Complexation and metallation of Ph2PC{triple bond, long}C(CH2)5C{triple bond, long}CPh2 in triosmium carbonyl clusters

Article abstract of DOI:10.1016/j.jorganchem.2007.05.003

Reaction of Ph₂PC{triple bond, long}C(CH₂)₅C{triple bond, long}CPh₂ with Os₃(CO)₁₀(NCMe)₂ affords Os₃(CO)₁₀(μ,η²-(Ph₂P)₂C₉H₁₀) (1) and the double cluster [Os₃(CO)₁₀]₂(μ,η²- (Ph₂P)₂C₉H₁₀)₂ (2), through coordination of the phosphine groups. Thermolysis of 1 in toluene generates Os₃(CO)₇(μ-PPh₂)(μ₃,η⁵-Ph₂PC₉H₁₀) (3) and Os₃(CO)₈(μ-PPh₂)(μ₃,η⁶-Ph₂P(C₉H₁₀)CO) (4). The molecular structures of 1, 3, and 4 have been determined by an X-ray diffraction study. Both 3 and 4 contain a bridging phosphido group and a carbocycle connected to an osmacyclopentadienyl ring, which are apparently derived from C-P bond activation and C-C bond rearrangement of the dpndy ligand governed by the triosmium clusters.

Full text of DOI:10.1016/j.jorganchem.2007.05.003

Journal of Organometallic Chemistry 692 (2007) 3619–3624
www.elsevier.com/locate/jorganchem
Complexation and metallation of Ph2PC„C(CH2)5C„CPh2
in triosmium carbonyl clusters
a
a,
b
b
Tsun-Wei Shiue , Wen-Yann Yeh *, Gene-Hsiang Lee , Shie-Ming Peng
a
Department of Chemistry, Center for Nanoscience and Nanotechnology, National Sun Yat-Sen University, Kaohsiung 804, Taiwan
b
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan
Received 16 March 2007; received in revised form 16 April 2007; accepted 1 May 2007
Available online 8 May 2007
Abstract
Reaction of Ph2PC„C(CH2)5C„CPh2 with Os3(CO)10(NCMe)2 affords Os3(CO)10(l,g2-(Ph2P)2C9H10) (1) and the double cluster
[Os3(CO)10]2(l,g2- (Ph2P)2C9H10)2 (2), through coordination of the phosphine groups. Thermolysis of 1 in toluene generates
Os3(CO)7(l-PPh2)(l3,g5-Ph2PC9H10) (3) and Os3(CO)8(l-PPh2)(l3,g6-Ph2P(C9H10)CO) (4). The molecular structures of 1, 3, and 4 have
been determined by an X-ray diffraction study. Both 3 and 4 contain a bridging phosphido group and a carbocycle connected to an osma-
cyclopentadienyl ring, which are apparently derived from C–P bond activation and C–C bond rearrangement of the dpndy ligand gov-
erned by the triosmium clusters.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Triosium; Cluster; Phosphine complex; Alkyne; Metallation
1. Introduction
We recently prepared the multifunctional molecule
Ph2PC„C(CH2)5C„CPPh2 (abbreviated as dpndy) and
showed its reactions with tungsten carbonyls to yield a pad-
dle-wheel complex [W(CO)3]2(l,g2-dpndy)3 and a tripodal
complex W(CO)3[(l,g2-dpndy)W(CO)3(g2-dpndy)]3 [16].
In these compounds, dpndy acts as a chelating/bridging
ligand through coordination of the phosphorous atoms,
while the nonadiynyl linkage remains intact. Our contin-
uing interest in the cluster chemistry and alkyne-coupling
reaction [17] prompted us to investigate the reaction of
dpndy with Os3(CO)10(NCMe)2.
The study of transition metal clusters has been an active
area of current chemical research [1–8]. Discrete, soluble
metal clusters often display catalytic activity and are stud-
ied as models for the surface of bulk metals [9,10]. In addi-
tion, the ability of a metal cluster to organize a flexible
ligand around it coordination sphere has led to design of
intramolecularly organized recognition sites [11]. Since
the cluster-bonded ligand is capable of interacting with sev-
eral metal centers, it frequently displays a reactivity differ-
ent from that found in the monometallic systems [12]. For
instance, the Ph2P(C6H4)CH@N(CH2)2(C5H4N) molecule
is a typical tridentate P–N–N ligand bound to a metal
ion [13] or a M(CO)3 species [14], while a sequence of the
methylene and imine C–H bond activation occurs in coor-
dination to a metal cluster [15].
2. Results and discussion
Treatment of Os3(CO)10(NCMe)2 with equimolar
amounts of Ph2PC„C(CH2)5C„CPh2 at ambient temper-
ature results in facile substitution of the labile acetonitrile
ligands by the phosphine groups to afford Os3(CO)10-
(l,g2-(Ph2P)2C9H10) (1; 63%) and the double cluster
[Os3(CO)10]2(l,g2-(Ph2P)2C9H10)2 (2; 4%) (Eq. (1)) as air-
stable, yellow crystalline solids. Johnson and coworkers
*
Corresponding author. Fax: +886 7 5253908.
E-mail address: wenyann@mail.nsysu.edu.tw (W.-Y. Yeh).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.05.003

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T.-W. Shiue et al. / Journal of Organometallic Chemistry 692 (2007) 3619–3624
previously reported the reaction of Os3(CO)10 (NCMe)2
and Ph2PC„CCPh2 (dppa) to yield the di-, tri-, and tetra-
meric clusters [Os3(CO)10(dppa)]n (n = 2–4) in moderate
yields [18]. It has been argued that the rigidity of the linear
The dpndy molecule bridges the Os1–Os2 edge with Os1–
P1 2.336(1) and Os2–P2 2.345(1) A. The two Os–P bonds
˚
are essentially equatorial with respect to the Os3 plane with
the torsional angles P1–Os1–Os2–Os3 171.0(8)°, P2–Os2–
Os3–Os1 171.6(1)°, and P1–Os1–Os2–P2 143.6(1)°. The
P–C„C–C backbones are slightly bowed as indicated by
the P–C„C angles (175.5(5)° to P1 and 171.4(6)° to P2)
and the C„C–C angles (176.3(6)o). The Os1, Os2, and
Os3 atoms are each connected to 3, 3, and 4 terminal car-
bonyl ligands, respectively, with the Os–C–O angles in the
range 174.4(5)–178.5(6)°. The axial carbonyls associated
with the Os2 atom are no longer perpendicular to the trios-
mium plane, with the angles Os1–Os2–C4 80.3(2)°, Os1–
Os2–C6 95.5(2)°, and Os3–Os2–C6 86.4(2)°, probably
because of steric interactions with the hydrocarbon chain.
Compound 2 presents the same elementary analysis to
1, while the FAB mass data indicate a dimeric cluster
formula [Os3(CO)10(dpndy)]2 for 2. It probably has a
structure analogous to [Os3(CO)10(dppa)]2 [19] that the
two triosmium clusters are linked by two dpndy ligands
in a macro-ring fashion. The 31P{1H} NMR spectrum
of 2 at 23 °C shows a signal at d ꢀ35.8, suggesting that
the four phosphine groups bridge the two Os3 clusters
symmetrically, or they are equivalent through a dynamic
process proposed for the M3(CO)10(PR3)2 complexes [20].
However, these cannot be verified by a variable-tempera-
ture NMR study due to the poor solubility of 2 at lower
temperatures.
˚
–C„C– unit and the lone P–P distance (4.7A) prevents
dppa to chelate one metal center or cross a metal–metal
bond [19]. For the dpndy molecule, however, the flexible
pentylene chain allows the two phosphine groups to span
one Os–Os edge to yield 1 as the major product.
Ph
Ph
P
+
Os3(CO)10(NCMe)2
Os (CO)4
Os
(CO)3
Os
P
(CO)3
PPh2
PPh2
Ph
Ph
Ph
1
+
Ph
Ph
Ph
P
P
(CO)3
(CO)3
Os
(OC)
4 Os
(CO)
Os
Os
4
Os
(CO)3
P
Os
(CO)3
P
2
Ph
Ph
Ph
Ph
ð1Þ
The 31P{1H} NMR spectrum of 1 presents two signals at
ꢀ33.6 and ꢀ35.8 ppm, suggesting the presence of two
1
inequivalent phosphorous atoms in the molecule. The H
NMR spectrum shows the phenyl proton resonances in
the range 7.80–7.20 ppm and three multiplets at 2.71
(4H), 1.86 (2H), and 1.77 (4H) ppm for the methylene pro-
tons. For structural characterization, an X-ray diffraction
study was carried out on a single crystal obtained from
n-hexane/toluene at ꢀ10 °C. An ORTEP diagram of 1 is
illustrated in Fig. 1. Compound 1 is a 48-electron cluster.
The molecule is based on a trimetallic array of osmium
atoms in which the individual bond lengths are Os1–Os2
Compound 1 is stable at 80 °C, while in refluxing tolu-
ene it decomposes within 3 h to generate several products.
After separation by TLC, two major compounds were
purified for characterization, namely Os3(CO)7(l-PPh2)-
(l3,g5-Ph2PC9H10) (3; 35%) and Os3(CO)8(l-PPh2)(l3,g6-
Ph2P(C9H10)CO) (4; 21%) (Eq. (2)). Compounds 3 and 4
form air-stable, yellow crystalline solids which have been
characterized by elemental analyses, mass, IR, and NMR.
˚
2.9081(3), Os2–Os3 2.9025(3), and Os1–Os3 2.8792(3) A.
O
(CO)
2 Os
+
(CO)
ð2Þ
1
Os
(CO)2
Os
Ph
3
Os
(CO)3
P
Ph
Ph
P
Ph
Ph
Os
(CO)3
P
P
Os
(CO)2
Ph
Ph
Ph
3
4
The FAB mass spectrum of 3 presents the molecular ion
peak at m/z 1254 corresponding to loss of three carbonyls
from 1 upon thermolysis. The 31P{1H} NMR spectrum
shows two singlets at ꢀ49.0 and ꢀ191.5 ppm, with the lat-
ter resonance assigned to a bridging phosphide ligand [21].
The 1H NMR spectrum is complicated, showing six sets of
multiplets in 3.38–1.92 ppm for the methylene protons. An
X-ray diffraction study was carried out, and the ORTEP
diagram is illustrated in Fig. 2. The dpndy ligand has
undergone a tremendous change that one C–PPh2 bond is
cleaved and the two alkyne units are coupled to form a
˚
Fig. 1. Molecular structure of 1. Selected bond lengths (A) and bond
angles (°): Os1–Os2 2.9081(3), Os1–Os3 2.8792(3), Os2–Os3 2.9025(3),
Os1–P1 2.336(1), Os2–P2 2.345(1), C11–P1 1.767(6), C11–C12 1.202(7),
C12–C13 1.462(7), C19–P2 1.761(6), C18–C19 1.195(8), C17–C18 1.468(8)
and Os1–Os2–Os3 59.406(4), Os1–Os3–Os2 60.395(7), Os2–Os1–Os3
60.199(7), Os1–P1–C11 113.7(2), P1–C11–C12 175.5(5), C11–C12–C13
176.3(5), Os2–P2–C19 109.7(2), P2–C19–C18 171.4(6), C19–C18–C17
176.3(6), Os1–Os2–C4 80.3(2), Os1–Os2–C6 95.5(2), Os3–Os2–C4 91.3(1),
Os3–Os2–C6 86.4(2).

T.-W. Shiue et al. / Journal of Organometallic Chemistry 692 (2007) 3619–3624
3621
Fig. 3. Molecular structure of 4. The C6H5 groups have been artificially
omitted, except the ipso carbon atoms, for clarity. Selected bond lengths
˚
(A) and bond angles (°): Os1–Os2 2.7748(3), Os1–P2 2.383(1), Os3–P2
2.491(1), Os3–P1 2.395(1), Os1–C10 2.212(5), Os1–C11 2.215(5), Os1–C12
2.307(5), Os1–C13 2.292(5), Os2–C10 2.090(5), Os2–C13 2.081(6), Os3–C9
2.167(5), C9–O9 1.200(6), C9–C11 1.541(7), C10–P1 1.794(5), C10–C11
1.445(7), C11–C12 1.434(7), C12–C13 1.423(8), C12–C18 1.520(8), C13–
C14 1.526(8) and Os3–P1–C10 103.4(2), Os1–P2–Os3 108.13(5), P1–Os3–
P2 90.68(5), Os2–C10–P1 133.4(3), Os2–C10–C11 116.1(3), C11–C10–P1
110.3(4), C11–C9–Os3 114.3(3), C11–C9–O9 120.0(5), C9–C11–C12
126.1(5), C10–C11–C12 114.7(5), C11–C12–C13 113.0(5), C11–C12–C18
124.7(5), C12–C13–C14 116.4(5), C12–C13–Os2 118.0(4), C14–C13–Os2
125.1(4).
Fig. 2. Molecular structure of 3. The C6H5 groups have been artificially
omitted, except the ipso carbon atoms, for clarity. Selected bond lengths
˚
(A) and bond angles (°): Os1–Os2 2.7978(6), Os1–Os3 2.8656(6), Os1–P1
2.334(3), Os2–P2 2.364(3), Os3–P2 2.444(3), Os1–C8 2.09(1), Os1–C16
2.05(1), Os3–C16 2.07(1), Os2–C8 2.19(1), Os2–C9 2.27(1), Os2–C15
2.295(9), Os2–C16 2.29(1), C8–P1 1.74(1), C8–C9 1.39(1), C9–C10 1.54(1),
C9–C15 1.47(1), C15–C14 1.51(1), C15–C16 1.38(1) and Os2–Os1–Os3
78.89(2), Os1–P1–C8 59.4(3), Os2–P2–Os3 96.9(1), P1–C8–C9 159.2(8),
P1–C8–Os1 74.5(4), C8–C9–C10 122.1(9), C8–C9–C15 109.7(9), C9–C15–
C14 125.0(9), C9–C15–C16 110.3(8), C14–C15–C16 124.6(9), C15–C16–
Os1 124.6(8), C15–C16–Os3 146.5(8), Os1–C16–Os3 88.2(4).
presents a broad peak at 1618 cmꢀ1 for a C–O stretching,
suggesting insertion (or migration) of a carbonyl group
into the dpndy link. The 31P{1H} NMR spectrum shows
two singlets at 55.1 and ꢀ87.3 ppm for the phosphine
and phosphide resonances, respectively. For structural
characterization of 4, an X-ray diffraction study was car-
ried out and the ORTEP diagram is illustrated in Fig. 3.
Compound 4 is a 52-electron cluster to exhibit only one
metallacycle. Compound 3 is a 50-electron cluster to con-
tain two Os–Os bonds (Os1–Os2 2.7978(6) and Os1–Os3
˚
2.8656(6) A) and one l-PPh2 group across the noninteract-
˚
ing metals (Os2ꢁ ꢁ ꢁOs3 3.599 A) with the lengths Os2–P2
˚
2.364(3) and Os3–P2 2.444(3) A, and the angle Os2–P2–
Os3 96.9(1)°. The dihedral angle between the plane (Os2,
P2, Os3) and the Os3 plane is 45.2(1)°. The Os1, C8, C9,
C15, and C16 atoms form a osmacyclopentadienyl ring,
˚
Os–Os bond (Os1–Os2 2.7748(3) A). The noninteracting
˚
metal–metal distances are Os1ꢁ ꢁ ꢁOs3 3.947 A and
˚
˚
where the carbon atoms are coplanar to within 0.01 A
Os2ꢁ ꢁ ꢁOs3 5.350 A. One C–PPh2 bond of the dpndy mol-
˚
and the Os1 atom is ca. 0.2 A away from the plane. The
ecule has been cleaved to generate a l-PPh2 group and the
two alkyne units are coupled to form a metallacycle,
together with migration of one carbonyl group to give
an acyl species. We note that the carbocycle (C14–C18)
is connected to the a,b-carbons of the metallacycle, while
it is in the b,b0-position for 3. The Os2, C10, C11, C12,
and C13 atoms form a osmacyclopentadienyl ring, and
the coordination about the Os1 atom can be viewed as a
three-legged piano stool by considering the metallacycle
as an g5-ligand. Thus, the Os–Os interaction is best
described as a dative bond by donating two nonbonding
electrons from Os1 to Os2 to satisfy the 18-electron rule
[22] for both osmium atoms. The coordination about the
Os3 atom is a distorted octahedron, which is linked to
three terminal carbonyls in a facial-fashion, an acyl group
C8–C9 unit can be described as a vinyl species which is
˚
r-bonded to the Os1 atom with C8–Os1 2.09(1) A and p-
bonded to the Os2 atom with C8–Os2 2.19(1) and C9–
˚
Os2 2.27(1) A. On the other hand, the C15–C16 unit is best
considered as a vinylidene ligand which bridges the Os1–
˚
Os3 edge with C16–Os1 2.05(1) and C16–Os3 2.07(1) A
and forms a p-bond to the Os2 atom with C16–Os2
˚
2.29(1) and C15–Os2 2.295(9) A. The phosphine group
occupies an equatorial site of the Os3 frame with Os1–P1
˚
2.334(3) A. The triangular arrangement of the C8, P1,
and Os1 atoms results in the angles P1–C8–C9 159.2(8)°
and C8–P1–Os1 59.4(3)° being substantially distorted from
the idealized values of 120° and 109.5°, respectively.
The molecular ion peak at m/z 1310 for 4 corresponds
to loss of one carbonyl ligand from 1. The IR spectrum
˚
with C9–Os3 2.167(5) A, a phosphine group with P1–Os3

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T.-W. Shiue et al. / Journal of Organometallic Chemistry 692 (2007) 3619–3624
were obtained on a Varian Unity INOVA-500 spectrome-
ter. Fast-atom-bombardment (FAB) mass spectra were
recorded on a JEOL JMS-SX102A mass spectrometer. Ele-
mental analyses were performed at the National Science
Council Regional Instrumentation Center at National
Chen-Kung University, Tainan, Taiwan.
H2
O
C
Ph
Ph
2
2 Os
2
Os
P
1
1
Ph
Os
P
Os
Os
3
Os
2P
Ph
1
1 P
Ph
3
Ph
Ph
3.2. Reaction of dpndy with Os3(CO)10 (NCMe)2
Ph
CO
3 CO
Os3(CO)10(NCMe)2 (60 mg, 0.064 mmol) and dpndy
(35 mg, 0.071 mmol) were placed in an oven-dried 50 ml
Schlenk flask, equipped with a magnetic stir bar and a rub-
ber serum stopper. Dichloromethane (10 ml) was intro-
duced into the flask and the solution was stirred at room
temperature for 24 h. The solution was concentrated to
ca. 2 ml on a rotary evaporator and then subjected to
TLC, eluting with dichloromethane/n-hexane (1:1, v/v).
Isolation of the material forming the first yellow band
afforded Os3(CO)10(l,g2-(Ph2P)2C9H10) (1; 54 mg, 63%),
and the second yellow band afforded [Os3(CO)10]2(l,g2-
(Ph2P)2C9H10)2 (2; 8 mg, 4%).
O
1 Os
P2
Ph
Os
2 Os
Os
3
3
Ph
Ph
Ph
Os
P
2
P
2
1
Os
1
P
Ph
1
Ph
Ph
Ph
4
3
Scheme 1.
3.2.1. Compound 1
˚
˚
2.395(1) A, and
a phosphido species with P2–Os3
Anal. Calc. for C43H30O10P2Os3: C, 38.57; H, 2.24.
Found: C, 38.62; H, 2.33%. IR (CH2Cl2, mCO): 2084w,
2016m, 1992s, 1960m cmꢀ1. MS (FAB): m/z 1338 (M+,
192Os). 1H NMR (CD2Cl2, 23 °C): 7.80–7.14 (m, 20H,
Ph), 2.71 (m, 4H), 1.86 (m, 2H), 1.77 (m, 4H, CH2) ppm.
31P{1H} NMR (CD2Cl2, 23 °C): ꢀ33.6 (s), ꢀ35.8 (s) ppm.
2.491(1) A. The bond angles C10–P1–Os3 103.4(2)° and
Os1–P1–Os3 108.13(5)° are normal, due to a unstrained
five-membered ring formed by the Os3, P1, C10, Os1,
and P2 atoms.
Compounds 3 and 4 are not interconvertible, so they are
likely derived from 1 via separate routes. scheme 1 illus-
trates the plausible bond reformation for the dpndy ligand,
where the gray and dash lines represent the chemical bonds
broken and generated, respectively. Since this reaction is
inhibited under a CO atmosphere, it is probable that ther-
mal decarbonylation of 1 induces C–P bond activation and
alkyne–alkyne coupling to generate 3, while the formation
of 4 is much complicated which also involves a C–C bond
rearrangement and a CO migration.
3.2.2. Compound 2
Anal. Calc. for C86H60O20P4Os6: C, 38.57; H, 2.24.
Found: C, 38.74; H, 2.19%. IR (CH2Cl2, mCO): 2020m,
1990s, 1966m cmꢀ1. MS (FAB): m/z 2660 (M+ꢀO,
192Os). 1H NMR (CD2Cl2, 23 °C): 7.76 (m, 16H), 7.45
(m, 24H, Ph), 2.64 (m, 8H), 1.74 (m, 4H, CH2), 1.63 (m,
8H, CH2) ppm. 31P{1H} NMR (CD2Cl2, 23 °C): ꢀ35.8
(s) ppm.
In summary, we have prepared the mono- and dimeric
Os3 clusters containing the dpndy ligand. Activation of
dpndy by the cluster to form a metallacycle and a carbocy-
cle presented herein is unique because this feature is not
available in the chemistry of the related Ph2P–C„C–
PPh2 [18,23] and Ph2P–C„C–C„C–PPh2 [24] molecules.
3.3. Thermal reaction of 1
Compound 1 (60 mg, 0.045 mmol) and toluene (5 ml)
was placed in Schlenk tube and the solution was heated
to reflux for 3 h under dinitrogen. The solvent was removed
under vacuum and the residue was subjected to TLC with
dichloromethane/n-hexane (1:1, v/v) as eluant. Isolation of
the material forming the first yellow band afforded
Os3(CO)7(l-PPh2)(l3,g5-Ph2PC9H10) (3; 20 mg, 35%), and
the second yellow band afforded Os3(CO)8(l-PPh2)(l3,g6-
Ph2P(C9H10)CO) (4; 13 mg, 21%).
3. Experimental
3.1. General methods
All manipulations were carried out under an atmosphere
of dinitrogen with standard Schlenk techniques.
Os3(CO)10(NCMe)2 [25] and bis(diphenylphosphino)-1,9-
nonadiyne (dpndy) [16] were prepared by literature
method. Solvents were dried over appropriate reagents
under dinitrogen and distilled immediately before use. Pre-
parative thin-layer chromatographic (TLC) plates were
prepared from silica gel (Merck). 1H and 31P NMR spectra
3.3.1. Compound 3
Anal. Calc. for C40H30O7P2Os3: C, 38.28; H, 2.39.
Found: C, 39.64; H, 2.15%. IR (CH2Cl2, mCO): 2060m,
1992s, 1982vs, 1940m, 1926m cmꢀ1. MS (FAB): m/z 1254
(M+, 192Os). 1H NMR (CD2Cl2, 23 °C): 7.84 (m, 2H),
7.30 (m, 18H, Ph), 3.38 (m, 1H), 3.23 (m, 1H), 2.90 (m,

T.-W. Shiue et al. / Journal of Organometallic Chemistry 692 (2007) 3619–3624
3623
1H), 2.77 (m, 1H), 2.28 (m, 1H), 1.92 (m, 5H, CH2) ppm.
Acknowledgement
31P{1H} NMR (CD2Cl2, 23 °C): ꢀ49.0 (s), ꢀ191.5 (s, l-
PPh2) ppm.
We are grateful for support of this work by the National
Science Council of Taiwan.
3.3.2. Compound 4
Anal. Calc. for C42H30O9P2Os3: C, 38.47; H, 2.29.
Found: C, 39.22; H, 2.13%. IR (CH2Cl2, mCO): 2092m,
Appendix A. Supplementary material
2056s, 2012s, 1988vs, 1976vs, 1958s, 1942s, 1618br cmꢀ1
.
CCDC 640119, 640120, and 64121 contain the supple-
mentary crystallographic data for 1, 3, and 4. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2007.05.003.
MS (FAB): m/z 1310 (M+, 192Os). 1H NMR (CD2Cl2,
23 °C):7.95 (m, 2H), 7.48 (m, 13H), 7.08 (m, 5H, Ph),
3.85 (dd, 1H), 3.23 (dd, 1H), 2.88 (t, 1H), 2.56 (t, 1H),
2.17 (m, 1H), 2.11 (m, 1H), 2.01 (m, 1H), 1.69–1.50 (m,
3H, CH2) ppm. 31P{1H} NMR (CD2Cl2, 23 °C): 55.1 (s),
ꢀ87.3 (s, l-PPh2) ppm.
3.4. Structure determination for 1, 3, and 4
The crystals of 1, 3, and 4 found suitable for X-ray
analysis were each mounted in a thin-walled glass capil-
lary and aligned on the Nonius KappaCCD (for 1) and
Bruker Smart ApexCCD (for 3 and 4) diffractometers,
with graphite-monochromated Mo Ka radiation (k =
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´
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25 (2006) 2960.
0.71073 A). The h range for data collection is 1.23–
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27.50° for 1, 1.43–25.00° for 3, and 1.22–27.50° for 4.
Of the 38136, 29867, and 27524 reflections collected
for 1, 3, and 4, 10830, 7057, and 9535 reflections were
independent, 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-square cycles. The non-
hydrogen atoms were refined anisotropically. Hydrogen
atoms were included but not refined. All calculations
were performed using the SHELXTL-97 package [26]. The
data collection and refinement parameters are presented
in Table 1.
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Table 1
Crystallographic data for 1, 3, and 4
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1
3
4
Formula
C
50H38O10
C43.5H33
O7Os3P2
Monoclinic
1300.24
C43H34O10
Os3P2
Triclinic
1343.24
Os3P2
Crystal system Triclinic
Formula
weight
1431.34
T (K)
150(1)
150(1)
P21/c
9.9588(2)
20.2106(5)
20.0447(5)
90
93.766(1)
90
4025.8(2)
4
295(2)
P1
ꢀ
ꢀ
Space group
P1
˚
a (A)
11.1243(1)
12.8273(1)
17.3882(2)
73.0486(6)
82.8708(7)
89.0696(8)
2354.53(4)
2
2.019
8.201
0.0299/0.0564
1.029
11.0436(5)
12.1385(6)
17.5392(8)
73.471(1)
88.316(1)
68.049(1)
2082.8(2)
2
2.142
9.263
0.0327/0.0719
1.028
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
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Raithby, W.-T. Wong, J. Organomet. Chem. 440 (1992) 219.
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Organometallics 7 (1988) 106;
3
˚
V (A )
Z
Dcalc (Mg/m3)
2.145
9.575
0.0422/0.0973
1.102
l (mmꢀ1
R1/wR2
)
(b) W.-Y. Yeh, Y.-J. Cheng, M.Y. Chiang, Organometallics 16
(1997) 918.
GOF on F2

3624
T.-W. Shiue et al. / Journal of Organometallic Chemistry 692 (2007) 3619–3624
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Metals, third ed., Wiley, New York, 2001;
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A.J. Carty, J. Am. Chem. Soc. 127 (2005) 5038.
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17 (1998) 2477.
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Dalton Trans. (1985) 1229.
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Nairn, J. Lewis, M. Martinelli, J. Chem. Soc., Dalton Trans. (1993) 1891.
[26] G.M. Sheldrick, SHELXTL-97, Program for crystal structure refine-
ment, University of Go¨ttingen, Germany, 1997.