WCl(η2-C2Ph2)(η6- C6Ph6H): A compound containing a metallacycloheptatriene unitfrom trimerization of diphenylacetylene with W(NMe3)(η2-C2Ph2)3

Article abstract of DOI:10.1021/om0201009

W(NCMe)(²-C₂Ph₂)₃ (1) has been previously synthesized by the reaction of W(CO)(η²-C₂Ph₂)₃ with Me₃NO in acetonitrile, while the same treatment in THF leads to the trimethylamine complex W(NMe₃)(η²-C₂Ph₂)₃ (2). Compound 2 is reactive. Stirring a mixture of 2 and diphenylacetylene in dichloromethane at room temperature affords WCl(η²-C₂Ph₂)(η⁶C₆ Ph₆H) (3), which apparently arises from trimerization of the alkyne ligands concomitant with solvent activation. The structures of 1-3 have been determined by an X-ray diffraction study. A carbene W=C double bond is evidenced in 3.

Full text of DOI:10.1021/om0201009

3058
Organometallics 2002, 21, 3058-3061
WCl(η2-C2P h 2)(η6-C6P h 6H): A Com p ou n d Con ta in in g a
Meta lla cycloh ep ta tr ien e Un it fr om Tr im er iza tion of
Dip h en yla cetylen e w ith W(NMe3)(η2-C2P h 2)3
Wen-Yann Yeh*
Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan 804
Shie-Ming Peng and Gene-Hsiang Lee
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106
Received February 11, 2002
Summary: W(NCMe)(η2-C2Ph2)3 (1) has been previously
synthesized by the reaction of W(CO)(η2-C2Ph2)3 with
Me3NO in acetonitrile, while the same treatment in THF
leads to the trimethylamine complex W(NMe3)(η2-C2Ph2)3
(2). Compound 2 is reactive. Stirring a mixture of 2 and
diphenylacetylene in dichloromethane at room temper-
ature affords WCl(η2-C2Ph2)(η6-C6Ph6H) (3), which ap-
parently arises from trimerization of the alkyne ligands
concomitant with solvent activation. The structures of
1-3 have been determined by an X-ray diffraction study.
A carbene WdC double bond is evidenced in 3.
to undergo multiple alkyne-alkyne coupling reactions
under mild conditions to yield the metallacyclonona-
pentaene complex W(η2-C2Ph2)(η8-C8Ph8) (4)9 and the
tungstenocene compound W(η5-C5Ph5)2 (5).10 In this
paper we wish to report the synthesis and reactivity of
W(NMe3)(η2-C2Ph2)3 (2), which contains a more labile
trimethylamine ligand.
Resu lts a n d Discu ssion
Previously, the reaction of W(CO)(η2-C2Ph2)3 with
Me3NO in an acetonitrile solvent was shown to produce
1,8 whereas the same treatment in THF affords the
trimethylamine complex 2 in 41% yield. In dichloro-
methane, the product mixture is complex and only a low
yield of 2 is obtained. Me3NO is a nucleophile and
attacks the electropositive carbon atom of the carbonyl
to produce Me3N and CO2.11 The Me3N weakly coordi-
nates to the vacant coordination site and is readily
displaced by a stronger electron-donating ligand, such
as nitrile, isonitrile, and phosphine. Although amines
are classical ligands in coordination chemistry, there are
not often used with organotransition metal complexes.12
An analogous primary amine complex W(NH2Et)(η2-C2-
Ph2)3 was obtained from reduction of the NCMe ligand
on 1,13 while treating 1 with NH2Et or NMe3 does not
lead to the corresponding amine complex.
In tr od u ction
One of the most fascinating aspects pertaining to
organometallic chemists concerns the cyclooligomeriza-
tion of alkynes.1 Mechanistic steps involving the forma-
tion of metallacycles, and their interconversions and
subsequent decay, are implicated in a number of im-
portant catalytic transformations. For example, metal-
promoted cyclization of alkynes to give cyclobutadienes,
arenes, and cyclooctatetraenes has frequently been
shown to proceed via metallacyclic intermediates.2
Polyalkyne complexes of the formula M(L)(η2-RCt
CR′)3, first prepared by Tate and co-workers,3 have
attracted much attention owing to their unique modes
of bonding4 and the potential to promote alkyne coupling
and polymerization.5 The parent compound W(CO)(C2-
Ph2)3 is robust6 and only reacts with molten diphenyl-
acetylene to produce complexes containing cyclobuta-
diene and cyclopentadienyl ligands.7 However, by re-
placing CO with NCMe, W(NCMe)(C2Ph2)3 (1)8 is able
Compound 2 forms an air-stable, white solid but
decomposes slowly in solution. It displays a higher
lability than 1, such that, reaction of 1 and diphenyl-
acetylene requires a gentle heating,9 while the same
(7) (a) Yeh, W.-Y.; Liu, L.-K. J . Am. Chem. Soc. 1992, 114, 2267. (b)
Yeh, W.-Y.; Peng, S.-M.; Lee, G.-H. J . Chem. Soc., Chem. Commun.
1993, 1056.
(8) Yeh, W.-Y.; Ting, C.-S.; Chih, C.-F. J . Organomet. Chem. 1991,
427, 257.
(9) Yeh, W.-Y.; Ho, C.-L.; Chiang, M. Y.; Chen, I.-T. Organometallics
1997, 16, 2698.
(10) (a) Yeh, W.-Y.; Peng, S.-M.; Lee, G.-H. J . Organomet. Chem.
1999, 572, 125. (b) Li, C.-I.; Yeh, W.-Y.; Peng, S.-M.; Lee, G.-H. J .
Organomet. Chem. 2001, 620, 106.
(1) (a) Grotjahn, D. B. In Comprehensive Organometallic Chemistry
II; Pergamon: Oxford, U.K., 1995; Vol. 12, p 741. (b) Schore, N. E.
Chem. Rev. 1988, 88, 1081. (c) Vollhardt, K. P. C. Acc. Chem. Res. 1977,
10, 1. (d) Masuda, T.; Higashimura, T. Acc. Chem. Res. 1984, 17, 51.
(2) (a) Crabtree, R. H. The Organometallic Chemistry of the Transi-
tion Metals; Wiley: New York, 1994. (b) Parshall, G. W.; Ittel, S. D.
Homogeneous Catalysis; Wiley: New York, 1992.
(3) Tate, D. P.; Augl, J . M. J . Am. Chem. Soc. 1963, 85, 2174. (b)
Tate, D. P.; Augl, J . M.; Ritchey, W. M.; Rose, B. L.; Grasselli, J . G. J .
Am. Chem. Soc. 1964, 86, 3261.
(4) (a) King, R. B. Inorg. Chem. 1968, 7, 1044. (b) Lane, R. M.;
Moriarty, R. E.; Bau, R. J . Am. Chem. Soc. 1972, 94, 1402. (c) Maher,
J . M.; Fox, J . R.; Foxman, B. M.; Cooper, N. J . J . Am. Chem. Soc. 1984,
106, 2347. (d) Wink, D. J .; Cooper, N. J . Organometallics 1991, 10,
494. (e) Mealli, C.; Masi, D.; Galindo, A.; Pastor, A. J . Organomet.
Chem. 1998, 569, 21.
(5) (a) Cairns, G. A.; Carr, N.; Green, M.; Mahon, M. F. Chem.
Commun. 1996, 2431. (b) Ku, R.-Z.; Chen, D.-Y.; Lee, G.-H.; Peng, S.-
M.; Liu, S.-T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2631.
(6) Wink, D. J .; Greagan, T. Organometallics 1990, 9, 328.
(11) Dyson, P. J .; Mclndoe, J . S. Transition Metal Carbonyl Cluster
Chemistry; Gordon and Breach Science Publishers: Amsterdam, The
Netherlands, 2000.
(12) (a) 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. (b) Shro, Y.; Abed,
M.; Blum, Y.; Lane, R. M. Isr. J . Chem. 1986, 27, 267. (c) Crobe, I.;
Kunik, P. H. Z. Anorg. Allg. Chem. 1993, 619, 47. (d) Gao, Y.-C.; Shi,
Q.-Z.; Kershner, D. L.; Basolo, F. Inorg. Chem. 1988, 27, 188.
(13) Yeh, W.-Y.; Ting, C.-S.; Peng, S.-M.; Lee, G.-H. Organometallics
1995, 14, 1417.
10.1021/om0201009 CCC: $22.00 © 2002 American Chemical Society
Publication on Web 06/01/2002

Notes
Organometallics, Vol. 21, No. 14, 2002 3059
Sch em e 1
F igu r e 1. Molecular structure of 1. Selected bond dis-
tances (Å): W-N(1) ) 2.174(3), C(43)-N(1) ) 1.124(4),
C(43)-C(44) ) 1.462(5), W-C(1) ) 2.065(3), W-C(2) )
2.074(3), W-C(3) ) 2.049(3), W-C(4) ) 2.065(4), W-C(5)
) 2.065(3), W-C(6) ) 2.071(4), C(1)-C(2) ) 1.326(5), C(3)-
C(4) ) 1.312(5), C(5)-C(6) ) 1.313(5). Selected bond angles
(deg): W-N(1)-C(43) ) 173.1(3), N(1)-C(43)-C(44) )
177.0(4), N(1)-W-C(1)
124.1(1), N(1)-W-C(3)
)
)
86.7(1), N(1)-W-C(2)
83.8(1), N(1)-W-C(4)
)
)
121.0(1), N(1)-W-C(5) ) 84.5(1), N(1)-W-C(6) ) 121.4-
(1), W-C(1)-C(2) ) 71.7(2), W-C(2)-C(1) ) 70.9(2),
W-C(3)-C(4) ) 72.1(2), W-C(4)-C(3) ) 70.8(2), W-C(5)-
C(6) ) 71.7(2), W-C(6)-C(5) ) 71.3(2), C(1)-W-C(3) )
119.9(1), C(1)-W-C(4)
124.6(1), C(1)-W-C(6)
118.5(1), C(2)-W-C(4)
122.1(1), C(2)-W-C(6)
113.3(1), C(3)-W-C(6)
)
)
116.5(1), C(1)-W-C(5)
119.0(1), C(2)-W-C(3)
93.2(1), C(2)-W-C(5)
95.0(1), C(3)-W-C(5)
116.3(1), C(4)-W-C(5)
)
)
)
)
)
)
)
)
reaction with 2 takes place at room temperature, and
the products are dependent on the solvents used. In
benzene solution compounds 4 and 5 are obtained
predominantly. On the contrary, the reaction in dichlo-
romethane (or 1,2-dichloroethane) leads to the metal-
lacycloheptatriene complex WCl(η2-C2Ph2)(η6-C6Ph6H)
(3), which apparently arises from trimerization of
diphenylacetylene concomitant with activation of the
solvent molecule (Scheme 1). A radical pathway is
probably involved, but we do not have mechanistic
information. This η6-C6R6H type of bonding is rare in
the literature,14 although the η4-C4R4H ligands are
relatively common.15 On the other hand, both 1 and 2
react with diphenylacetylene to produce 4 and 5 in
refluxing benzene or 1,2-dichloroethane solvent, sug-
gesting that 4 and 5 are the kinetic products at elevated
temperatures.
114.8(1), C(4)-W-C(6) ) 94.7(1).
diffraction. The molecular structures of 1 and 2, shown
in Figures 1 and 2, are closely resemblant. If taking the
centers of the alkynes, the coordination about each
tungsten atom can be described as a distorted tetrahe-
dron. The three acetylene groups are essentially eclipsed
but inclined with respect to the W-N(1) bond by an
average tilt angle of 13.5° for 1 and 16.2° for 2, which
are comparable with those measured for W(CO)(η2-C2-
Ph2)3 (av 13.4°),4b W(PMe3)(η2-C2Ph2)3 (av 13.2°),16
W(NHdCMe2)(η2-C2Ph2)3 (av 13.1°),13 and [W(SnPh3)(η2-
C2Ph2)3]- (av 15.3°).4c The coordinated NCMe (W-N(1)
) 2.174(3) Å) and NMe3 (W-N(1) ) 2.329(2) Å) ligands
give rise to slightly different W-C distances, such that
in 1 the upper W-C lengths are ca. 0.01 Å shorter than
the lower W-C lengths, while in 2 the order is reversed,
with the upper W-C lengths being slightly longer. The
acetylene CtC lengths are about equal for 1 (1.32 (
0.01 Å) and 2 (1.316 ( 0.006 Å), and the phenyl groups
are bent back from the CtC axes with the angles
ranging from 133.2(3)° to 142.9(4)°. It is noteworthy that
the space-congested NMe3 group is sterically forcing the
upper phenyl rings to lie proximately perpendicular to
the W-C2(alkyne) planes, whereas they are arranged
in a paddlewheel feature in 1.
The new compounds 2 and 3 have been characterized
1
by mass and H and 13C NMR spectroscopy. To evaluate
the electronic and steric effects of NtCMe and NMe3
ligands on the coordination configuration around the W
atom, single crystals of 1 and 2 were studied by X-ray
(14) Agh-Atabay, N. M.; Davidson, J . L.; Douglas, G.; Muir, K. W.
J . Chem. Soc., Chem. Commun. 1989, 549.
(15) (a) Morrow, J . R.; Tonker, T. L.; Templeton, J . L. J . Am. Chem.
Soc. 1985, 107, 5004. (b) Deeth, R. J .; Dossett, S. J .; Green, M.; Mahon,
M. F.; M. F.; Rumble, S. J . J . Chem. Soc., Chem. Commun. 1995, 593.
(c) Carlton, L.; Agh-Atabay, N. M.; Davidson, J . L. J . Organomet. Chem.
1991, 413, 205. (d) Green, M.; Mahon, M. F.; Molloy, K. C.; Nation, C.
B. M.; Woolhouse, C. M. J . Chem. Soc., Chem. Commun. 1991, 1587.
(e) Yeh, W.-Y.; Peng, S.-M.; Liu, L.-K. Inorg. Chem. 1993, 32, 2965.
(16) Yeh, W.-Y.; Ting, C.-S.; Chien, S.-M.; Peng, S.-M.; Lee, G.-H.
Inorg. Chim. Acta 1997, 255, 335.

3060 Organometallics, Vol. 21, No. 14, 2002
Notes
F igu r e 2. Molecular structure of 2. Selected bond dis-
tances (Å): W-N(1) ) 2.329(2), C(43)-N(1) ) 1.480(4),
C(44)-N(1) ) 1.489(4), C(45)-N(1) ) 1.496(4), W-C(1) )
2.069(3), W-C(2) ) 2.054(3), W-C(3) ) 2.066(3), W-C(4)
) 2.059(3), W-C(5) ) 2.070(3), W-C(6) ) 2.057(3), C(1)-
C(2) ) 1.314(4), C(3)-C(4) ) 1.318(4), C(5)-C(6) )
1.314(4). Selected bond angles (deg): N(1)-W-C(1) )
F igu r e 3. Molecular structure of 3. Selected bond dis-
tances (Å): W-Cl) 2.360(2), W-C(1) ) 2.058(6), W-C(2)
) 2.065(6), W-C(3) ) 2.200(6), W-C(4) ) 2.346(6), W-C(5)
) 2.309(6), W-C(6) ) 2.408(6), W-C(7) ) 2.504(6), W-C(8)
) 2.025(7), C(1)-C(2) ) 1.308(9). Selected bond angles
(deg): Cl-W-C(1) ) 87.6(2), Cl-W-C(2) ) 123.3(2), Cl-
W-C(3) ) 88.0(2), Cl-W-C(4) ) 124.1(2), Cl-W-C(5) )
128.2(2), Cl-W-C(6) ) 94.3(2), Cl-W-C(7) ) 88.7(2), Cl-
W-C(8) ) 104.1(2), W-C(1)-C(2) ) 71.8(4), W-C(2)-C(1)
) 71.2(4), C(1)-W-C(3) ) 121.8(2), C(2)-W-C(3) )
87.2(1), N(1)-W-C(2)
86.4(1), N(1)-W-C(4)
86.6(1), N(1)-W-C(6)
)
)
)
124.2(1), N(1)-W-C(3)
123.3(1), N(1)-W-C(5)
123.7(1), W-C(1)-C(2)
)
)
)
70.8(2), W-C(2)-C(1) ) 72.0(2), W-C(3)-C(4) ) 71.1(2),
W-C(4)-C(3) ) 71.7(2), W-C(5)-C(6) ) 70.9(2), W-C(6)-
C(5) ) 72.0(2), C(1)-W-C(3) ) 117.6(1), C(1)-W-C(4) )
109.2(3), C(1)-W-C(8)
) 102.7(3), C(2)-W-C(8) )
118.7(1), C(1)-W-C(5)
114.2(1), C(2)-W-C(3)
92.0(1), C(2)-W-C(5)
92.0(1), C(3)-W-C(5)
120.6(1), C(4)-W-C(5)
92.0(1).
)
)
118.3(1), C(1)-W-C(6)
112.5(1), C(2)-W-C(4)
117.8(1), C(2)-W-C(6)
123.1(1), C(3)-W-C(6)
115.6(1), C(4)-W-C(6)
)
)
)
)
)
100.3(3).
)
)
)
The molecular structure of 3 is illustrated in Figure
3. The diphenylacetylene ligand is eclipsed but tilted
(15.8°) with respect to the W-Cl bond. The W(η6-C6-
Ph6H) moiety forms a metallacycle, which appears to
have a tungsten-carbon double bond to C(8) (2.025(7)
Å), a single bond to C(3) (2.220(6) Å), and π-donation
from the diene unit (C(4)-C(7)) to the tungsten atom.
The W-C distances to the diene linkage are variable,
such that W-C(7) ) 2.504(6) Å and W-C(6) ) 2.408(6)
Å are significantly longer than W-C(5) ) 2.309(6) Å
and W-C(4) ) 2.346(6) Å. The bond lengths and angles
around the η6-C6Ph6H skeleton are illustrated in Figure
4. The C(3), C(4), C(27), C(5), C(6), and C(33) atoms and
the C(39), C(6), C(7), and C(45) atoms are about
coplanar. The atoms W, C(8), C(51), and C(7) are also
on the same plane, and the angle C(7)-C(8)-C(51) is
128.6(6)°, implying an alkylidene carbon for the C(8)
atom. The hydrogen atom, giving a proton resonance
at δ 3.96, is believed to bind the terminal carbon C(3)
on the basis of the W-C(3)-C(21), W-C(8)-C(4), and
C(4)-C(3)-C(51) bond angles, which sum up to 309.5°.
Formation of a WdC double bond in 3 is further
evidenced by the 13C{1H} NMR spectrum, which shows
a low-field signal at δ 261.3 characteristic of an alky-
lidene type carbon.17 A high-field resonance at δ 73.4 is
attributed to the CHPh carbon. The acetylene carbons
give a sharp singlet at δ 218.8, suggesting a facile
rotation for the W-alkyne bonding.
F igu r e 4. Bond distances (Å) and bond angles (deg)
around the η6-C6Ph6H skeleton of 3.
In summary, the results presented here describe
synthesis of a labile NMe3 complex 2, which undergoes
an unusual alkyne coupling reaction in chlorinated
solvents to yield 3 containing a trans (or E)-η6-C6Ph6H
ligand. Currently we are engaged in the reactions of 2
and acids in attempting to remove the basic NMe3
ligand to produce binary complexes of the type [Wx(C2-
Ph2)y].
Exp er im en ta l Section
Gen er a l Com m en ts. All manipulations were carried out
under an atmosphere of purified dinitrogen with standard
Schlenk techniques. Solvents were dried over appropriate
reagents under dinitrogen.18 W(CO)(η2-C2Ph2)33 and W(NCMe)-
(η2-C2Ph2)3 (1)8 were prepared as described in the literature.
(17) Mann, B. E.; Taylor, B. F. 13C NMR Data for Organometallic
Compounds; Academic Press: New York, 1981.

Notes
Organometallics, Vol. 21, No. 14, 2002 3061
Ta ble 1. Cr ysta llogr a p h ic Da ta for
W(NCM)(η2-C2P h 2)3 (1), W(NMe3)(η2-C2P h 2)3 (2), a n d
WCl(η2-C2P h 2)(η6-C6P h 6H) (3)
Anhydrous Me3NO was obtained from Me3NO‚2H2O (Aldrich)
by sublimation under vacuum twice. Preparative thin-layer
chromatographic (TLC) plates were prepared from silica gel
(Kieselgel, DGF254). Infrared spectra were recorded on a
Hitachi I-2001 IR spectrometer. 1H and 13C NMR spectra were
1
2
3
chem formula
cryst syst
space group
fw
a, Å
b, Å
C
44H33NW
C45H39NW
monoclinic
P21/c
C56H41ClW
monoclinic
Cc
934.20
13.286(3)
15.150(3)
21.303(4)
90
98.60(3)
90
4240(2)
4
obtained on
a Varian VXR-300 spectrometer. Fast-atom-
monoclinic
P21/c
bombardment (FAB) mass spectra were recorded by using a
VG Blotch-5022 mass spectrometer. Elemental analyses were
performed at the National Chen-Kung University, Tainan,
Taiwan.
P r ep a r a tion of 2. W(CO)(η2-C2Ph2)3 (745 mg, 1.0 mmol)
and Me3NO (150 mg, 1.95 mmol) were placed in an oven-dried
100 mL Schlenk flask, equipped with a magnetic stir bar and
a rubber serum stopper. Freshly distilled THF (20 mL) was
introduced into the flask via a syringe through the serum
stopper. The mixture was stirred at room temperature for 4
759.56
17.2850(2)
9.9082(1)
19.9590(2)
90
92.291(1)
90
3415.51(6)
4
777.62
16.3984(2)
15.5170(3)
16.6394(3)
90
118.933(1)
90
3705.5(1)
4
1.394
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
D
calc, g cm-1
1.477
3.413
1.464
2.862
µ, mm-1
3.148
h, resulting in
a pale yellow solution plus a gray solid
a
precipitate. The mixture was filtered, and the filtrate was
concentrated to ca. 5 mL on a rotary evaporator. Methanol (15
mL) was added, and the solution was cooled to -10 °C in a
freezer. A colorless crystalline solid was afforded, characterized
as W(NMe3)(η2-C2Ph2)3 (2; 318 mg, 41%). MS(FAB): m/z 777
(M+, 184W), 718 (M+ - NMe3). 1H NMR (CDCl3, 20 °C): δ 7.34-
6.84 (m, Ph), 3.15 (s, NMe3). 13C{1H} NMR (CDCl3, 20 °C): δ
204.2, 188.6 (tC), 146.6, 143.2 (ipso-C6H5), 129.5, 128.1, 127.4,
127.1, 125.6, 124.8 (o, m, p-C6H5), 57.0 (N(CH3)3). Anal. Calcd
for C45H39NW: C, 69.50; H, 5.06; N, 1.80. Found: C, 69.31; H,
5.00; N, 1.68.
P r ep a r a tion of 3. Compound 2 (150 mg, 0.19 mmol) and
PhCtCPh (42 mg, 0.23 mmol) were placed in a 50 mL Schlenk
flask. Dichloromethane (10 mL) was added into the flask, and
the resulting mixture was stirred at ambient temperature for
48 h and then filtered. The filtrate was concentrated to ca. 2
mL and subjected to TLC, with n-hexane/dichloromethane
(3:1, v/v) as eluant. The material forming the major orange-
yellow band was isolated and crystallized from n-hexane/
dichloromethane to afford air-stable, orange-red crystals of
WCl(η2-C2Ph2)(η6-C6Ph6H) (3; 29 mg, 16%). MS(FAB): m/z 932
(M+, 184W and 35Cl), 897 (M+ - Cl), 719 (M+ - Cl - C2Ph2). 1H
NMR (CDCl3, 20 °C): δ 7.48-6.31 (m, Ph), 3.96 (s, CHPh).
13C{1H} NMR (CDCl3, 20 °C): δ 261.3 (WdC), 218.8 (CtC),
R1/wR2
0.0347/0.0585 0.0313/0.0489 0.0313/0.0751
(I > 2σ(I))
GOF on F2
1.031 1.040 1.048
a
2
2
4
R1 ) ∑||Fo| - |Fc||/∑|Fo|; wR2 ) {∑[w(|Fo| - |Fc| )2]/∑w|Fo| }}1/2
.
0.40 × 0.30 × 0.20 mm3) were each mounted in a thin-walled
glass capillary and aligned on the Bruker SMART-CCD (for 1
and 2) and Nonius CAD4 (for 3) diffractometers, with graphite-
monochromated Mo KR radiation (λ ) 0.71073 Å). The data
were collected at 295(2) K. All data were corrected for the
effects of absorption. The structures were solved by the direct
method and refined by full-matrix least-squares on F2. The
program used was the SHELXTL package.19 All non-hydrogen
atoms were refined with anisotropic displacement parameters.
Hydrogen atoms were included but not refined. A summary
of relevant crystallographic data is provided in Table 1.
Ack n ow led gm en t. We are grateful for support of
this work by the National Science Council of Taiwan.
Su p p or tin g In for m a tion Ava ila ble: Complete tables of
crystallographic data, positional parameters, anisotropic ther-
mal parameters, bond angles, bond distances, and torsional
angles of 1-3. This material is available free of charge via
the Internet at http://pubs.acs.org.
141.0-118.8 (C-C6H5), 73.4 (W-CH). Anal. Calcd for C56H41
ClW: C, 72.07; H, 4.43. Found: C, 72.32; H, 4.53.
-
X-r a y Str u ctu r e Deter m in a tion . A crystal of 1 (ca. 0.60
× 0.14 × 0.09 mm3), 2 (ca. 0.40 × 0.22 × 0.18 mm3), and 3 (ca.
OM0201009
(18) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 3rd ed.; Pergamon Press: Oxford, U.K., 1988.
(19) Sheldrick, G. M. SHELXTL; University of Go¨ttingen: Germany,
1985.