Synthesis of Ph2PC≡C(CH2) 5C≡CPPh2 ligand and its complexation with tungsten carbonyls to form a dinuclear paddle-wheel and a tetranuclear tripodal compound

Article abstract of DOI:10.1021/om0603722

The multifunctional ligand bis(diphenylphosphino)-1,9-nonadiyne (1; abbreviated as dpndy) has been prepared by sequential treatment of HC≡C(CH₂)₅C≡CH with BuLi and PPh ₂Cl. Compound 1 reacts with W(CO)₄(NCMe)₂ to give W(CO)₄(η²-dpndy) (2), while the reaction of 1 and W(CO)₃(Me₃tach) (Me₃tach = 1,3,5-trimethyl-1,3,5-triazacyclohexane) produces W(CO)₃(η ²-dpndy)(η¹-dpndy) (3), [W(CO)₃-(η ²-dpndy)]₂(μ,η²-dpndy) (4), and the paddle-wheel complex [W(CO)₃]₂(μ,η ²-dpndy)₃ (5). Further treatment of W(CO) ₃(Me₃tach) with 3 generates the tripodal compound W(CO)₃[(μ,η²-dpndy)W(CO)₃(η ²-dpndy)]₃ (6). The molecular structures of 2 and 5 have been determined by an X-ray diffraction study.

Full text of DOI:10.1021/om0603722

4150
Organometallics 2006, 25, 4150-4154
Synthesis of Ph2PCtC(CH2)5CtCPPh2 Ligand and Its
Complexation with Tungsten Carbonyls to Form a Dinuclear
Paddle-Wheel and a Tetranuclear Tripodal Compound
Tsun-Wei Shiue and Wen-Yann Yeh*
Center for Nanoscience and Nanotechnology, Department of Chemistry, National Sun Yat-Sen UniVersity,
Kaohsiung, Taiwan 804
Gene-Hsiang Lee and Shie-Ming Peng
Department of Chemistry, National Taiwan UniVersity, Taipei, Taiwan 106
ReceiVed May 1, 2006
The multifunctional ligand bis(diphenylphosphino)-1,9-nonadiyne (1; abbreviated as dpndy) has been
prepared by sequential treatment of HCtC(CH2)5CtCH with BuLi and PPh2Cl. Compound 1 reacts
with W(CO)4(NCMe)2 to give W(CO)4(η2-dpndy) (2), while the reaction of 1 and W(CO)3(Me3tach)
(Me3tach ) 1,3,5-trimethyl-1,3,5-triazacyclohexane) produces W(CO)3(η2-dpndy)(η1-dpndy) (3), [W(CO)3-
(η2-dpndy)]2(µ,η2-dpndy) (4), and the paddle-wheel complex [W(CO)3]2(µ,η2-dpndy)3 (5). Further treatment
of W(CO)3(Me3tach) with 3 generates the tripodal compound W(CO)3[(µ,η2-dpndy)W(CO)3(η2-dpndy)]3
(6). The molecular structures of 2 and 5 have been determined by an X-ray diffraction study.
chemistry of multifunctional ligands,12 herein we present the
synthesis of a new diphosphine molecule, Ph2PCtC(CH2)5Ct
CPPh2, and its coordination to tungsten carbonyls.
Introduction
Recent work on assembly of metal complexes (or ions) with
suitable bridging ligands allows the preparation of well-defined
inorganic supramolecular architectures in solution.1-6 The
tertiary diphosphine ligands, R2P-(L)-PR2, have been interest-
ing to chemists due to their various modes of coordination with
metal atoms7 and possible catalytic activities of many of their
complexes.8 They also stabilize a variety of ligands of interest
to organometallic chemistry as their diphosphine complexes.9
Most importantly, the electronic and steric properties of diphos-
phines can be altered in a systemic and predictable way over a
wide range by varying the electron-donating ability and steric
size of R and the configuration of L, which can be rigid in the
Ph2P(CtC)nPPh2, Ph2P(C6H4)nPPh2, and Ph2P(C10H6)2PPh2
(BINAP) ligands or flexible in the Ph2P(CH2)nPPh2 and (C5H4-
PPh2)2Fe ligands.10 In addition, the two phosphine groups can
be incorporated into a medium-sized ring,11 which offers unique
opportunities to study the interactions between phosphorus
atoms. As part of our interest in the design and coordination
Results and Discussion
Sequential treatment of 1,9-nonadiyne with 2 equiv of
n-butyllithium and chlorodiphenylphosphine affords a slightly
air-sensitive, colorless crystalline solid of bis(diphenylphos-
phino)-1,9-nonadiyne (1) in 48% yield (eq 1) after purification
by column chromatography and crystallization from dichlo-
romethane/n-hexane. The FAB mass spectrum of 1 presents the
molecular ion peak at m/z 488. This compound is symmetric in
that the 1H NMR spectrum shows three multiplet signals in the
range δ 7.71-7.04 (20H) for the phenyl protons and two broad
signals at δ 2.04 (4H) and 1.23 (6H) for the methylene protons,
and only one 31P resonance signal is recorded at δ -31.96.
(1) Lehn, J.-M. Supramolecular Chemistry: Concepts and PerspectiVes;
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istry; Wiley-VCH: Weinheim, Germany, 1999.
(4) Brammer, L. Chem. Soc. ReV. 2004, 33, 476.
The linear acetylene backbone in the parent Ph2PCtCPPh2
molecule (dppa) constrains the two phosphine moieties to bridge
between metal centers.13 Compound 1 consists of two rigid
(5) Gianneschi, N. C.; Masar, M. S., III; Mirkin, C. A. Acc. Chem. Res.
2005, 38, 825.
(6) Steel, P. J. Acc. Chem. Res. 2005, 38, 243.
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Wiley: New York, 1992. (b) Noyori, R. Asymmetric Catalysis in Organic
Synthesis; Wiley: New York, 1994.
(9) Crabtree, R. H. The Orgnometallic Chemistry of the Transition Metals,
3rd ed.; Wiley: New York, 2001.
(10) Downing, J. H.; Smith, M. B. In ComprehensiVe Coordination
Chemistry II; Elsevier: Oxford, U.K., 2004; Vol. 1, p 253.
(11) Alder, R. W.; Read, D. Coord. Chem. ReV. 1998, 176, 113.
(12) Yeh, W.-Y.; Hsiao, S.-C.; Peng, S.-M.; Lee, G.-H. Organometallics
2005, 24, 3365. (b) Hsu, S. C. N.; Yeh, W.-Y. J. Chem. Soc., Dalton Trans.
1998, 125. (c) Yeh, W.-Y.; Cheng, Y.-J.; Chiang, M. Y. Organometallics
1997, 16, 918.
(13) Johnson, B. F. G.; Lewis, J.; Massey, A. D.; Raithby, P. R.; Wong,
W. T. J. Organomet. Chem. 1990, 397, C28. (b) Louattani, E.; Suades, J.
J. Organomet. Chem. 2000, 604, 234. (c) Falvello, L. R.; Fornie´s, J.; Go´mez,
J.; Lalinde, E.; Mart´ın, A.; Mart´ınez, F.; Moreno, M. T. J. Chem. Soc.,
Dalton Trans. 2001, 2132.
10.1021/om0603722 CCC: $33.50 © 2006 American Chemical Society
Publication on Web 07/12/2006

Synthesis of Ph2PCtC(CH2)5CtCPPh2 Ligand
Organometallics, Vol. 25, No. 17, 2006 4151
Scheme 1
Figure 1. 1H NMR spectrum of 2 in the methylene resonance
region.
CtCPPh2 groups linked by a flexible pentylene chain and might
serve as both a bridging and a chelating agent.14 Thus, the
reaction of Mo(CO)4(NCMe)2 and Ph2PCtCPPh2 was shown
to produce [Mo(CO)4]2(µ,η2-dppa)2 predominantly,15 while
W(CO)4(NCMe)2 reacts with 1 to generate the chelated complex
W(CO)4(η2-dpndy) (2) as the major product (Scheme 1).
Compound 2 forms air-stable, yellow crystals. The 31P{1H}
NMR spectrum presents one sharp singlet at δ -5.46 with
appropriate 183W satellites. Coordination of the dpndy ligand
makes the methylene proton resonances resolved, shown in
Figure 1, which can be assigned on the basis of coupling
patterns. The spectral data are in agreement with a Cs symmetry
for 2 in solution. The molecular structure of 2, depicted in Figure
2, shows that the dpndy ligand chelates the W(CO)4 moiety in
a cis position. The C5-P1-W angle of 112.70(9)° and the
C13-P2-W angle of 111.82(9)° are only slightly deviated from
the ideal value of 109.5°, indicating little strain within the
metallacycle, while the obtuse P1-W-P2 bite angel of 98.56-
(2)° is likely arising from steric repulsions between the bulky
PPh2 groups. The W-CO distances to the C3 (1.982(3) Å) and
C4 (2.000(3) Å) atoms are slightly but significantly shorter than
those to the C1 (2.034(3) Å) and C2 (2.026(3) Å) atoms,
consistent with the stronger net donor capacity of the PPh2R
ligand compared with CO.16 The four acetylene carbon atoms
(C5, C6, C12, and C13) are coplanar to within 0.03 Å, which
makes a dihedral angle of 72° with the P1-W-P2 plane. The
P-CtC-C links are slightly bowed from linearity, as indicated
by the CtC-P angles (174.5(3)° to P1 and 169.4(3)° to P2)
and the CtC-C angles (176.0(3)° to C7 and 177.3(3)° to C11).
Since no dinuclear products were isolated from the reaction
of 1 and W(CO)4(NCMe)2, the trisubtituted complex W(CO)3-
(Me3tach) (Me3tach ) 1,3,5-trimethyl-1,3,5-triazacyclohexane)
was prepared to react with 1 in a 2:3 ratio at room temperature,
producing W(CO)3(η2-dpndy)(η1-dpndy) (3; 22%), [W(CO)3-
Figure 2. Molecular structure of 2. Selected bond distances (Å):
W-P1 ) 2.5255(7), W-P2 ) 2.5150(6), W-C1 ) 2.034(3),
W-C2 ) 2.026(3), W-C3 ) 1.982(3), W-C4 ) 2.000(3), C5-
C6 ) 1.193(4), C12-C13 ) 1.190(4). Selected bond angles
(deg): P1-W-P2 ) 98.56(2), P1-W-C3 ) 174.27(7), P2-W-
C4 ) 172.75(8), C1-W-C2 ) 177.7(1), C5-P1-W ) 112.70(9),
C6-C5-P1 ) 174.3(3), C5-C6-C7 ) 176.0(3), C13-P2-W )
111.82(9), C12-C13-P2 ) 169.4(3), C13-C12-C11 ) 177.3(3).
(η2-dpndy)]2(µ,η2-dpndy) (4; 31%), and [W(CO)3]2(µ,η2-dpndy)3
(5; 5%) after separation by TLC and crystallization. Compounds
3-5 form air-stable, yellow crystalline solids and have been
properly characterized by elemental analysis and mass, IR, and
NMR spectroscopies. The IR spectra of these compounds in
the carbonyl region display two strong absorptions around 1940
and 1840 cm-1, a pattern in agreement with a facial-
W(CO)3LLL′ configuration.17
The molecular ion peak at m/z 1244 for 3 is the combination
of W(CO)3 and two dpndy species. The 31P{1H} NMR spectrum
presents a 2P doublet at δ -0.96 (JP-P ) 24 Hz) with 183W
satellites (JP-W ) 234 Hz), a 1P triplet at δ -2.87 with 183W
satellites, and a 1P singlet at δ -32.8. Thus an octahedral facial-
W(CO)3PPP′ configuration can be constructed for 3, with the
tungsten atom being chelated by a dpndy ligand and coordinated
by one phosphorus atom of another dpndy ligand.
(14) Empsall, H. D.; Mentzer, E.; Pawson, D.; Shaw, B. L.; Mason, R.;
Williams, G. A. Chem. Commun. 1977, 311. (b) Mason, R.; Williams, G.
A. Inorg. Chim. Acta 1978, 29, 273.
(15) Hogarth, G.; Norman, T. Polyhedron 1996, 15, 2859.
(16) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles
and Applications of Organotransition Metal Chemistry; University Science
Books: Mill Valley, CA, 1987.
(17) Lukehart, C. M. Fundamental Transition Metal Organometallic
Chemistry; Brooks/Cole Publishing Company: Monterey, CA, 1985.

4152 Organometallics, Vol. 25, No. 17, 2006
Shiue et al.
Figure 3. Molecular structure of 5. The C6H5 groups have been artificially omitted, except the ipso carbon atoms, for clarity. Selected
bond distances (Å): W1-P1 ) 2.528(2), W1-P3 ) 2.532(2), W1-P5 ) 2.525(2), W1-C1 ) 1.978(7), W1-C2 ) 1.966(8), W1-C3 )
1.969(7), W2-P2 ) 2.507(2), W2-P4 ) 2.535(2), W2-P6 ) 2.529(2), W2-C4 ) 1.950(8), W2-C5 ) 1.989(8), W2-C6 ) 1.946(8).
Selected bond angles (deg): P1-W1-P3 ) 90.62(5), P1-W1-P5 ) 90.63(6), P3-W1-P5 ) 94.98(6), P2-W2-C4 ) 171.8(2),
P6-W2-C5 ) 172.4(2), P4-W2-C6 ) 177.6(2), P2-W2-P4 ) 92.86(6), P2-W2-P6 ) 94.01(6), P4-W2-P6 ) 89.11(6), C8-C7-
P1 ) 177.1(6), C7-C8-C9 ) 176.1(8), C14-C15-P2 ) 167.1(7), C13-C14-C15 ) 177.8(8), C41-C40-P3 ) 178.1(7), C40-C41-
C42 ) 178.4(8), C47-C48-P4 ) 173.2(6), C46-C47-C48 ) 177.7(8), C74-C73-P5 ) 168.3(7), C73-C74-C75 ) 174.5(9), C80-
C81-P6 ) 173.1(6), C79-C80-C81 ) 176.4(7).
4 gives no reaction, compound 5 is more likely formed by direct
assembling of W(CO)3(Me3tach) and the ligands in the solution.
Figure 4. Projection of 5 down the W2-W1 vector to show the
paddle-wheel arrangement of the ligands.
Compound 3 contains a pendent phosphine group and may
The molecular ion peak of 4 at m/z 2000 suggests a dinuclear
act as an organomatallic ligand for further structural construc-
[W(CO)3]2(dpndy)3 species. The 31P{1H} NMR spectrum con-
tion.18 Thus, reaction of W(CO)3(Me3tach) with 3 equiv of 3 in
tains two sets of resonance signals: a 4P doublet at δ -1.51
dichloromethane at ambient temperature affords a tetratungsten
with 183W satellites and a 2P triplet at δ -3.58 with 183W
tripodal macromolecule, W(CO)3[(µ,η2-dpndy)W(CO)3(η2-
satellites. Apparently, compound 4 consists of two identical
dpndy)]3 (6), in 54% yield after purification by TLC and
W(CO)3(η2-dpndy) moieties bridged by a dpndy ligand.
crystallization. Compound 6 forms a pale yellow, air-stable solid.
Compound 5 is isomeric to 4 to present the same molecular
There are two strong carbonyl stretching absorptions at 1940
ion peaks and elemental analysis. However, the 1H NMR
and 1844 cm-1, indicating a facial-W(CO)3 arrangement for all
spectrum of 5 is complicated, and only one 31P resonance is
tungsten atoms. The coordination modes of dpndy ligands in 6
recorded at δ 5.39 with 183W satellites. A single-crystal X-ray
can be assigned on the basis of the 31P{1H} NMR spectrum
diffraction study was conducted to reveal the structure of 5.
shown in Figure 5. The phosphorus resonance pattern resembles
The crystals contain solvent molecules (dichloromethane and
that recorded for 3, except that the singlet peak at δ -32.8 for
diethyl ether). There are two independent but structurally similar
3 is shifted downfield to δ -2.67 and accompanied with 183
W
complexes in the asymmetric unit, and one is depicted in Figure
3, which consists of two facially substituted W(CO)3 groups
bridged by three dpndy lignads to show a cryptand-like cage.
The coordination of each tungsten atom is a distorted octahedral
such that the C-W-C angles range from 83.2(3)° to 88.6(3)°
and the P-W-P angles are in the range 89.11(6)-94.98(6)°.
The W-P-C(acetylene) angles range from 114.4(2)° to 119.2-
(2)°, consistent with steric strain arising from syn-coordination
of three phosphine groups. The P-CtC-C backbones are
slightly bowed, as indicated by the P-CtC angles (167.1(7)-
178.1(7)°) and the CtC-C angles (174.5(9)-178.4(8)°).
Interestingly, the rigid CtC units constrain the dpndy ligands
in a paddle-wheel arrangement, shown in Figure 4. There is a
large void at the center, such that the W1‚‚‚W2 distances is
15.17 Å and the distances between the middle methylene carbon
atoms are 5.13 Å on average. It is plausible that compound 5 is
derived from 4 by opening of the chelated rings. Since heating
satellites for 6. We are not able to obtain suitable crystals of 6
for an X-ray diffraction study. The energy-minimized configu-
raton constructed for 6 suggests a disklike feature for the tripodal
framework (Chart 1), likely due to great steric bulk of the
terminal η2-dpndy groups. The complex is estimated to be 38
Å wide, where the distance between the central and the
peripheral tungsten atoms is ca. 14 Å.
In conclusion, the new diphosphine ligand, dpndy, has been
prepared and reacted with substituted tungsten carbonyls to
generate a variety of complexes, which are of interest within
the context of coordination and supramolecular chemistry.
Previously, alkyne-alkyne coupling to generate carbocycles was
demonstrated in the W2(CO)6(Ph2PCtCPPh2)319 and [PtCl2(Ph2-
(18) Appleby, T.; Woolins, J. D. Coord. Chem. ReV. 2002, 235, 121.
(19) Yeh, W.-Y.; Peng, S.-M.; Lee, G.-H. J. Organomet. Chem. 2003,
671, 145.

Synthesis of Ph2PCtC(CH2)5CtCPPh2 Ligand
Organometallics, Vol. 25, No. 17, 2006 4153
on a Varian Unity INOVA-500 spectrometer. Fast-atom-bombard-
ment (FAB) mass spectra were recorded on a JEOL JMS-SX102A
mass spectrometer. Elemental analyses were performed at the
National Science Council Regional Instrumentation Center at
National Chen-Kung University, Tainan, Taiwan.
Preparation of 1. 1,9-Nonadiyne (344 mg, 2.87 mmol) and THF
(50 mL) were placed in an oven-dried 100 mL Schlenk flask,
equipped with a magnetic stir bar and a rubber serum stopper. The
flask was placed in a cold bath at -20 °C, and BuLi (3.8 mL, 6.08
mmol) were introduced slowly via a syringe. The resulting mixture
was stirred at -20 °C for 20 min, warmed to room temperature to
stir for another 20 min, and then cooled to 0 °C in an ice bath.
PPh2Cl (1.35 g, 6.1 mmol) was added into the flask via a syringe
over a period of 15 min, and the solution was warmed to room
temperature and stirred for 6 h. The volatile materials were removed
under vacuum, and the crude products were purified by column
chromatography (silica gel, 3 × 25 cm). The column was first
flashed with 150 mL of dichloromethane/n-hexane (1:9, v/v) and
then eluted with 200 mL of dichloromethane/n-hexane (1:1, v/v).
The eluant was evaporated to dryness on a rotary evaporator, and
the residue was crystallized from dichloromethane/n-hexane to
afford colorless crystals of Ph2PCtC(CH2)5CtCPPh2 (1; 673 mg,
48%). Anal. Calcd for C33H30P2: C, 81.13; H, 6.19. Found: C,
Figure 5. 31P{1H} NMR spectrum of 6 in CD2Cl2 at 22 °C.
Chart 1
1
81.01; H, 5.96. MS (FAB): m/z 488 (M+). H NMR (C6D6, 23
°C): δ 7.71 (m, 8H), 7.11 (m, 8H), 7.04 (m, 4H, Ph), 2.04 (br, 4H,
CH2CtC), 1.23 (br, 6H, CH2). 31P{1H} NMR (C6D6, 23 °C): δ
-31.96.
Preparation of 2. Compound 1 (75 mg, 0.15 mmol) and
W(CO)4(NCMe)2 (53 mg, 0.14 mmol) were placed in an oven-
dried 50 mL Schlenk flask under a dinitrogen atmosphere. Dichlo-
romethane (10 mL) was added into the flask, and the solution was
stirred at room temperature for 48 h. The solution was concentrated
to ca. 2 mL under vacuum and then subjected to TLC with
dichloromethane/n-hexane (1:4, v/v) as eluant. Isolation of the
material forming the first yellow band gave yellow crystals of
W(CO)4(η2-dpndy) (2; 56 mg, 51%) after crystallization from
dichloromethane/n-hexane. Anal. Calcd for C37H30O4P2W: C,
56.65; H, 3.85. Found: C, 56.80; H, 3.95. IR (CH2Cl2, νCO): 2012
(m), 1922 (s), 1898 (s) cm-1. MS (FAB): m/z 784 (M+, 184W). 1H
NMR (CD2Cl2, 23 °C): δ 7.60 (m, 8H), 7.27 (m, 12H, Ph), 2.59
(t, 4H, JH-H ) 6 Hz, CH2CtC), 1.96 (p, 2H, JH-H ) 7 Hz), 1.69
(p, 4H, CH2). 31P{1H} NMR (CD2Cl2, 22 °C): δ -5.46 (s; with
183W satellites JP-W ) 239 Hz).
Reaction of 1 and W(CO)3(η3-(MeNCH2)3). W(CO)3(η3-
(MeNCH2)3) (43 mg, 0.11 mmol) and compound 1 (80 mg, 0.16
mmol) were placed in an oven-dried 50 mL Schlenk flask under a
dinitrogen atmosphere. Dichloromethane (16 mL) was added into
the flask, and the solution was stirred at room temperature for 48
h. The solution was concentrated to ca. 2 mL under vacuum and
then subjected to TLC with dichloromethane/n-hexane (1:1, v/v)
as eluant. Three major pale yellow bands were developed. Isolation
of the material forming the first band afforded W(CO)3(η2-dpndy)-
(η1-dpndy) (3; 30 mg, 22%), the second band afforded [W(CO)3-
(η2-dpndy)]2(µ,η2-dpndy) (4; 34 mg, 31%), and the third band
afforded [W(CO)3]2(µ,η2-dpndy)3 (5; 6 mg, 5%).
PCtC-CtCPPh2)]n (n ) 2, 3)20 systems. There are several
free alkyne moieties in 2-6, and their similar reactivity is
currently under investigation.
Experimental Section
General Methods. All manipulations were carried out under an
Characterization of 3. Anal. Calcd for C69H60O3P4W: C, 66.57;
H, 4.86. Found: C, 66.14; H, 4.87. IR (CH2Cl2, νCO): 1940 (s),
1842 (s) cm-1. MS (FAB): m/z 1244 (M+, 184W). 1H NMR (CD2-
Cl2, 23 °C): δ 7.73 (m, 4H), 7.61 (m, 12H), 7.30 (m, 24H, Ph),
2.46 (t, 2H, JH-H ) 7 Hz), 2.15 (m, 4H), 1.94 (t, 2H, JH-H ) 8 Hz,
CH2CtC), 1.59 (m, 2H), 1.50 (m, 4H), 1.42 (m, 4H), 1.27 (m,
2H, CH2). 31P{1H} NMR (CD2Cl2, 22 °C): δ -0.96 (d, 2P,
JP-P ) 24 Hz; with 183W satellites JP-W ) 234 Hz), -2.87 (t, 1P,
JP-P ) 24 Hz; with 183W satellites JP-W ) 232 Hz), -32.8 (s, 1P).
atmosphere of dinitrogen with standard Schlenk techniques. W(CO)4-
21
(NCMe)2 and W(CO)3(Me3tach)22 were prepared by literature
methods. 1,9-Nonadiyne, PPh2Cl, and BuLi (1.6 M in hexane) were
purchased from Aldrich. Solvents were dried over appropriate
reagents under dinitrogen and distilled immediately before use.
Preparative thin-layer chromatographic (TLC) plates were prepared
1
from silica gel (Merck). H and 31P NMR spectra were obtained
(20) Martin-Redondo, M. P.; Scoles, L.; Sterenberg, B. T.; Udachin, K.
A.; Carty, A. J. J. Am. Chem. Soc. 2005, 127, 5038.
(21) Tate, D. P.; Knipple, W. R.; Augl, J. M. Inorg. Chem. 1962, 1,
433.
Characterization of 4. Anal. Calcd for C105H90O6P6W2: C,
63.01; H, 4.53. Found: C, 62.96; H, 4.94. IR (CH2Cl2, νCO): 1940
1
(22) Baker, M. V.; North, M. R. J. Organomet. Chem. 1998, 565, 225.
(s), 1844 (s) cm-1. MS (FAB): m/z 2000 (M+, 184W). H NMR

4154 Organometallics, Vol. 25, No. 17, 2006
Shiue et al.
Table 1. Crystallographic Data for 2 and 5
(CD2Cl2, 23 °C): δ 7.73 (m, 8H), 7.60 (m, 16H), 7.28 (m, 36H,
Ph), 2.16 (m, 8H), 1.98 (t, 4H, JH-H ) 7 Hz, CH2CtC), 1.52 (m,
6H), 1.39 (m, 4H), 1.25 (m, 8H, CH2). 31P{1H} NMR (CD2Cl2, 22
°C): δ -1.51 (d, JP-P ) 24 Hz; with 183W satellites JP-W ) 235
Hz), -3.58 (t, JP-P ) 24 Hz; with 183W satellites JP-W ) 232 Hz).
Characterization of 5. Anal. Calcd for C105H90O6P6W2: C,
63.01; H, 4.53. Found: C, 63.28; H, 4.51. IR (CH2Cl2, νCO): 1940
2
5
chem formula
cryst syst
fw
C37H30O4P2W
monoclinic
784.40
C109.5H101ClO7P6W2
monoclinic
2117.87
T, K
150(1)
150(1)
space group
a, Å
P21/n
P21/c
(s), 1844 (s) cm-1. MS (FAB): m/z 2000 (M+, 184W). H NMR
1
10.3289(6)
13.7759(8)
22.94106(13)
102.810(1)
3183.0(3)
4
1.637
3.769
0.0224/0.0500
1.117
21.1762(6)
22.3612(6)
41.0111(10)
90.3001(8)
19419.5(9)
8
1.449
2.550
0.0478/0.1125
1.020
b, Å
c, Å
(CD2Cl2, 23 °C): δ 8.16 (m, 24H), 7.02 (m, 36H, Ph), 2.10 (m,
6H), 1.94 (m, 6H, CH2CtC), 1.73 (m, 3H), 1.23 (m, 3H), 1.98
(m, 12H, CH2). 31P{1H} NMR (CD2Cl2, 22 °C): δ 5.39 (s; with
183W satellites JP-W ) 237 Hz). The crystals found suitable for an
X-ray diffraction study were grown from toluene/n-hexane at
-15 °C.
â, deg
V, Å3
Z
D
calc, g cm-3
µ, mm-1
R1/wR2
Reaction of 3 and W(CO)3(η3-(MeNCH2)3). W(CO)3(η3-
(MeNCH2)3) (5 mg, 0.0126 mmol), compound 3 (49 mg, 0.04
mmol), and dichloromethane (6 mL) were placed in an oven-dried
50 mL Schlenk flask under a dinitrogen atmosphere. The solution
was stirred at room temperature for 48 h. The solvent was removed
under vacuum, and the residue was applied on TLC, eluting with
dichloromethane/n-hexane (2:1, v/v). Isolation of the material
forming the fifth major band gave a pale yellow solid of W(CO)3-
[(µ,η2-dpndy)W(CO)3(η2-dpndy)]3 (6; 27 mg, 54%). Anal. Calcd
for C210H180O12P12W4: C, 63.01; H, 4.53. Found: C, 62.86; H, 4.36.
GOF on F2
the 41 104 and 133 620 reflections collected for 2 and 5, 7315 and
34 028 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-squares cycles. The non-hydrogen atoms were
refined anisotropically. Hydrogen atoms were included with a riding
model. All calculations were performed using the SHELXTL-97
package.23 The data collection and refinement parameters are
presented in Table 1.
1
IR (CH2Cl2, νCO): 1940 (s), 1844 (s) cm-1. H NMR (CD2Cl2,
23 °C): δ 7.69 (m, 12H), 7.60 (m, 36H), 7.23 (m, 72H, Ph), 2.10
(m, 18H), 1.96 (t, 6H, JH-H ) 7 Hz, CH2CtC), 1.47 (m, 12H),
1.28 (m, 24H, CH2). 31P{1H} NMR (CD2Cl2, 22 °C): δ -1.39 (d,
JP-P ) 24 Hz; with 183W satellites JP-W ) 235 Hz), -2.67 (s; with
Acknowledgment. We are grateful for support of this work
by the National Science Council of Taiwan.
183W satellites JP-W ) 233 Hz), -3.56 (t, JP-P ) 24 Hz; with 183
satellites JP-W ) 232 Hz).
W
Supporting Information Available: Crystal data of 2 and 5
in CIF format. This material is available free of charge via the
Internet at http://pubs.acs.org.
Structure Determination for 2 and 5. The crystals of 2 and 5
found suitable for X-ray analysis were each mounted in a thin-
walled glass capillary and aligned on Bruker Smart ApexCCD (for
2) and Nonius KappaCCD (for 5) diffractometers, with graphite-
monochromated Mo KR radiation (λ ) 0.71073 Å). The θ range
for data collection is 1.74-27.50° for 2 and 1.04-25.00° for 5. Of
OM0603722
(23) Sheldrick, G. M. SHELXTL-97, Program for crystal structure
refinement; University of Go¨ttingen: Germany, 1997.