C60){P(2-Fu)Ph2}2] (2): This complex was
prepared similarly, with P(2-Fu)Ph2 (0.025 g, 0.10 mmol) instead of
P(2-Fu)3; 0.042 g (63%) of 2 was obtained as a black solid. M.p. Ͼ
300 °C. 1H NMR (200 MHz, CDCl3, TMS): δ ϭ 6.35 (s, 2 H, 2
H4 of furan ring), 6.78 (s, 2 H, 2 H3 of furan ring), 7.14Ϫ7.75 (m,
22 H, 4 C6H5, 2 H5 of furan ring) ppm. 31P NMR (81.0 MHz,
CDCl3, H3PO4): δ ϭ 7.04 (s, 2 P) ppm. IR (KBr disk): ν˜ ϭ 1481
(m), 1434 (m) (C60), 1356 (m), 1212 (m), 1183 (m) (C60), 1120 (m),
1097 (m), 1009 (s), 904 (m), 874 (m), 742 (s), 693 (s), 577(m) (C60),
524 (s) (C60), 489 (m), 432 (m) cmϪ1. UV/Vis (PhCl): λmax (log ε) ϭ
285.0 (4.91), 333.3 (4.93), 405.8 (4.17), 437.5(3.99) nm.
C92H26O2P2Pd (1331.58): calcd. C 82.98, H 1.97; found C 82.93,
H 2.10.
Figure 4. The Pd coordination sphere in 7 (lengths in angstroms
and angles in degrees); values for its PPh3 analogue[17] are given
in brackets
donation.[1b] In addition, the Pd coordination geometries of
7 and [Pd(η2-C60)(PPh3)2] are square planar, the five atoms
C(1), C(2), P(1), P(2) and Pd being coplanar, with devi-
˚
ations from the least-squares plane of less than 0.02 A for
2
[17]
˚
7 and 0.06 A for [Pd(η -C60)(PPh3)2].
Preparation of [Pd(η2-C60)(PPh2H)2] (3): This complex was pre-
pared similarly, with PPh2H (0.019 g, 0.10 mmol) in place of P(2-
Fu)3; 0.056 g (93%) of 3 was obtained as a black solid. M.p.
Interestingly, complex 7 could be regarded as a hybrid of
a metallocrown ether and a fullerene, in which the Pd atom,
part of an eleven-membered metallocrown ether ring
[Pd(1)P(1)C(73)C(74)O(1)C(75)C(76)O(2)C(77)C(78)P(2)],
is bound to the fullerene through the C(1)ϪC(2) 6:6 bond.
In view of the unique structures and novel properties of
both crown ether and fullerene, it can be expected that
such modified hybrids might find practical applications in
catalysis, molecular recognition and materials science.[1,18]
1
282Ϫ283 °C. H NMR (200 MHz, CDCl3, TMS): δ ϭ 7.48Ϫ7.74
(m, 20 H, 4 C6H5), 8.08 (d, J ϭ 484 Hz, 2 H, 2 HP) ppm. 31P
NMR (81.0 MHz, CDCl3, H3PO4): δ ϭ 22.50 (s, 2 P) ppm. IR
(KBr disk): ν˜ ϭ 2923 (m), 1457 (m), 1435 (m) (C60), 1183 (m) (C60),
1107 (m), 1036 (m), 1000 (m), 821 (m), 746 (m), 696 (s), 577(m)
(C60), 524 (s) (C60), 489 (m), 430 (m) cmϪ1. UV/Vis (PhCl): λmax
(log ε) ϭ 285.0 (4.50), 331.7 (4.42), 405.8 (3.85), 436.0 (3.92) nm.
C84H22P2Pd (1199.47): calcd. C 84.11, H 1.85; found C 84.15, H
2.00.
Experimental Section
Preparation of [Pd(η2-C60){P(Fc)Ph2}2] (4): This complex was pre-
pared similarly, with P(Fc)Ph2 (0.037 g, 0.10 mmol) instead of P(2-
Fu)3; 0.053 g (68%) of 4 was obtained as a black solid. M.p. Ͼ 300
General: All reactions were carried out under a highly purified ni-
trogen atmosphere using standard Schlenk or vacuum-line tech-
niques. Toluene and hexane were distilled from Na/benzophenone
ketyl. Other solvents were bubbled with nitrogen for at least 20
minutes before use. Pd(dba)2,[19] Pd2(dba)3,[20] P(Fc)3,[21]
1
°C. H NMR (200 MHz, CDCl3, TMS): δ ϭ 3.84 (s, 4 H, 2 H3, 2
H4), 4.01 (s, 10 H, 2 C5H5), 4.19 (s, 4 H, 2 H2, 2 H5), 7.25Ϫ7.75
(m, 20 H, 4 C6H5) ppm. 31P NMR (81.0 MHz, CDCl3, H3PO4):
δ ϭ 17.16 (s, 2 P) ppm. IR (KBr disk): ν˜ ϭ 3052 (m), 1570 (m),
1480 (m), 1458 (m), 1434 (m) (C60), 1354 (m), 1306 (m), 1185 (m)
(C60), 1160(m), 1098 (m), 1028 (m), 1001 (m), 820 (s), 741 (s), 696
(s), 622 (m), 579(m) (C60), 524 (s) (C60), 485 (s), 430 (m) cmϪ1. UV/
Vis (PhCl): λmax (log ε) ϭ 287.0 (4.82), 333.0 (4.73), 405.6 (4.12),
432.5 (4.04) nm. C104H38Fe2P2Pd (1567.51): calcd. C 79.69, H 2.44;
found C 79.50, H 2.54.
P(Fc)2Ph,[22] P(Fc)Ph2,[22] PPh2H,[23] P(2-Fu)3,[24] P(2-Fu)Ph2
[25]
and Pt(dba)2 [26] were prepared according to literature methods. C60
(99.9%) is available commercially.
1H NMR and 31P NMR were recorded on a Bruker AC-P200 spec-
trometer, UV/Vis spectra on a Shimadzu UV-240 spectrometer and
IR spectra on a Bio-Rad FTS 135 spectrometer. Elemental analysis
was performed on an Elementar Vario EL analyzer. Melting points
were determined on a Yanaco MP-500 apparatus.
Preparation of [Pd(η2-C60){P(Fc)2Ph}2] (5): This complex was pre-
pared similarly, with Pd2(dba)3·C6H6 (0.026 g, 0.025 mmol) and
Preparation of [Pd(η2-C60){P(2-Fu)3}2] (1): A 50-mL three-necked P(Fc)2Ph (0.048 g, 0.10 mmol) instead of Pd(dba)2 and P(2-Fu)3;
flask equipped with a magnetic stir-bar, a rubber septum and a
nitrogen inlet tube was charged with C60 (0.036 g, 0.05 mmol) and
toluene (16 mL). Pd(dba)2 (0.029 g, 0.05 mmol) was added to the
purple toluene solution and then the mixture was stirred at room
temperature for 0.5 h to give a black suspension. P(2-Fu)3 (0.023 g,
0.10 mmol) was added to this suspension and the new mixture was
stirred for another 0.5 h to produce a deep green solution. The
0.068 g (76%) of 5 was obtained as a black solid. M.p. Ͼ 300 °C.
1H NMR (200 MHz, CDCl3, TMS): δ ϭ 4.18 (s, 8 H, 4 H3, 4 H4),
4.38 (s, 20 H, 4 C5H5), 4.83, 5.03 (s, s, 8 H, 4 H2, 4 H5), 7.30Ϫ7.95
(m, 10 H, 2 C6H5) ppm. 31P NMR (81.0 MHz, CDCl3, H3PO4):
δ ϭ 13.84 (s, 2 P) ppm. IR (KBr disk): ν˜ ϭ 2923 (m), 2851(m),
1456 (m), 1434 (m) (C60), 1185 (m) (C60), 1161 (m), 1056 (m), 1106
(m), 1026 (m), 1002 (m), 821 (s), 740 (m), 697 (s), 578(m) (C60),
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521 (s) (C60), 438 (s), 431 (m) cmϪ1. UV/Vis (PhCl): λmax (log ε) ϭ 0.05 mmol)
and
Ph2PCH2(CH2OCH2)2CH2PPh2
(0.024 g,
285.0 (4.90), 333.3 (4.91), 405.8 (4.32), 435.6 (3.88) nm. 0.05 mmol) instead of Pd(dba)2 and P(2-Fu)3; 0.066 g (94%) of 10
C
112H46Fe4P2Pd (1783.35): calcd. C 75.43, H 2.59; found C 75.49,
was obtained as a black solid, M.p. Ͼ 300 °C. 1H NMR (200 MHz,
CDCl3, TMS): δ ϭ 2.50Ϫ2.75 (m, 4 H, 2 CH2P), 3.65Ϫ3.95 (m, 8
H, 4 CH2O), 7.10Ϫ7.70 (m, 20 H, 4 C6H5) ppm. 31P NMR
(81.0 MHz, CDCl3, H3PO4): δ ϭ 19.34 (s, JP-Pt ϭ 3949 Hz, 2 P)
ppm. IR (KBr disk): ν˜ ϭ 2921 (m), 2853 (m), 1479 (m), 1459 (s),
1434 (s) (C60), 1331 (m), 1279 (m), 1184 (m) (C60), 1128 (s), 1099
(s), 994 (s), 743 (s), 696 (s), 673 (m), 577(m) (C60), 527 (s) (C60),
484 (m), 414 (m) cmϪ1. UV/Vis (PhCl): λmax (log ε) ϭ 285.0 (4.69),
314.2 (5.15), 318.3 (5.16), 440 (3.84) nm. C90H32O2P2Pt (1402.27):
calcd. C 77.09, H 2.30; found C 76.99, H 2.38.
H 2.48.
Preparation of [Pd(η2-C60)(Ph2PCH2CH2OCH2CH2PPh2)] (6):
This complex was prepared similarly, with Ph2PCH2-
CH2OCH2CH2PPh2 (0.022 g, 0.05 mmol) instead of P(2-Fu)3;
0.056 g (88%) of 6 was obtained as a black solid. M.p. Ͼ 300 °C.
1H NMR (200 MHz, CDCl3, TMS): δ ϭ 2.63 (s, 4 H, 2 CH2P),
3.78Ϫ4.03 (m, 4 H, 2 CH2O), 7.08Ϫ7.78 (m, 20 H, 4 C6H5) ppm.
31P NMR (81.0 MHz, CDCl3, H3PO4): δ ϭ 13.60 (s, 2 P) ppm. IR
(KBr disk): ν˜ ϭ 2852 (m), 1570 (m), 1480 (m), 1459 (m), 1433 (s)
(C60), 1353 (m), 1183 (m) (C60), 1101(s), 930 (s), 821 (m), 739 (s),
Preparation of [Pt(η2-C60){Ph2PCH2(CH2OCH2)3CH2PPh2}] (11):
This complex was prepared similarly, with Pt(dba)2 (0.033 g,
693 (s), 666 (m), 578(m) (C60), 526 (s) (C60), 499 (s), 438 (m) cmϪ1
UV/Vis (PhCl): λmax (log ε) ϭ 290.0 (5.34), 333.3 (5.28), 405.5
(4.22), 437.5 (4.50) nm. C88H28OP2Pd (1269.56): calcd. C 83.25, H
2.22; found C 83.10, H 2.30.
.
0.05 mmol)
and
Ph2PCH2(CH2OCH2)3CH2PPh2
(0.026 g,
0.05 mmol) instead of Pd(dba)2 and P(2-Fu)3; 0.064 g (89%) of 11
was obtained as a black solid, M.p. Ͼ 300 °C. 1H NMR (200 MHz,
CDCl3, TMS): δ ϭ 2.60Ϫ2.85 (m, 4 H, 2 CH2P), 3.50Ϫ3.95 (m,
12 H, 6 CH2O), 7.11Ϫ7.70 (m, 20 H, 4 C6H5) ppm. 31P NMR
(81.0 MHz, CDCl3, H3PO4): δ ϭ 19.35 (s, JP-Pt ϭ 3946 Hz, 2 P)
ppm. IR (KBr disk): ν˜ ϭ 2910 (m), 2853 (m), 1481 (m), 1459 (m),
1434 (s) (C60), 1332 (m), 1280 (m), 1183 (m) (C60), 1141 (m),
1101(s), 976 (m), 903 (m), 740 (s), 694 (s), 577(m) (C60), 526 (s)
(C60), 489 (m) cmϪ1. UV/Vis (PhCl): λmax (log ε) ϭ 287.0 (5.09),
333.0 (5.09), 405.0 (4.25), 438.5 (4.17) nm. C92H36O3P2Pt (1446.32):
calcd. C 76.40, H 2.51; found C 76.42, H 2.54.
Preparation of [Pd(η2-C60){Ph2PCH2(CH2OCH2)2CH2PPh2}] (7):
This complex was prepared similarly, with Ph2PCH2-
(CH2OCH2)2CH2PPh2 (0.024 g, 0.05 mmol) instead of P(2-Fu)3;
0.040 g (61%) of 7 was obtained as a black solid. M.p. Ͼ 300 °C.
1H NMR (200 MHz, CDCl3, TMS): δ ϭ 2.50Ϫ2.70 (m, 4 H, 2
CH2P), 3.68Ϫ3.90 (m, 8 H, 4 CH2O), 7.10Ϫ7.75 (m, 20 H, 4 C6H5)
ppm. 31P NMR (81.0 MHz, CDCl3, H3PO4): δ ϭ 17.95 (s, 2 P)
ppm. IR (KBr disk): ν˜ ϭ 2858 (m), 1481 (m), 1460 (m), 1433 (s)
(C60), 1352 (m), 1184 (m) (C60), 1127 (m), 1098(s), 994 (m), 739 (s),
695 (s), 578(m) (C60), 525 (s) (C60), 434 (m), 412 (m) cmϪ1. UV/Vis
(PhCl): λmax (log ε) ϭ 286.7 (5.24), 333.3 (5.13), 405.8 (4.37), 437.5
(4.24), nm. C90H32O2P2Pd (1313.61): calcd. C 82.29, H 2.46; found
C 82.42, H 2.45.
Determination of the Optical Limiting Properties: The investigation
of the optical limiting properties of the fullerene derivatives was
conducted at a wavelength of 532 nm. They were housed in quartz
cells with a path 2 mm long with the same linear transmittance
of 83%. The laser pulses used in experiments were supplied by a
frequency-doubled, Q-switched, mode-locked Continuum ns/ps
Nd:YAG laser system, which provides linearly polarized 8 ns
(FWHM) optical pulses at 532 nm with a repetition of 1 Hz. The
transverse mode of the laser pulses is nearly Gaussian. The input
laser pulses adjusted by an attenuator were split into two beams.
One was employed as reference to monitor the incident laser en-
ergy, and the other was focused onto the sample cell by using a
lens with 30 cm focal length. The sample was positioned at the
focus. The incidence and transmitting laser pulses were monitored
by utilizing two energy detectors (818J-09B, Newport Corp). The
optical limiting was studied by measuring the nonlinear fluence
transmittance change with input fluence.
Preparation of [Pd(η2-C60){Ph2PCH2(CH2OCH2)3CH2PPh2}] (8):
This complex was prepared similarly, with Ph2PCH2-
(CH2OCH2)3CH2PPh2 (0.026 g, 0.05 mmol) instead of P(2-Fu)3;
0.050 g (74%) of 8 was obtained as a black solid. M.p. Ͼ 300 °C.
1H NMR (200 MHz, CDCl3, TMS): δ ϭ 2.46Ϫ2.60 (m, 4 H, 2
CH2P), 3.70 (s, 12 H, 6 CH2O), 7.12Ϫ7.65 (m, 20 H, 4 C6H5) ppm.
31P NMR (81.0 MHz, CDCl3, H3PO4): δ ϭ 13.89 (s, 2 P) ppm. IR
(KBr disk): ν˜ ϭ 2865 (m), 1571 (m), 1480 (m), 1459 (m), 1433 (s)
(C60), 1352 (m), 1183 (s) (C60), 1099 (s), 974 (m), 739 (s), 695 (s),
577(m) (C60), 525 (s) (C60), 486 (m), 434 (m) cmϪ1. UV/Vis (PhCl):
λmax (log ε) ϭ 287.0 (5.27), 333.0 (5.28), 405.5 (4.10), 438.0 (4.15)
nm. C92H36O3P2Pd (1357.66): calcd. C 81.39, H 2.67; found C
81.35, H 2.56.
Preparation of [Pt(η2-C60)(Ph2PCH2CH2OCH2CH2PPh2)] (9):
This complex was prepared similarly, with Pt(dba)2 (0.033 g,
0.05 mmol) and Ph2PCH2CH2OCH2CH2PPh2 (0.022 g, 0.05 mmol)
instead of Pd(dba)2 and P(2-Fu)3; 0.064 g (94%) of 9 was obtained
as a black solid. M.p. Ͼ 300 °C. 1H NMR (200 MHz, CDCl3,
TMS): δ ϭ 2.60Ϫ2.85 (m, 4 H, 2 CH2P), 3.85Ϫ4.02 (m, 4 H, 2
CH2O), 7.23Ϫ7.70 (m, 20 H, 4 C6H5) ppm. 31P NMR (81.0 MHz,
CDCl3, H3PO4): δ ϭ 16.59 (s, JP,Pt ϭ 3876 Hz, 2 P) ppm. IR (KBr
disk): ν˜ ϭ 2920 (m), 2853 (m), 1480 (m), 1459 (m), 1434 (s) (C60),
1332 (m), 1280 (m), 1184 (m) (C60), 1101(s), 928 (m), 906 (m), 823
(m), 741 (s), 694 (s), 577(m) (C60), 527 (s) (C60), 502 (s), 480 (m)
cmϪ1. UV/Vis (PhCl): λmax (log ε) ϭ 285.0 (4.62), 314.0 (5.10),
318.6 (5.11), 437.5(3.94) nm. C88H28OP2Pt (1358.22): calcd. C
77.82, H 2.08; found C 77.75, H 2.10.
Crystal Structure Determination of 7: Single crystals of 7 suitable
for X-ray diffraction analysis were obtained by slow diffusion of
MeOH into a toluene solution of 7 at room temperature. A crystal
of 7 was glued to a glass fiber and mounted on a Bruker SMART
1000 automated diffractometer. Data were collected at room tem-
perature, using graphite monochromated Mo-Kα radiation (λ ϭ
˚
0.71073 A) in the ω-2θ scanning mode. Absorption correction was
performed with SADABS.[27] The structure was solved by direct
methods using the SHELXS-97 program and refined by full-matrix
least-squares techniques (SHELXL-97) on F2.[28] Hydrogen atoms
were located by using the geometric method. The crystal data and
structural refinements details are listed in Table 2. CCDC-216076
contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/
conts/retrieving.html [or from the Cambridge Crystallographic
Preparation of [Pt(η2-C60){Ph2PCH2(CH2OCH2)2CH2PPh2}] (10): Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax:
This complex was prepared similarly, with Pt(dba)2 (0.033 g, (internat.) ϩ44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
870
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 866Ϫ871

Synthesis, Characterization and Properties of Pd/Pt [60]Fullerene Complexes
Polyhedron 1998, 17, 469Ϫ473.
FULL PAPER
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L.-C. Song, Y.-H. Zhu, Q.-
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Empirical formula
Formula mass
Temperature (K)
Crystal system
Space group
C91H32O2P2Pd·MeOH
1345.54
293(2)
[6]
[7]
[8]
triclinic
¯
P1
˚
a (A)
9.986 (7)
13.934(10)
20.089(14)
73.834(13)
77.823(15)
80.527(15)
2608(3)
2
1.714
0.487
1364
10488, 0.0924
6687
1.069
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
[9]
3
˚
V (A )
[10]
[11]
[12]
Z
Dcalcd.(mg/mm3)
µ (mmϪ1
F (000)
)
Unique reflections, Rint
Observed reflections
Goodness-of-fit on F2
R [I Ͼ 2σ(I)]
[13]
[14]
[15]
R1 ϭ 0.1426, wR2 ϭ 0.3314
Acknowledgments
We are grateful to the National Natural Science Foundation of
China and the Research Fund for the Doctoral Program of Higher
Education of China for financial support of this work.
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Y. -
Received July 28, 2003
Early View Article
Published Online January 19, 2004
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Eur. J. Inorg. Chem. 2004, 866Ϫ871
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
871