Complexation and C-H/C-P bond activation of the (PPh2)C 60H molecule on triosmium carbonyl clusters

Article abstract of DOI:10.1021/om900914a

Reaction of (PPh₂)C₆₀H (1) and Os₃(CO) ₁₀(NCMe)2 produces Os₃(CO)₁₀(μη ³-(PPh₂)C₆₀H) (2), with one edge of the triosmium cluster bridged by the phosphine gr

Full text of DOI:10.1021/om900914a

604 Organometallics 2010, 29, 604–609
DOI: 10.1021/om900914a
Complexation and C-H/C-P Bond Activation of the (PPh2)C60H
Molecule on Triosmium Carbonyl Clusters
Wen-Yann Yeh* and Kune-You Tsai
Department of Chemistry and Center for Nanoscience and Nanotechnology,
National Sun Yat-Sen University, Kaohsiung 804, Taiwan
Received October 19, 2009
Reaction of (PPh2)C60H (1) and Os3(CO)10(NCMe)2 produces Os3(CO)10(μ,η3-(PPh2)C60H) (2),
with one edge of the triosmium cluster bridged by the phosphine group and one CdC double bond of
1. Treating compound 1 with Os3(CO)11(NCMe) affords Os3(CO)11((PPh2)C60H) (3), with the
phosphine ligand coordinated to one osmium atom. Thermolysis of 2 in refluxing chlorobenzene
leads to orthometalation of one phenyl group and C-H/C-P bond activation of the (PPh2)C60H
ligand to afford the phosphido cluster (μ-H)2Os3(CO)9(μ3,η2-PPh(C6H4)) (4) and C60 molecule.
Compound 3 undergoes thermal decarbonylation in refluxing toluene to produce 2. The molecular
structures of compounds 1-BH3, 2, and 3 were determined by an X-ray diffraction study.
Introduction
various complexes.5 Furthermore, coordination to two or
three of the double bonds of a hexagon was found in several
ruthenium,6 osmium,7 rhenium,8 and iridium9 cluster com-
plexes, such that the metals are η2-bound to adjacent bonds
of a C6 face. Syntheses of σ-bonded fullerene metal deriva-
The availability of gram quantities of the fullerene C60 has
facilitated the study of the reactivity of this intriguing
molecule.1 The first fullerene-transition metal complex
was reported by Fagan in the reaction of [Cp*Ru(NCMe)3]þ
and C60.2 Because the p-orbitals within a hexagon of the C60
framework are tilted away from the center of the ring,3 the
C60 hexagons behave more like a cyclohexatriene unit, and
complexation of transition metals to the fullerene core
proceeds similarly to well-established reactions of electron-
deficient olefins in a dihapto manner to one or more
π-bonds.4 The binding of C60 to transition metals in a
η2-fashion becomes clearly evident by the formation of
2-
tives are usually from reaction of fullerene dianion C60
with organometal halides,10 hydrometalation of metal-hy-
dride compounds,11 or metalation of fullerene with metal-
centered radicals through photodissociation of dimetallic
complexes.12 Remarkably, pentahaptofullerene metal com-
-
plexes have been obtained by treating C60HR5 or C60R5
(R = alkyl and aryl) with precursory metal complexes or
metal salts.13
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*Corresponding author. E-mail: wenyann@mail.nsysu.edu.tw.
€
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pubs.acs.org/Organometallics
Published on Web 01/05/2010
2010 American Chemical Society

Article
With the development of an extensive organic chemistry of
Organometallics, Vol. 29, No. 3, 2010 605
Scheme 1
fullerenes, it is now possible to construct a variety of
modified fullerenes that incorporate a metal-binding group
into their structure.14 The syntheses of such fullerene-con-
taining ligands offer the potential to exploit the chemical
reactivity, redox and electron-acceptor characteristics,
photochemical behavior, electron-withdrawing properties,
and novel structural features that a fullerene group pro-
vides.15 For instance, the fullerene-phosphines have been
made through addition of phosphide or borane-protected
phosphide nucleophiles to C60 and subsequent protonation
of the resulting anion.16 Some mononuclear palladium and
platinum complexes of the type (C60-phosphine)2MCl2 were
prepared, which display catalytic activity in Grignard re-
agent/styrene cross-coupling reactions.16a As part of our
interest in cluster and phosphine chemistry,17 herein we
present the complexation of (PPh2)C60H to triosmium car-
bonyl clusters and show their thermal reactivity leading to
C-H/C-P bond activation of the fullerene-phosphine
molecule mediated by the trimetallic framework.
Compound 1-BH3 presents the phenyl proton resonances
at δ 8.52 (m, 4H) and 7.65 (6H) and the H-C60 proton
resonance at δ 6.96 (d, JP-H = 24 Hz). In contrast, the 1H
NMR spectrum of 2 shows four multiplet signals at δ 8.91,
8.33, 7.68, and 7.55 in a ratio of 1:2:6:1, likely due to steric
constraints of the phenyl groups upon coordination of the
phosphorus atom to the Os3 cluster. Most strikingly, the
H-C60 proton resonance shows a substantial upfield shift to
δ 6.10 (d, JP-H = 23 Hz), which may be attributed to
shielding by ring current of the phenyl groups.18
Results and Discussion
Functionalization of fullerene with a protected diphenyl-
phosphenyl group was prepared by treating C60 with H3B-
PPh2- at low temperature, followed by protonation to afford
(H3B-PPh2)C60H (1-BH3), according to the method reported
by Nakamura and co-workers.16 The (PPh2)C60H (1) mole-
cule was generated by removing the BH3 protecting group
with N(C2H4)3N (DABCO)16 immediately before use. The
reaction of 1 and Os3(CO)10(NCMe)2 in refluxing toluene
results in substitution of the labile acetonitrile ligands by
the phosphine group and one CdC double bond of 1 to
generate Os3(CO)10(μ,η3-(PPh2)C60H) (2) in 54% yield after
separation by TLC and crystallization from CS2/MeOH. On
the other hand, treating 1 with Os3(CO)11(NCMe) produces
Os3(CO)11((PPh2)C60H) (3) in 55% yield, with the acetoni-
trile ligand being replaced by the phosphine group. The
reactions are summarized in Scheme 1.
The 1H NMR spectrum of 3 at room temperature shows
only two broad signals at δ 8.31 (4H) and 7.62 (6H) for the
phenyl protons, indicating the molecule is fluxional in solu-
tion, likely through Os-P-C(C60) bond rotation or scram-
bling of the phosphine group in different sites of the cluster.
Isomerism of phosphine-substituted triosmium clusters is
1
well documented in the literature.19 The slow-exchange H
NMR spectrum taken at -80 °C reveals the H-C60 proton
resonance at δ 6.93 (d, JP-H = 24 Hz) and seven multiplet
signals in the range δ 8.00-7.09 for the phenyl proton
resonances.
Compounds 2 and 3 form an air-stable, black and yellow-
brown crystalline solid, respectively, and have been charac-
terized by elemental analysis, mass, IR, and NMR spectros-
copy. The molecular ion peak at m/z 1762 (192Os) for 2 is the
combination of Os3(CO)10 and one (PPh2)C60H moiety. On
the contrary, the FAB and EI mass spectra of 3 did not give
resolvable ion peaks with m/z > 1000, while the MALDI
mass spectrum displays the highest ion peak at m/z 1678
The molecular structure of 1-BH3 is illustrated in Figure 1.
Addition of one PPh2(BH3) group and one hydrogen atom to
a (6:6)-double bond causes distortion of the C60 framework
from an idealized Ih symmetry. The P1-C14 length is
˚
1.886(4) A, and the bond angles imposed on the phosphorus
atom, 105.3(2)-113.0(2)°, are only slightly deviated from the
˚
ideal 109.5°. The distances C14-C38 = 1.58(6) A, C14-C15 =
˚
˚
1.537(6) A, C14-C18 = 1.537(5) A, C37-C38 = 1.521(5)
(
isotope distribution matches the calculated pattern.
192Os), corresponding to the [Mþ-4CO] fragment, and the
˚
˚
A, and C38-C39 = 1.512(6) A are typical C-C single-bond
˚
lengths, while the remaining C-C lengths are 1.38 A (av)
˚
(6:6-ring junctions) and 1.45 A (av) (6:5-ring junctions). The
C14 and C38 atoms are sp3 hybridized to show a distorted
tetrahedral bonding, where the P-C-C and C-C-C angles
centered on the C14 atom are in the range 99.9(3)-116.0(3)°,
and the C-C-C angles centered on the C38 atom are
101.5(3)-115.2(4)°. Overall, the fullerene architecture is
elongated compared with the unperturbed C60 molecule,
such that the angles between the C14-C38 vector and the
planes defined by C15-C14-C18 and C37-C38-C39 are
(14) (a) Taylor, R. Lecture Notes on Fullerene Chemistry; Imperial
College Press: London, UK, 1999. (b) Hirsch, A.; Brettreich, M. Fullerenes;
Wiley-VCH: Weinheim, Germany, 2005. (c) Thilgen, C.; Diederich, F.
Chem. Rev. 2006, 106, 5049. (d) Murata, M.; Murata, Y.; Komatsu, K.
Chem. Commun. 2008, 6083.
(15) (a) Guldi, D. M. Chem. Soc. Rev. 2002, 31, 22. (b) Martín, N.
Chem. Commun. 2006, 2093. (c) Langa, F.; Nierengarten, J.-F. Fullerenes:
Principles and Applications; RSC Publication: Cambridge, UK, 2007.
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(d) Thompson, B. C.; Frechet, J. M. J. Angew. Chem., Int. Ed. 2008, 47, 58.
(16) (a) Yamago, S.; Yanagawa, M.; Nakamura, E. J. Chem. Soc.,
Chem. Commun. 1994, 2093. (b) Yamago, S.; Yanagawa, M.; Mukai, H.;
Nakamura, E. Tetrahedron 1996, 52, 5091.
(17) (a) Yeh, W.-Y.; Shiue, T.-W.; Peng, S.-M.; Lee, G.-H. Organo-
metallics 2003, 22, 2990. (b) Yeh, W.-Y.; Liu, Y.-C.; Peng, S.-M.; Lee, G.-H.
Organometallics 2003, 22, 2361. (c) Yeh, W.-Y.; Hsiao, S.-C.; Peng, S.-M.;
Lee, G.-H. Organometallics 2005, 24, 3365. (d) Shiue, T.-W.; Yeh, W.-Y.;
Lee, G.-H.; Peng, S.-M. Organometallics 2006, 25, 4150.
(18) Drago, R. S. Physical Methods for Chemists, 2nd ed.; Saunders
College Publishing: FL, 1992.
(19) (a) Deeming, A. J.; Donovan-Mtunzi, S.; Kabir, S. E.; Manning,
P. J. J. Chem. Soc., Dalton Trans. 1985, 1037. (b) Leong, W. K.; Liu, Y.
J. Organomet. Chem. 1999, 584, 174. (c) Yeh, W.-Y.; Li, C.-I.; Peng, S.-M.;
Lee, G.-H. J. Organomet. Chem. 2004, 689, 105.

606 Organometallics, Vol. 29, No. 3, 2010
Yeh and Tsai
˚
Figure 1. Molecular structure of 1-BH3. The phenyl hydrogens have been artificially omitted. Selected bond distances (A): P1-C14 =
1.886(4), P1-C1 = 1.802(5), P1-C7 = 1.819(4), P1-B1 = 1.913(5), C14-C15 = 1.537(6), C14-C18 = 1.537(5), C14-C15 =
1.537(6), C14-C38 = 1.586(6), C15-C41 = 1.373(6), C15-C16 = 1.428(6), C37-C38= 1.521(5), C38-C39 = 1.512(6), C39-C40 =
1.363(6), C40-C41 = 1.474(6), C37-C48 = 1.435(6), C47-C48 = 1.446(6), C39-C47 = 1.442(6). Selected bond angles (deg):
C1-P1-C7 = 109.9(2), C1-P1-B1 = 113.0(2), C1-P1-C14 = 105.3(2), C7-P1-B1 = 112.3(2), C7-P1-C14 = 108.0(2),
B1-P1-C14 = 108.0(2), P1-C14-C15 = 116.0(3), P1-C14-C18 = 106.0(3), P1-C14-C38 = 113.9(4), C15-C14-C18 = 99.9(3),
C15-C14-C38 = 113.9(4), C18-C14-C38 = 114.3(3), C14-C15-C16 = 109.9(4), C15-C16-C17 = 108.7(4), C14-C18-C17 =
110.1(3), C14-C38-C37 = 114.9(3), C14-C38-C39 = 115.2(4), C37-C38-C39 = 101.5(3).
˚
Figure 2. Molecular structure of 3. The phenyl hydrogens have been artificially omitted. Selected bond distances (A): P1-C24 =
1.95(2), P1-C12 = 1.84(1), P1-C18 = 1.81(2), P1-Os1 = 2.362(4), Os1-Os2 = 2.887(1), Os1-Os3 = 2.9139(9), Os2-Os3 =
2.885(1), C24-C25 = 1.54(2), C24-C29 = 1.58(2), C24-C33 = 1.54(2), C28-C29 = 1.51(2), C29-C30 = 1.53(2). Selected bond
angles (deg): Os1-Os2-Os3 = 60.65(2), Os1-Os3-Os2 = 59.71(2), Os2-Os1-Os3 = 59.64(3), Os1-P1-C24 = 118.1(5),
Os1-P1-C12 = 109.9(6), Os1-P1-C18 = 121.0(5), C12-P1-C18 = 103.1(7), C12-P1-C24 = 105.2(6), C18-P1-C24 =
97.6(7), P1-C24-C25 = 106.7(9), P1-C24-C29 = 111.1(9), P1-C24-C33 = 112(1), C24-C29-C28 = 116(1), C24-C29-C30 =
116(1), C28-C29-C30 = 101(1), C25-C24-C29 = 113(1), C25-C24-C33 = 101(1), C29-C24-C33 = 113(1).
57.8° and 55.1°, respectively, while such angles are 31° in
free C60.
The molecular structure of 3, shown in Figure 2, is
derived from the mother molecule Os3(CO)12 by replacing
an equatorial carbonyl group with a phosphine ligand. The
Os1-P1 bond is slightly tilted from the trimetallic plane by
4.4°. The Os3 unit forms an isosceles triangle with the
˚
Os1-Os3 distance (2.9139(9) A) being slightly longer

Article
Organometallics, Vol. 29, No. 3, 2010 607
˚
Figure 3. Molecular structure of 2. The phenyl hydrogens have been artificially omitted. Selected bond distances (A): P1-C23 =
1.93(1), P1-C11 = 1.81(1), P1-C17 = 1.80(1), P1-Os1 = 2.380(3), Os1-Os2 = 2.9360(8), Os1-Os3 = 2.8607(8), Os2-Os3 =
2.8866(8), Os2-C29 = 2.20(1), Os2-C30 = 2.25(1), C23-C24 = 1.52(2), C23-C28 = 1.50(2), C23-C42 = 1.52(2), C24-C25 =
1.50(2), C24-C39 = 1.51(2), C28-C29 = 1.51(2), C29-C30 = 1.43(2), C29-C43 = 1.48(2), C42-C43 = 1.43(2), C43-C44 =
1.38(2), C44-C45 = 1.40(2), C45-C46 = 1.34(2). Selected bond angles (deg): Os1-Os2-Os3 = 58.85(2), Os1-Os3-Os2 = 61.44(2),
Os2-Os1-Os3 = 59.72(2), Os1-P1-C23 = 116.0(4), Os1-P1-C11 = 110.2(5), Os1-P1-C17 = 117.7(4), C11-P1-C17 =
103.1(6), C11-P1-C23 = 106.3(6), C17-P1-C23 = 102.2(5), P1-C23-C24 = 116.4(8), P1-C23-C28 = 108.2(8), P1-C23-
C42 = 103.5(7), C24-C23-C28 = 114(1), C24-C23-C42 = 114(1), C28-C23-C42 = 98.9(9), C23-C24-C25 = 117(1), C23-
C24-C39 = 117(1), C25-C24-C39 = 100(1).
˚
(ca. 0.03 A) than the other two Os-Os bonds. The average
transition metal complexes.5 The Os-C60 distances are
˚
˚
˚
˚
Os-Os distance for 3 (2.895(1) A) is ca. 0.02 A longer than
that determined for Os3(CO)11(η2-C60)7a and may be attribu-
ted to the stronger net donor but weaker acceptor cap-
ability of phosphine compared with olefin. The P1-C24
bond (1.95(2) A) is ca. 0.06 A longer than that in 1-BH3, and
the Os1-P1-C24 angle (118.1(5)°) increases by 10° com-
pared with the B1-P1-C14 angle (108.0(2)°) in 1-BH3,
consistent with steric repulsions between the bulky Os3
cluster and C60 moiety. Conversely, the C-P1-C angles
are compressed, ranging from 97.6(7)° to 105.2(6)°. The
dihedral angle between the Os1-P1-C24 plane and the Os3
triangle is 32.9(5)°. The Os1, Os2, and Os3 atoms are each
linked to three, four, and four terminal carbonyl groups.
Individual Os-CO distances range from 1.87(2) to 2.00(2)
A, C-O distances range from 1.08(2) to 1.17(2) A, and
the Os-C-O angles are in the range 172(2)-177(2)°.
The axial carbonyls are roughly orthogonal to the Os3
surface (85.6(5)-92.8(9)°) and eclipsed to each other
(1.05-4.87°).
The ORTEP diagram of 2 is presented in Figure 3, where
the (PPh2)C60H unit is coordinated to two equatorial sites of
the Os3 cluster through the phosphine group and one CdC
double bond in a μ,η3-bonding feature. The bond lengths
Os2-C29 = 2.20(1) A and Os2-C30 = 2.25(1) A, which
are comparable to the values found in Os3(CO)11(η2-C60) and
related complexes.7 The dihedral angle between the
C29-Os2-C30 and Os3 planes is 10.8(8)°. The distance
˚
˚
˚
˚
C29-C30 = 1.43(2) A is elongated (ca. 0.05 A) in compar-
ison with other unperturbed (6:6)-double bonds and may be
attributed to π-back-donation from the Os2 atom. On the
other hand, the C29 and C30 atoms are pulled away from the
fullerene surface, such that the angles between the C29-C30
edge and the C28-C29-C43 and C31-C30-C46 planes are
45.2° and 47.9°, respectively, while the corresponding angles
for the C35-C36 edge of 3 are 32.3° and 39.0°. The trime-
tallic parts are based on a triangular array of osmium atoms
˚
in which the Os1-Os2 distance of 2.9360(8) A is significantly
˚
˚
longer than the other two intermetallic distances, Os1-
˚
˚
Os3 = 2.8607(8) A and Os2-Os3 = 2.8866(8) A. The Os1,
Os2, and Os3 atoms are each associated with three, three,
and four terminal carbonyl ligands. Individual Os-CO
˚
˚
distances range from 1.90(2) A (for Os1-C1) to 2.08(2) A
(for Os3-C7), C-O distances range from 1.05(2) A (for
C7-O7) to 1.15(2) A (for C3-O3), and the Os-C-O angles
˚
˚
are in the range 173(2)-179(2)°. Coordination of the bulky
(PPh2)C60H species in a μ,η3-fashion causes substantial
distortions for the carbonyl arrangements on the Os3 triangle
(Figure 4). For instance, the axial carbonyl groups are
not perpendicular to the Os3 plane with the Os-Os-CO
angles ranging from 79.9(4)° (Os1-Os2-C4) to 96.5(4)°
˚
˚
Os1-P1= 2.380(3) A and P1-C23 = 1.93(1) A and the
angle Os1-P1-C23 = 116.0(4)° are compatible with those
in 3. The C60 moiety is bound to the Os2 atom in an η2-
fashion through a 6:6-ring junction, as found in other η2-C60

608 Organometallics, Vol. 29, No. 3, 2010
Yeh and Tsai
Figure 4. View of 2 and 3, showing the distorted C60 framework and the arrangement of carbonyl ligands on triosmium clusters.
for 2 h produces 2 in 72% yield. A proposed mechanism is
illustrated in Scheme 2. Apparently, decomplexation of the
fullerene CdC double bond at elevated temperature gener-
ates a vacant coordination site suitable to undergo ortho-
H-C(Ph) bond metalation, and the resulting intermediate
might place the H-C60 bond in proximity to one osmium
atom that facilitates the second C-H bond activation;
subsequent cleavage of the P-C60 bond to release steric
crowding would produce 4 and C60. Another possibility
involves the initial loss of CO from the Os(CO)4 moiety,
followed by ligand activation. On the other hand, thermo-
lysis of 3 results in decarbonylation to create a vacant site,
followed by complexation of the fullerene moiety to give 2.
Scheme 2
Experimental Section
General Methods. All manipulations were carried out under
an atmosphere of purified dinitrogen with standard Schlenk
techniques. (H3B-PPh2)C60H (1-BH3),16 (PPh2)C60H (1),16 Os3-
(CO)10(NCMe)2,21 and Os3(CO)11(NCMe)22 were prepared as
described in the literature. Solvents were dried over appropriate
reagents under dinitrogen and distilled immediately before use.
Preparative thin-layer chromatographic (TLC) plates were pre-
pared from silica gel (Merck). Infrared spectra were recorded on
a Jasco FT/IR-4100 IR spectrometer. 1H spectra were obtained
on a Varian Unity INOVA-500 spectrometer at 500 MHz. Fast-
atom-bombardment (FAB) and matrix-assisted laser desorp-
tion ionization (MALDI) mass spectra were recorded on a
JEOL JMS-SX102A and Bruker Microflex-LT mass spectro-
meter, respectively. Elemental analyses were performed at the
National Science Council Regional Instrumentation Center at
National Chen-Kung University, Tainan, Taiwan.
(Os1-Os2-C5) and are staggered with the C-Os-Os-C
torsional angles in the range 16.1-22.9°.
Compound 2 remains intact in refluxing toluene (110 °C)
over 3 days. Activation of the H-C60 bond of 2 by the Os3
cluster is accessible in refluxing chlorobenzene (132 °C).
However, this thermal reaction is also concomitant with
orthometalation of one phenyl group and cleavage of the
P-C60 bond to release C60 and generate the known phos-
phido cluster complex (μ-H)2Os3(CO)9(μ3,η2-PPh(C6H4))20
(4) in 58% yield. In contrast, heating 3 in refluxing toluene
(21) Braga, D.; Grepioni, F.; Parisini, E.; Johnson, B. F. G.; Martin,
C. M.; Nairn, J. G. M.; Lewis, J.; Martinelli, M. J. Chem. Soc., Dalton
Trans. 1993, 1891.
(20) Colbran, S. B.; Irele, P. T.; Johnson, B. F. G.; Lahoz, F. J.;
Lewis, J.; Raithby, P. R. J. Chem. Soc., Dalton Trans. 1989, 2023.
(22) Drake, S. R.; Khattar, R. Inorg. Synth. 1990, 28, 234.

Article
Organometallics, Vol. 29, No. 3, 2010 609
Table 1. Crystallographic Data for 1-BH3, 2, and 3
(m, 2H, Ph), 7.71 (m, 1H, Ph), 7.63 (m, 1H, Ph), 7.45 (m, 2H,
Ph), 7.32 (m, 2H, Ph), 7.09 (m, 1H, Ph), 6.93 (d, 1H, JP-H = 24
Hz, C60H). 31P{1H} NMR (CS2þC6D6, 25 °C): δ 34.1 (br).
Thermolysis of 2. Compound 2 (9 mg, 0.0051 mmol) and
chlorobenzene (10 mL) were placed in an oven-dried 50 mL
Schlenk flask, equipped with a condenser, under a dinitrogen
atmosphere. The solution was heated to reflux for 12 h until no
IR absorptions due to the starting compound were present. The
solution was cooled to room temperature, and the solvent was
removed under vacuum. The residue was subjected to TLC,
eluting with carbon disulfide. The first purple band gave C60 (3
mg, 82%), and the second pale yellow band gave the known
phosphido cluster complex (μ-H)2Os3(CO)9(μ3,η2-PPh(C6H4))
1-BH3
2
3
chem formula
cryst solvent
cryst syst
fw
T, K
space group
C
CS2
monoclinic
996.74
200(2)
72H14BP
C82H11O10Os3P
0.5 CS2
tetragonal
1795.55
200(2)
C83H11O11Os3P
CS2
triclinic
1861.62
293(2)
P21/c
P4/n
P1
˚
a, A
12.8935(3)
32.524(1)
9.9545(3)
29.0200(4)
29.0200(4)
14.4970(2)
13.5272(2)
14.7670(3)
15.3027(4)
100.780(1)
99.911(1)
107.088(1)
2785.1(1)
2
2.220
7.009
0.0689/0.1545
1.060
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
106.646(2)
1
(4; 3 mg, 58%). MS (FAB): m/z 1014 (Mþ, 192Os). H NMR
3
˚
V, A
3999.5(2)
4
1.655
0.233
0.0575/0.1336
0.788
12208.8(3)
8
1.954
6.358
0.0614/0.1724
1.062
(CDCl3, 23 °C): δ 7.79 (m, 1H, C6H4), 7.60-7.52 (m, 5H, Ph),
6.88 (m, 1H, C6H4), 6.71 (m, 1H, C6H4), 6.22 (m, 1H, C6H4),
-17.10 (br, 2H, μ-H). 31P{1H} NMR (CDCl3, 23 °C): δ 41.62 (s).
IR (n-hexane, νCO): 2108 (m), 2078 (s), 2051 (s), 2039 (m), 2028
Z
Dcalc, g cm-3
μ, mm-1
R1/wR2
(m), 2011 (s), 1999 (m), 1981 (m) cm-1
.
GOF on F2
Thermolysis of 3. Compound 3 (10 mg, 0.0055 mmol) and
toluene (5 mL) were placed in an oven-dried 25 mL Schlenk
flask, equipped with a condenser, under a dinitrogen atmo-
sphere. The solution was heated to reflux for 2 h and cooled to
room temperature, and the solvent was removed under vacuum.
The residue was separated by TLC with carbon disulfide as
eluant to obtain 2 (7 mg, 72%).
Synthesis of 2. Compound 1 (50 mg, 0.055 mmol) and Os3-
(CO)10(NCMe)2 (51 mg, 0.055 mmol) were placed in an oven-
dried 50 mL Schlenk flask, equipped with a condenser, under a
dinitrogen atmosphere. Toluene (30 mL) was introduced into
the flask via a syringe, and the solution was first stirred at room
temperature for 5 h and then heated to reflux for 1 h. The volatile
materials were removed under vacuum, and the residue was
subjected to TLC, eluting with carbon disulfide. Isolation of the
material forming the second dark brown band gave black
crystals of Os3(CO)10(μ,η3-(PPh2)C60H) (2; 52 mg, 0.029 mmol,
54%) after crystallization from CS2/MeOH. MS (FAB): m/z
1762 (Mþ, 192Os). Anal. Calcd for C82H11O10Os3P: C, 56.03; H,
0.63. Found: C, 56.35; H, 0.77. IR (n-hexane, νCO): 2106 (s),
2069 (vw), 2055 (w), 2039 (m), 2026 (vs), 2007 (w), 1994 (w), 1983
(w), 1975 (w), 1965 (vw) cm-1. 1H NMR (CS2þCDCl3, 23 °C): δ
8.91 (m, 1H, Ph), 8.33 (m, 2H, Ph), 7.68 (m, 6H, Ph), 7.55 (m,
1H, Ph), 6.10 (d, 1H, JP-H = 23 Hz, C60H). 31P{1H} NMR
(CS2þCDCl3, 23 °C): δ 38.0 (s).
Structure Determination for 1-BH3, 2, and 3. The crystals of
1-BH3, 2, and 3 found suitable for X-ray analysis, grown from
CS2/MeOH at room temperature, were each mounted in a thin-
walled glass capillary and aligned on the Nonius Kappa CCD
diffractometer, with graphite-monochromated Mo KR radia-
˚
tion (λ = 0.71073 A). The θ range for data collection is
1.65-25.09° for 1-BH3, 2.11-25.04° for 2, and 2.27-24.99°
for 3. Of the 23 595, 71 893, and 24 107 reflections collected,
7054, 10 808, and 9756 reflections were independent for 1-BH3,
2, and 3, respectively. All data were corrected for Lorentz and
polarization effects and for the effects of absorption. The
structure was solved by the direct method and refined by least-
squares cycles. The non-hydrogen atoms were refined anisotro-
pically. Hydrogen atoms were included but not refined. All
calculations were performed using the SHELXTL-97 pack-
age.23 The data collection and refinement parameters are pre-
sented in Table 1.
Synthesis of 3. Compound 1 (20 mg, 0.022 mmol) and Os3-
(CO)11(NCMe) (20 mg, 0.022 mmol) were placed in an oven-
dried 50 mL Schlenk flask, equipped with a condenser, under a
dinitrogen atmosphere. Dichloromethane (30 mL) was intro-
duced into the flask via a syringe, and the solution was stirred at
room temperature for 2 h. The volatile materials were removed
on a rotary evaporator, and the residue was subjected to TLC,
eluting with carbon disulfide. Isolation of the material forming
the second brown band afforded yellow-brown crystals of Os3-
(CO)11((PPh2)C60H) (3; 21 mg, 0.012 mmol, 55%) after crystal-
lization from CS2/MeOH. MS (MALDI): m/z 1678 (Mþ-4CO,
192Os). Anal. Calcd for C84H11O11Os3PS2: C, 54.19; H, 0.60.
Found: C, 54.24; H, 0.60. IR (CH2Cl2, νCO): 2110 (m), 2059 (s),
Acknowledgment. We are grateful for support of this
work by the National Science Council of Taiwan. We
thank Mr. Ting-Shen Kuo (National Taiwan Normal
University, Taipei) for X-ray diffraction analysis.
Supporting Information Available: X-ray crystal files in CIF
format for 1-BH3, 2, and 3. This material is available free of
charge via the Internet at http://pubs.acs.org.
2036 (s), 2021 (vs), 1991 (m), 1980 (sh) cm-1 1H NMR
.
(CS2þCD2Cl2, 25 °C): δ 8.31 (br, 4H, Ph), 7.62 (br, 6H, Ph).
€
(23) Sheldrick, G. M. SHELXTL-97; University of Gottingen:
Germany, 1997.
1H NMR (CS2þCD2Cl2, -80 °C): δ 8.00 (m, 1H, Ph), 7.76