Synthesis and structural characterization of configurational isomers of tungsten - Palladium complexes with bridging diphenyl(dithioalkoxycarbonyl)phosphine as a ligand and phosphine transfer from tungsten to palladium

Article abstract of DOI:10.1021/ic9904438

Treatment of the complex [W(CO)₅[PPh₂(CS₂Me)]] (2) with [Pd(PPh₃)₄] (1) affords binuclear complexes such as anti-[(Ph₃P)₂Pd[μ-η¹,η²-(CS₂Me)PPh₂]W(CO)₅] (3), syn-[(Ph₃P)₂Pd[μ-η¹,η²-(CS₂Me)PPh₂]W(CO)₅] (4), and trans-[W(CO)₄(PPh₃)₂] (5). In 3 and 4, respectively, the W and Pd atoms are in anti and syn configurations with respect to the P-CS₂ bond of the diphenyl(dithiomethoxycarbonyl)phosphine ligand, PPh₂(CS₂Me). Complex 3 undergoes extensive rearrangement in CHCl₃ at room temperature by transfer of a PPh₃ ligand from Pd to W, eliminating [W(CO)₅(PPh₃)] (7), while the PPh₂CS₂Me ligand transfers from W to Pd to give [[(Ph₃P)Pd[μ-η¹,η²-(CS₂Me)-PPh₂]]₂] (6). In complex 6, the [Pd(PPh₃)] fragments are held together by two bridging PPh₂(CS₂Me) ligands. Each PPh₂(CS₂Me) ligand is π-bonded to one Pd atom through the C = S linkage and σ-bonded to the other Pd through the phosphorus atom, resulting in a six-membered ring. Treatment of Pd(PPh₃)₄ with [W(CO)₅[PPh₂-[CS₂(CH₂)(n)CN]]] (n = 1, 8a; n = 2, 8b) in CH₂Cl₂ affords syn-[(Ph₃P)₂Pd[μ-η¹,η²-[CS₂(CH₂)(n)CN]PPh₂]W(CO)₅] (n = 1, 9a; n = 2, 9b). Similar configurational products syn-[(Ph₃P)₂Pd[μ-η¹,η²-(CS₂R)PPh₂]W(CO)₅] (R = C₂H₅, C₃H₅, C₂H₄OH, C₃H₆CN, 11a-d) are synthesized by the reaction of Pd(PPh₃)₄ with [W(CO)₅[PPh₂(CS₂R)]] (R = C₂H₅, C₃H₅, C₂H₄OH, C₃H₆CN, 10a-d). Although complexes 11a-d have the same configuration as 9a,b, the SR group is oriented away from Pd in the former and near Pd in the latter. In these complexes, the diphenyl(dithioalkoxycarbonyl)phosphine ligand is bound to the two metals through the C = S π-bonding and to phosphorus through the σ-bonding. All of the complexes are identified by spectroscopic methods, and the structures of complexes 3, 6, 9a, and 11d are determined by single-crystal X-ray diffraction. Complexes 3, 9, and 11d crystallize in the triclinic space group P1 with Z = 2, whereas 6 belongs to the monoclinic space group P2/c with Z = 4. The cell dimensions are as follows: for 3, a = 10.920(3) A, b = 14.707(5) A, c = 16.654(5) A, α = 99.98(3)°, β = 93.75(3)°, γ = 99.44(3)°; for 6, a = 15.106(3) A, b = 9.848(3) A, c = 20.528(4) A, β = 104.85(2)°; for 9a, a = 11.125(3) A, b = 14.089(4) A, c = 17.947(7) A, α = 80.13(3)°, β = 80.39(3)°, γ = 89.76(2)°; for 11d, a = 11.692(3) A, b = 13.602(9) A, c = 18.471(10) A, α = 81.29(5)°, β = 80.88(3)°, γ = 88.82(1)°.

Full text of DOI:10.1021/ic9904438

Inorg. Chem. 2000, 39, 2445-2451
2445
Synthesis and Structural Characterization of Configurational Isomers of
Tungsten-Palladium Complexes with Bridging Diphenyl(dithioalkoxycarbonyl)phosphine as
a Ligand and Phosphine Transfer from Tungsten to Palladium
Kuang-Hway Yih,*,† Gene-Hsiang Lee,‡ and Yu Wang‡
Department of Applied Cosmetology, Hung Kuang Institute of Technology, Sahlu, Taichung,
Taiwan 433, Republic of China, and Department of Chemistry, National Taiwan University,
Taiwan 106, Republic of China
ReceiVed April 23, 1999
Treatment of the complex [W(CO)5[PPh2(CS2Me)]] (2) with [Pd(PPh3)4] (1) affords binuclear complexes such as
anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W(CO)5] (3), syn-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W(CO)5] (4), and trans-
[W(CO)4(PPh3)2] (5). In 3 and 4, respectively, the W and Pd atoms are in anti and syn configurations with respect
to the P-CS2 bond of the diphenyl(dithiomethoxycarbonyl)phosphine ligand, PPh2(CS2Me). Complex 3 undergoes
extensive rearrangement in CHCl3 at room temperature by transfer of a PPh3 ligand from Pd to W, eliminating
[W(CO)5(PPh3)] (7), while the PPh2CS2Me ligand transfers from W to Pd to give [[(Ph3P)Pd[µ-η1,η2-(CS2Me)-
PPh2]]2] (6). In complex 6, the [Pd(PPh3)] fragments are held together by two bridging PPh2(CS2Me) ligands.
Each PPh2(CS2Me) ligand is π-bonded to one Pd atom through the CdS linkage and σ-bonded to the other Pd
through the phosphorus atom, resulting in a six-membered ring. Treatment of Pd(PPh3)4 with [W(CO)5[PPh2-
[CS2(CH2)nCN]]] (n ) 1, 8a; n ) 2, 8b) in CH2Cl2 affords syn-[(Ph3P)2Pd[µ-η1,η2-[CS2(CH2)nCN]PPh2]W-
(CO)5] (n ) 1, 9a; n ) 2, 9b). Similar configurational products syn-[(Ph3P)2Pd[µ-η1,η2-(CS2R)PPh2]W(CO)5] (R
) C2H5, C3H5, C2H4OH, C3H6CN, 11a-d) are synthesized by the reaction of Pd(PPh3)4 with [W(CO)5[PPh2-
(CS2R)]] (R ) C2H5, C3H5, C2H4OH, C3H6CN, 10a-d). Although complexes 11a-d have the same configuration
as 9a,b, the SR group is oriented away from Pd in the former and near Pd in the latter. In these complexes, the
diphenyl(dithioalkoxycarbonyl)phosphine ligand is bound to the two metals through the CdS π-bonding and to
phosphorus through the σ-bonding. All of the complexes are identified by spectroscopic methods, and the structures
of complexes 3, 6, 9a, and 11d are determined by single-crystal X-ray diffraction. Complexes 3, 9, and 11d
crystallize in the triclinic space group P1h with Z ) 2, whereas 6 belongs to the monoclinic space group P2/c with
Z ) 4. The cell dimensions are as follows: for 3, a ) 10.920(3) Å, b ) 14.707(5) Å, c ) 16.654(5) Å, R )
99.98(3)°, â ) 93.75(3)°, γ ) 99.44(3)°; for 6, a ) 15.106(3) Å, b ) 9.848(3) Å, c ) 20.528(4) Å, â ) 104.85-
(2)°; for 9a, a ) 11.125(3) Å, b ) 14.089(4) Å, c ) 17.947(7) Å, R ) 80.13(3)°, â ) 80.39(3)°, γ ) 89.76(2)°;
for 11d, a ) 11.692(3) Å, b ) 13.602(9) Å, c ) 18.471(10) Å, R ) 81.29(5)°, â ) 80.88(3)°, γ ) 88.82(1)°.
Introduction
a variety of insertion15,16 and disproportionation17 reactions.
Moreover, CS2-containing metal complexes can be used as
Since the first CS2 metal complex [Ni2(CS2)2(PPh3)2] was
prepared by Baird and Wilkinson1 in 1967, transition metal-
CS2 complexes have attracted considerable attention. Carbon
disulfide, CS2, has proved to be a versatile ligand, being capable
of coordinating to one2-11 or more12-14 metals and it showing
models for CO2 complexes, which are much more difficult to
-
investigate.18,19 Consequently, three CS2 derivatives, R3P+CS2
,
R2PCS2-, and R2NCS2-, were synthesized to understand vari-
able coordination chemistry.
† Huang Kuang Institute of Technology.
(10) Ibers, J. A. Chem. Soc. ReV. 1982, 11, 57.
(11) Bianchini, C.; Mealli, C.; Meli, A.; Sabat, M.; Silvestre, J.; Hoffmann,
R. Organometallics 1986, 5, 1733.
(12) Southern, T. G.; Oehmichen, U.; Le Marouille, J. Y.; Le Bozec, H.;
Grandjean, D.; Dixneuf, P. H. Inorg. Chem. 1980, 19, 2976.
(13) Bianchini, C.; Mealli, C.; Meli, A.; Orlandini, A.; Sacconi, L. Inorg.
Chem. 1980, 19, 2968.
‡ National Taiwan University.
(1) Baird, M. C.; Wilkinson, G. J. Chem. Soc. A 1967, 865.
(2) Kashiwagi, T.; Yasuoka, N.; Ueki, T.; Kasai, N.; Kakudo, M.;
Takahashi, S.; Hagihara, N. Bull. Chem. Soc. Jpn. 1968, 296.
(3) Clark, G. R.; Collins, T. J.; James, S. M.; Roper, W. R. J. Organomet.
Chem. 1977, 125, C23.
(4) Werner, H.; Leonhard, K.; Burschka, C. J. Organomet. Chem. 1978,
160, 291.
(5) Bozec, H. L.; Dixneuf, P. H.; Carty, A. J.; Taylor, N. J. Inorg. Chem.
1978, 17, 2568.
(14) Brennan, J. G.; Andersen, R. A.; Zalkin, A. Inorg. Chem. 1986, 25,
1756.
(15) Rossi, R.; Marchi, A.; Duatti, A.; Magon, L. J. Chem. Soc., Dalton
Trans. 1988, 899.
(6) Fachinetti, G.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. J. Chem.
Soc., Dalton Trans. 1979, 1612.
(7) Werner, H. Coord. Chem. ReV. 1982, 43, 165.
(8) Mason, M. G.; Swepston, P. N.; Ibers, J. A. Inorg. Chem. 1983, 22,
411.
(16) Yih, K. H.; Chen, S. C.; Lin, Y. C.; Cheng, M. C.; Wang, Y. J.
Organomet. Chem. 1995, 494, 149.
(17) Butler, I. S.; Fenster, A. E. J. Organomet. Chem. 1974, 66, 161.
(18) Lisy, J. M.; Dobrzynski, E. D.; Angelici, R. J.; Clardy, J. J. Am. Chem.
Soc. 1975, 97, 656.
(9) Bianchini, C.; Ghilardi, C. A.; Meli, A.; Orlandini, A. J. Organomet.
Chem. 1984, 270, 251.
(19) Herberhold, M.; Suss-Fink, M.; Kreiter, C. G. Angew. Chem., Int. Ed.
Engl. 1977, 16, 193.
10.1021/ic9904438 CCC: $19.00 © 2000 American Chemical Society
Published on Web 05/19/2000

2446 Inorganic Chemistry, Vol. 39, No. 12, 2000
Yih et al.
Scheme 1
-
20-25
A typical example, the zwitterionic R3P+CS2
ligand,
On the basis of these experimental results, we investigated
the existence of configurational isomers in complexes between
[diphenyl(dithioalkoxycarbonyl)phosphine]tungsten(0) com-
pounds and Pd(PPh3)4. We report our results in this article, along
with four X-ray crystal structure analyses that were carried out
to provide accurate structural parameters.
has various bonding modes, which include monodentate coor-
dination through one S atom,20 chelation21 or bridging22 through
two S atoms, and dinuclear pesudoallylic bridging forms, i.e.,
an η3,σ mode with donation of six electrons22-24 and an η2,η3
mode with donation of eight electrons.25 The anionic ligands
-
- 26,27
R2PCS2 and R2NCS2
normally show monodentate co-
Results and Discussion
ordination through P or S and bidentate coordination through P
and S and through N and S, respectively. Little effort has been
directed toward investigating the reactivity of the ligand
R2PCS2- and its derivative R2PCS2R. To date, the neutral alkyl
(diorganothiophosphinoyl)dithioformate compound, R2P(S)C-
(S)R, is the only analogous example that has been used to react
with [Pt(PPh3)2C2H4], forming the CdS π-coordination com-
plex.28 Notably, in metal complexes containing the above-
mentioned ligands, no phosphine transfer reactions or configu-
rational isomers have been observed.
Recently, we developed an efficient method to synthesize
metal complexes with the diphenyl(dithioalkoxycarbonyl)-
phosphine ligand, Ph2P(CS2R),29 which allows more extensive
exploration of the chemistry of these complexes. In a previous
communication,30 we reported the Ph2P(CS2Me) ligand transfer
reaction between [Pd(PPh3)4] (1) and [W(CO)5[PPh2(CS2Me)]]
(2), forming anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W(CO)5] (3)
as an intermediate.
Reaction of [Pd(PPh3)4] (1) with [W(CO)5[PPh2(CS2Me)]]
(2). The reaction of [Pd(PPh3)4] (1) and [W(CO)5[PPh2(CS2-
Me)]] (2) in refluxing diethyl ether affords a yellow crystalline
product, identified as anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W-
(CO)5] (3) (Scheme 1), in 55% yield. Compound 3 is moderately
soluble in dichloromethane and acetonitrile, slightly soluble in
diethyl ether and tetrahydrofuran, and insoluble in n-hexane.
The spectroscopic and analytical data of 3 are in agreement
with the formulation. The FAB mass spectrum of 3 exhibits a
base peak corresponding to its molecular mass. In the IR
spectrum of 3, three terminal carbonyl stretching bands at 2060
(m), 1914 (vs), and 1887 (s) cm-1 are observed, which is a
typical pattern for an LM(CO)5 unit in octahedral geometry.
1
The H NMR spectrum of 3 exhibits a resonance at δ 2.09
assignable to the methyl protons of the PPh2(CS2Me) ligand,
and the corresponding 13C{1H} NMR signal appears at δ 18.7.
In the 13C{1H} NMR spectrum of 3, three resonances appear
in the carbonyl region. The two resonances at δ 214.9 and 198.8
with a ratio of 1/4 are attributed to the trans and cis carbonyl
groups, respectively. The resonance at δ 208.2 is assigned to
the carbon atom of CS2 in the PPh2(CS2Me) ligand. In the 31P-
{1H} NMR spectrum of 3, a resonance at δ 51.6 with a tungsten
satellite (1JW-P ) 257.6 Hz) and two broad resonances at δ
22.2 and 22.4 indicate P-coordination of the PPh2(CS2Me) ligand
to W and of the two triphenylphosphine ligands to Pd in the
cis geometry.
To confirm the bonding mode of the PPh2(CS2Me) ligand,
complex 3 was characterized by an X-ray diffraction analysis.
Its ORTEP diagram with atom labeling is shown in Figure 1.
Table 2 contains selected bond distances and angles. The most
remarkable features of the whole structure are the π-bonding
of the CdS moiety in the PPh2(CS2Me) ligand to the Pd atom
(20) Bianchini, C.; Meli, A.; Orlandini, A. Inorg. Chem. 1982, 21, 4161.
(21) George, R. C.; Terrence, J. C.; Suzanne, M. J.; Warren, R. R.; Keith,
G. T. Chem. Commun. 1976, 475.
(22) Alvarez, B.; Miguel, D.; Riera, V. Organometallics 1991, 10, 384.
(23) Kreissl, F. R.; Ullrich, N.; Wirsing, A.; Thewalt, U. Organometallics
1991, 10, 3275.
(24) Galindo, A.; Gutierrez-Puebla, E.; Monge, A.; Munoz, M. A.; Pastor,
A.; Ruiz, C.; Carmona, E. J. Chem. Soc., Dalton Trans. 1992, 2307.
(25) Miguel, D.; Perez-Martinez, J. A.; Riera, V. Organometallics 1993,
12, 1394.
(26) Kunze, U.; Jawad, H.; Burghardt, R.; Tittmann, R.; Kruppa, V. J.
Organomet. Chem. 1986, 302, C30.
(27) Ambrosius, H. P. M. M.; Van Hemert, A. W.; Bosman, W. P.; Hoordik,
J. H.; Ariaans, G. J. A. Inorg. Chem. 1984, 23, 2678-2685.
(28) Carr, W. S.; Colton, R.; Dakternieks, D. Inorg. Chem. 1984, 23, 720.
(29) Yih, K.-H.; Lin, Y.-C.; Cheng, M.-C.; Wang, Y. J. Chem. Soc., Dalton
Trans. 1995, 1305.
(30) Yih, K.-H.; Lin, Y.-C.; Cheng, M.-C.; Wang, Y. J. Organomet. Chem.
1994, 474, C34.

Isomers of Tungsten-Palladium Complexes
Inorganic Chemistry, Vol. 39, No. 12, 2000 2447
CH2N(CH2CH2PPh2)2Ni(CS2Me)][BPh4].9 In this compound, the
nickel atom is coordinated in an η2 fashion by the CdS moiety
and the carbon in the thiocarbonyl shows an sp3 hybridization
character, albeit the nickel complex is mononuclear, unlike the
binuclear complex 3, in which the two metals are bridged by
PPh2CS2Me ligand.
The reaction of 1 and 2 yields not only complex 3 but also
small amounts of complexes syn-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)-
PPh2]W(CO)5] (4) (10%) and trans-[W(CO)4(PPh3)2] (5) (20%)
(Scheme 1). Although complex 4 is too unstable for its 13C-
{1H} NMR spectrum to be obtained, its mass spectrum is the
same as that of complex 3. Interestingly, complex 4 exhibits
an 31P{1H} NMR pattern significantly different from that of
complex 3. The 31P{1H} NMR spectrum of 4 displays a
resonance at δ 28.8 with a tungsten satellite (1JW-P ) 204.5
Hz, 3JP-P ) 7.0 Hz) which is coupled with a resonance of one
of the PPh3 ligands on Pd. Two other peaks resonating at δ
21.7 (d, 2JP-P ) 39.1 Hz) and δ 25.2 (dd, 3JP-P ) 7.0 Hz, 2JP-P
) 39.1 Hz) with low coupling constants are in favor of a cis
geometry for the phosphines on Pd. In complex 3, the PPh2(CS2-
Me) ligand on W does not couple with a PPh3 on Pd, but in
complex 4, such coupling does occur. Clearly, complexes 3 and
4 possess the same molecular weight but differ in their
configurations. This is possibly due to different coordinations
of the thiocarbonyl group of [W(CO)5[PPh2(CS2Me)]] (2) with
[Pd(PPh3)4]. The thiocarbonyl group may coordinate with the
Pd fragment in two ways: one is to form the anti configurational
complex by occupying the two metal atoms on opposite sides
of the P-CS2R bond and the other is to form the syn
configurational complex by occupying the Pd and W atoms on
the same side of the P-CS2R bond.
Figure 1. ORTEP plot of the molecular structure of compound 3. The
phenyl groups are omitted for clarity.
and the σ-bonding to the W atom through the phosphorus atom.
Notably, the two metal atoms are on two different sides with
respect to the P-CS2 bond of the PPh2(CS2Me) ligand. The Pd
atom and its neighboring atoms, P(1), P(2), S(1), and C(6), lie
in a distorted square plane, the distortion being mainly due to
the short bite of the CdS linkage [C-Pd-S ) 46.09(21)°].
The W-Pd bond distance in 3, 5.620(2) Å, indicates that there
is no bonding interaction between the two metal atoms. The
sulfur-carbon bond lengths in the PPh2(CS2Me) ligand range
from 1.736(8) to 1.794(8) Å. Compared with the typical S-C
single- and double-bond lengths of 1.81 and 1.71 Å, these
parameters are indicative of delocalized bonding for the four
atoms S(1), C(6), S(2), and C(7). Moreover, the C(6)-S(1) bond
distance of 1.736(8) Å is longer than the corresponding carbon-
sulfur bond distances observed in η2-CS2 (sp2) transition metal
complexes [1.65(3) Å in [(PPh3)2Pd(η2-CS2)],2 1.66 Å in
[(PPh3)2Ru(η2-CS2Me)(CO)2][ClO4],3 1.68(1) Å in [CpCo-
(PMe3)(η2-CS2)],4 1.676(7) Å in [Fe(PPh3)(PMe3)(CO)2(η2-
CS2)],5 1.667(4) Å in [(Cp)2V(η2-CS2)],6 1.68(1) Å in [(triphos)-
Co(η2-CS2)],12 1.658(6) Å in [(PhMe2P)2(CO)2FeCS2Mn-
(CO)2Cp],13 1.63(1) Å in [(PPh3)Ni(µ-CS2)2Ni(PPh3)],31 and
1.674(6) Å in [(PPh3)Pt(µ-CS2)2Pt(PPh3)]32]. The C-S bond
lengths are longer than those in free CS2 (1.554 Å), indicating
coordination of CS2 in an η2 fashion, which reduces the bond
order of the CdS bonds. A comment must be made about the
carbon atom of the CS2 group. An examination of its bond
distances and angles shows a geometrical environment charac-
teristic of an sp3 hybridization. The Pd-C(6)-S(1) angle, 71.0-
(3)°, is significantly different from the others, which are in the
range 107.0(5)-124.1(4)°.
In the reaction of 1 and 2, the complex trans-[W(CO)4(PPh3)2]
(5) is also isolated. Hieber33 and co-workers synthesized it 40
years ago. An improved preparation of tertiary phosphines and
related substitution products of group VI metal carbonyls in
high yields through sodium borohydride catalysis in boiling
ethanol was developed by Chatt34 in 1971.
Disproportionation Reaction of Complex 3. At room-
temperature, complex 3 is unstable in CHCl3 and slowly forms
the complex [Pd(PPh3)[PPh2(CS2Me)]]2 (6) in 31% isolated yield
and the complex [W(CO)5(PPh3)] (7) in 40% yield (Scheme
1). Compound 6 is an air-stable, yellow solid that is readily
soluble in polar organic solvents such as dichloromethane,
toluene, and acetonitrile but insoluble in saturated hydrocarbons.
The identification of 6 as [Pd(PPh3)[PPh2(CS2Me)]]2 was
based on the spectroscopic data. The FAB mass spectrum of 6
shows a peak at m/z 1243 which corresponds to a fragment
formed by the cleavage of the SMe group from 6. The 1H NMR
spectrum of 6 exhibits a singlet at δ 2.18 assignable to the
thiomethoxy protons, and the corresponding 13C{1H} NMR
signal is at δ 19.7. A downfield singlet at δ 53.7 without a
tungsten satellite in the 31P{1H} NMR spectrum is assigned to
the PPh2(CS2Me) ligand whereas a signal at higher field (δ 22.2)
is due to the PPh3 group on Pd. The 13C{1H} NMR spectrum
of 6 displays one set of resonances for the PPh2(CS2Me) ligand.
In addition, no carbonyl absorption in the IR spectrum and
tungsten isotope distribution in the mass spectrum have been
observed. It can be summarized that the diphenyl(dithiomethox-
ycarbonyl)phosphine ligand is transferred from tungsten to
palladium to form a dipalladium complex.
For the PPh3 ligands, the average values of C-P-C′S and
Pd-P-C′S are 103 and 115°, respectively, and the geometry
around the P atom is distorted tetrahedral. The Pd-P(1) distance
in 3, 2.317(2) Å, is considerably shorter than the sum of covalent
radii (2.42 Å). This value is similar to those in [(C4H7)PdPPh3]
(2.31 Å) and [(PPh3)2Pd(η2-CS2)] (2.316(8) Å). The Pd-S(1)
distance, 2.278(2) Å, is within the normal Pd-S length range
(2.23-2.31 Å).5 The Pd-C(6) bond length, 2.145(8) Å, is also
within the usual range for Pd-C(sp3) σ bonds. No bonding
interaction between the palladium and the phenyl carbon atoms
is apparent.
The singularity of the diphenyl(dithiomethoxycarbonyl)-
phosphine complex 3 does not allow a direct comparison with
any other compounds reported in the literature. However, 3
shows some structural analogies with the complex [Ph2PCH2-
(31) Bianchini, C.; Ghilardi, C. A.; Meli, A.; Midollini, S.; Orlandini, A.
J. Chem. Soc., Chem. Commun. 1983, 753.
(32) Farrar, D. H.; Gukathasan, R. R.; Morris, S. A. Inorg. Chem. 1984,
23, 3258.
(33) Hieber, W.; Peterhans, J. Z. Naturforsch. 1959, 14B, 462.
(34) Chatt, J.; Leigh, G. J.; Thankarajan, N. J. Organomet. Chem. 1971,
29, 105.

2448 Inorganic Chemistry, Vol. 39, No. 12, 2000
Yih et al.
Table 1. Crystal Data and Refinement Details for Complexes 3, 6, 9a, and 11d‚CHCl3
3
6
9a
11d‚CHCl3
empirical formula
fw
space group
a, Å
b, Å
C55H43O5P3S2PdW
1231.22
P1h
C64H56P4S4Pd2
1290.07
P2/c
15.106(3)
9.848(3)
20.528(4)
C56H42NO5P3S2PdW
1256.23
P1h
C59H47Cl3NO5P3S2PdW
1403.66
P1h
10.920(3)
14.707(5)
16.654(5)
99.98(3)
93.75(3)
99.44(3)
2586.3(14)
2
1.581
28.268
0.70930
25
0.040
11.125(3)
14.089(4)
17.947(7)
80.13(3)
80.39(3)
89.76(2)
2731.7(15)
2
1.527
26.785
0.71073
25
0.047
11.692(3)
13.602(9)
18.471(10)
81.29(5)
80.88(3)
88.82(1)
2867(3)
2
1.626
25.538
0.71073
25
0.038
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
104.85(2)
2934.2(12)
2
1.46
8.843
0.71073
25
0.034
0.037
F
calcd, g cm-3
µ(Mo KR), cm-1
λ, Å
T, °C
Ra
b
Rw
0.042
0.044
0.041
2
a R ) ∑||Fo| - |Fc||/∑|Fo|. b Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2; w ) 1/σ2(|Fo|).
Table 2. Selected Interatomic Distances (Å) and Angles (deg) for
3, 6, 9a, and 11d
bond lengths
bond angles
Compound 3
Pd-S(1)-C(6)
W-P(3)
2.542(2)
2.317(2)
2.364(2)
2.278(2)
2.145(8)
1.736(8)
1.794(8)
1.871(8)
62.9(3)
71.0(3)
Pd-P(1)
Pd-P(2)
Pd-S(1)
Pd-C(6)
C(6)-S(1)
C(6)-S(2)
C(6)-P(3)
Pd-C(6)-S(1)
S(1)-Pd-C(6)
S(2)-C(6)-Pd
W-P(3)-C(6)
P(1)-Pd-P(2)
P(3)-C(6)-Pd
P(3)-C(6)-S(2)
46.09(21)
117.6(4)
114.1(3)
105.73(8)
124.1(4)
110.4(4)
Compound 6
Pd-P(1)
Pd-P(2)
Pd-S(1)
Pd-C(1)
C(1)-S(1)
C(1)-S(2)
C(1)-P(1)
2.310(1)
2.340(2)
2.296(1)
2.106(5)
1.734(5)
1.793(5)
1.836(5)
Pd-S(1)-C(1)
Pd-C(1)-S(1)
S(1)-Pd-C(1)
S(2)-C(1)-Pd
C(1)-P(1)-Pd
P(1)-Pd-P(2)
P(1)-C(1)-Pd
61.14(16)
72.73(18)
46.13(13)
118.50(25)
116.81(16)
108.02(5)
112.97(23)
Figure 2. ORTEP plot of the molecular structure of compound 6. The
phenyl groups are omitted for clarity.
six-membered ring. A least-squares plane calculation reveals
the planarity of the P(2)P(1)C(1)S(1) core (largest deviation
0.07(1) Å). The Pd-PPh3 distance, 2.325(2) Å, is significantly
longer than the corresponding value of 2.267(2) Å found in
[PdCl(CH2SMe)(PPh3)2],5 possibly because of the influence of
the CdS coordination.
In the literature, two six-membered-ring doubly CS2-bridged
binuclear complexes, [(PPh3)Ni(µ-CS2)2Ni(PPh3)]31 and [(PPh3)-
Pt(µ-CS2)2Pt(PPh3)],32 were reported by Bianchini and Farrar.
The differences between the doubly CS2-bridged and doubly
PPh2(CS2Me)-bridged complexes are due to the hybridization
of the carbon atom of the CdS moiety. Because of the sp3
hybridization of the C atom, the six-membered ring of complex
6 adopts a distorted chair conformation. However, sp2 hybrid-
ization of the C atom results in planarity of the Ni(µ-CS2)2Ni
entity (largest deviation from the mean plane 0.034 Å), creating
the possibility of an overall electronic delocalization.
Thus, the (dithiomethoxycarbonyl)phosphine transfer reaction
between [Pd(PPh3)4] and [W(CO)5[PPh2(CS2Me)]] (2) forms
[[(Ph3P)Pd[µ-η1,η2-(CS2Me)PPh2]]2] (6) as the ultimate product.
The reaction proceeds via an η2-coordination of the CdS
fragment to Pd, giving anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W-
(CO)5] (3) as an intermediate. To the best of our knowledge,
there is no previous report of diphenyl(dithiomethoxycarbonyl)-
phosphine acting as a doubly bridging ligand and of the
phenomenon of a phosphine transfer reaction.
Compound 9a
W-P(1)
2.565(3)
2.333(3)
2.323(3)
2.249(3)
2.217(10)
1.734(10)
1.836(10)
1.811(11)
Pd-S(1)-C(1)
Pd-C(1)-S(1)
S(1)-Pd-C(1)
S(2)-C(1)-Pd
W-P(1)-C(1)
P(2)-Pd-P(3)
P(1)-C(1)-Pd
P(1)-C(1)-S(2)
66.2(3)
68.1(3)
45.7(3)
111.1(5)
119.6(3)
103.68(11)
127.7(5)
113.9(5)
Pd-P(3)
Pd-P(2)
Pd-S(1)
Pd-C(1)
C(1)-S(1)
C(1)-S(2)
C(1)-P(1)
Compound 11d
W-P(1)
2.558(3)
2.341(2)
2.344(3)
2.261(2)
2.235(8)
1.727(8)
1.813(8)
1.846(8)
Pd-S(1)-C(1)
Pd-C(1)-S(1)
S(1)-Pd-C(1)
S(2)-C(1)-Pd
W-P(1)-C(1)
P(2)-Pd-P(3)
P(1)-C(1)-Pd
P(1)-C(1)-S(2)
66.6(3)
68.2(3)
Pd-P(3)
Pd-P(2)
Pd-S(1)
Pd-C(1)
C(1)-S(1)
C(1)-S(2)
C(1)-P(1)
45.18(20)
114.6(4)
120.6(3)
104.00(9)
124.3(4)
111.3(4)
We also performed an X-ray diffraction study of 6. It ORTEP
drawing with atom labeling is shown in Figure 2. Table 2
contains selected bond distances and angles. The two Pd(PPh3)
fragments, which are related by a crystallographic inversion
center, are held together by two doubly bridging PPh2CS2Me
moieties. Each PPh2(CS2Me) ligand is π-bonded to one Pd atom
through the CdS linkage and σ-bonded to the other Pd through
the phosphorus atom, resulting in a six-membered ring. The
coordination around each Pd atom is a distorted square plane,
the distortion being mainly due to the short bite of the CdS
linkage [C-Pd-S ) 46.13(13)°] and the requirements of the
The R2P(S)C(S)SR ligand has successfully been used in
reactions with [Pt(PPh3)2C2H4] to form η2-CS complexes.28 In
an attempt to find another preparation method for complex 6,

Isomers of Tungsten-Palladium Complexes
Inorganic Chemistry, Vol. 39, No. 12, 2000 2449
Figure 3. ORTEP plot of the molecular structure of compound 9a.
The phenyl groups are omitted for clarity.
Figure 4. ORTEP plot of the molecular structure of compound 11d.
The phenyl groups are omitted for clarity.
we treated PPh2(CS2Me) with Pd(PPh3)4 in CH2Cl2 at ambient
temperature. Although the CdS π-coordination complex was
observed, more than six other complexes were also found and
the reaction was not pursued further. Et2N(CS2Me) and Et2N-
[C(S)NHPh] were also treated with [Pd(PPh3)4], but no reaction
occurred even under extreme experimental conditions.
It is clear that the palladium and tungsten metal centers are in
a syn configuration with respect to the P-CS2 bond of the
PPh2(CS2CH2CN) ligand. The Pd-S(1) and Pd-C(1) bond
distances of 9a are 2.249(3) and 2.217(10) Å, respectively,
which are considered to be normal for Pd-S bonds (2.23-2.31
Å) and Pd-C(sp3) σ bonds.5 The C(1)-Pd, W-P(1), and C(1)-
S(2)R bond distances of 2.217(10), 2.565(3), and 1.836(10) Å
in 9a are longer than those of 2.145(8), 2.542(2), and 1.794(3)
Å, respectively, in 3, but the C(1)-P(1) (1.811(11) Å) and
S(1)-Pd (2.249(3) Å) bond distances in 9a are shorter than
those in 3 [1.871(8) and 2.278(2) Å, respectively]. This is due
to the large steric hindrance of the syn configuration and can
be confirmed by the W-Pd bond distances, 5.620(2) Å in 3
and 4.610(2) Å in 9a.
Synthesis of syn-[(Ph3P)2Pd[µ-η1,η2-[CS2(CH2)nCN]PPh2]W-
(CO)5] (n ) 1, 9a; n ) 2, 9b). The proposed differently
configured complexes, 3 and 4, were identified only by their
31P{1H} NMR spectra. Unfortunately, we could not obtain a
good-quality sample of the syn product 4 for X-ray diffraction
analysis. Steric hindrance of the chemical reactions controls the
reactive direction, which influences the stereoselectivity of the
product. To explore the syn configurational complex, we carried
out the reactions of the two hindered thionitrile complexes 8a,b
with [Pd(PPh3)4] (Scheme 1).
Reaction of [W(CO)5[PPh2(CS2R)]] (R ) C2H5, C3H5,
C2H4OH, C3H6CN, 10a-d) with [Pd(PPh3)4]. To investigate
the factors that influence the stability of η2-CS2 bonds to
palladium and the configurations of the binuclear complexes,
we extended the range of diphenyl(dithioalkoxycarbonyl)-
phosphine ligands in [W(CO)5[PPh2(CS2R)]] (R ) C2H5, C3H5,
C2H4OH, C3H6CN, 10a-d). Complexes of the type syn-
[[(Ph3P)2Pd[µ-η1,η2-(CS2R)PPh2]W(CO)5]] (R ) C2H5, C3H5,
C2H4OH, C3H6CN, 11a-d) were achieved by the reactions of
[W(CO)5[PPh2(CS2R)]] (R ) C2H5, C3H5, C2H4OH, C3H6CN,
10a-d) with [Pd(PPh3)4] in CH2Cl2. Compounds 11a-d are
air-stable, yellow solids and are readily soluble in polar organic
solvents such as dichloromethane and acetonitrile, slightly
soluble in tetrahydrofuran, and insoluble in saturated hydrocar-
bons. All of the spectroscopic and analytical data of 11a-d
are in agreement with their formulations. The most interesting
observation is the 31P{1H} NMR pattern of these complexes.
The 31P{1H} NMR spectrum of 11a shows a resonance at δ
52.6 with a tungsten satellite (1JW-P ) 249.0 Hz) and a singlet
resonance at δ 22.7 with a ratio of 1/2, indicating that one PPh2-
(CS2C2H5) ligand is P-coordinated to W and two triphenylphos-
phines are coordinated to Pd in a cis geometry. Complex 11a
is very stable in the solid state and does not decompose in air
over a period of 1 week. The structures of 11a-d were proposed
to have syn configurations, which were proved by an X-ray
structural analysis of 11d. Figure 4 shows its ORTEP diagram
with atom labeling. Selected bond distances and angles are
presented in Table 2. It is apparent that the palladium and
tungsten metal centers are in a syn configuration with respect
to the P-CS2 bond of the PPh2(CS2C3H6CN) ligand and the
thioalkoxy portion points away from the Pd metal. The CdS,
The reactions of [W(CO)5[PPh2[CS2(CH2)nCN]]] (n ) 1, 8a;
n ) 2, 8b) with [Pd(PPh3)4] in CH2Cl2 at room temperature
were monitored by 31P{1H} NMR spectroscopy. Only one kind
of product was detected which was identified as syn-[(Ph3P)2-
Pd[µ-η1,η2-CS2(CH2)nCNPPh2]W(CO)5] (n ) 1, 9a; n ) 2, 9b)
(Scheme 1). Complexes 9a and 9b were isolated in 85 and 90%
yields, respectively. They are yellow, moderately air-stable, and
readily soluble in chlorinated solvents but insoluble in nonpolar
solvents. The FAB mass spectra show two base peaks at m/z
1216 corresponding to (Ph3P)2Pd[(S2C)PPh2]W(CO)5+, formed
by the loss of CH2CN and C2H4CN groups from 9a and 9b,
respectively. In the 1H NMR spectra of 9a and 9b, AB
resonances (δ 2.81, 3.19) and two triplet resonances (δ 2.90,
3.44) are respectively assignable to the thiomethylene and
thioethylene protons. The corresponding 13C{1H} NMR signals
appear at δ 20.1 and at δ 15.2, 21.7, respectively. The 31P{1H}
NMR spectrum of 9a exhibits a resonance at δ 54.2 with a
3
tungsten satellite (1JW-P ) 255.0 Hz, JP-P ) 10.0 Hz) and a
small coupling with PPh3 on Pd. Two other signals exhibit AB
2
3
resonances at δ 22.5 (dd, JP-P ) 37.1 Hz, JP-P ) 10.0 Hz)
and δ 24.7 (2JP-P ) 37.1 Hz). The three 31P{1H} NMR
resonances of 9b appear at δ 55.7 (1JW-P ) 258.4 Hz), δ 23.4
(dd, 2JP-P ) 33.5 Hz, 3JP-P ) 7.9 Hz), and δ 24.2 (d, 2JP-P
)
33.5 Hz), respectively. The most interesting point is that the
31P{1H} NMR patterns of 9a,b are similar to that of 4. We thus
believe that complexes 9a,b and 4 have similar configurations.
To verify this hypothesis, the structure of complex 9a was
determined identified by a single-crystal X-ray diffraction
analysis. Figure 3 shows its ORTEP drawing with atom labeling
of 9a. Selected bond distances and angles are listed in Table 2.

2450 Inorganic Chemistry, Vol. 39, No. 12, 2000
Yih et al.
Elemental analyses and X-ray diffraction studies were carried out at
the Regional Center of Analytical Instrumentation located at the
National Taiwan University.
C-Pd, S-Pd, P-CS, and W-P bond distances of 11d are
similar to those of compound 9a within experimental error. The
W-Pd bond distance in 11d, 4.575(3) Å, is shorter than that
(5.620(2) Å) in 3, indicating no bonding interaction between
the two metal atoms. The conspicuously short C-SR bond
distance of 11d (1.813(8) Å) is attributed to the smaller
hindrance between the SC3H6CN moiety and the Pd atom. To
the best of our knowledge, the anti and syn dimetallic complexes
3, 9a,b, and 11a-d are the first examples prepared with different
PPh2(CS2R) ligands. Complexes 3, 9a,b, and 11a-d show three
kinds of 31P{1H} NMR patterns owing to the different thio-
alkoxy groups in [W(CO)5[PPh2(CS2R)]]. The effects of the
geometric positions of the two phosphorus atoms, the metal,
and the remaining ligands and the types of substituents bound
to phosphorus on the 31P{1H} NMR patterns and coupling
constants of the [Pd(X)2(PR3)2] system have already been
reported in the literature.35 We attempted to produce dipalladium
complexes like 6 from the disproportionation reactions of the
two syn configurational complexes 9a and 11a, but neither
reaction occurred nor was there any exchange of the syn and
anti configurations, even by refluxing in CHCl3 for 1 h.
anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W(CO)5] (3), syn-[(Ph3P)2Pd-
[µ-η1,η2-(CS2Me)PPh2]W(CO)5] (4), and trans-[W(CO)4(PPh3)2] (5).
Diethyl ether (30 mL) was added to a flask (100 mL) containing [Pd-
(PPh3)4] (1) (1.155 g, 1.0 mmol) and [W(CO)5[PPh2(CS2Me)]] (2)
(0.600 g, 1.0 mmol). The solution was refluxed for 3 min, and the
31P{1H} NMR spectrum indicated that the reaction was complete. The
solvent was removed under reduced pressure, and the residue was
purified by chromatography on activated silica gel (length of column
20 cm). PPh3 was eluted with diethyl ether. Three fractions were
separated with 1/5 CH2Cl2/diethyl ether. The yellow product from band
1 was concentrated and cooled to -18 °C for 12 h to give a crystalline
solid. This product was recrystallized from 2/1 n-hexane/CH2Cl2 to give
the yellow complex anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W(CO)5] (3).
Yield: 0.68 g, 55%. IR (KBr, cm-1): ν(CO) 2060 (m), 1914 (vs), 1887
(s). 31P{1H} NMR (81 MHz, CDCl3, 298 K): δ 22.2, 22.4 (br, PPh3),
1
51.6 (1JW-P ) 257.6 Hz, PPh2CS2Me). H NMR (200 MHz, CDCl3,
298 K): δ 2.09 (s, 3H, SCH3), 7.0-7.4 (m, 40H, Ph). 13C{1H} NMR
(50 MHz, CDCl3, 298 K): δ 18.7 (s, SCH3), 127-134 (m, C of Ph),
198.8 (d, 2JP-C ) 6.7 Hz, cis CO), 208.2 (s, CS2), 214.9 (s, trans CO).
MS (FAB, NBA, m/z): 1231 [M+], 1216 [M+ - CH3]. Anal. Calcd
for C55H43O5P3PdS2W: C, 53.65; H, 3.52. Found: C, 53.41; H, 3.65.
The yellow-orange product from band 2 was recrystallized from 5/1
n-hexane/CH2Cl2 to give the complex syn-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)-
PPh2]W(CO)5] (4). Yield: 0.12 g, 10%. IR (KBr, cm-1): ν(CO) 2059
(m), 1914 (sh), 1875 (s). 31P{1H} NMR (81 MHz, CDCl3, 298 K): δ
Conclusion
We have compared the reactions of a range of diphenyl-
(dithioalkoxycarbonyl)phosphine complexes [W(CO)5[PPh2-
(CS2R)]] with [Pd(PPh3)4]. PPh2(CS2R), which acts as a bridging
ligand through phosphorus σ-bonding and CdS π-bonding
forms syn and anti configurational dimetallic complexes. The
diphenyl(dithiomethoxycarbonyl)phosphine transfer reaction
between [Pd(PPh3)4] and [W(CO)5[PPh2(CS2Me)]] (2) forms
[[(Ph3P)Pd[µ-η1,η2-(CS2Me)PPh2]]2] (6) as the ultimate product.
The reaction proceeds via a η2-coordination of the CdS
fragment to Pd, giving anti-[(Ph3P)2Pd[µ-η1,η2-(CS2Me)PPh2]W-
(CO)5] (3) as an intermediate. Increased hindrance of the
thioalkoxy groups exerts stereospecific control leading to the
formation of syn configurational complexes. Useful 31P{1H}
NMR patterns are able to differentiate configurational com-
pounds. In the syn form, one of the triphenylphosphines couples
with PPh2(CS2R) to give a doublet of doublet resonance or only
one singlet resonance when the thioalkoxy group is oriented
away from the Pd metal. In the anti form, the two singlet
resonances of the triphenylphosphines on Pd do not couple with
the response of the PPh2(CS2R) ligand on W.
2
3
2
21.7 (d, JP-P ) 39.1 Hz, PPh3), 25.2 (dd, JP-P ) 7.0 Hz, JP-P
)
39.1 Hz, PPh3), 28.8 (d, 1JW-P ) 204.5 Hz, 3JP-P ) 7.0 Hz, PPh2CS2-
Me). 1H NMR (200 MHz, CDCl3, 298 K): δ 2.22 (s, 3H, SCH3), 7.0-
7.4 (m, 40H, Ph). MS (FAB, NBA, m/z): 1231 [M+]. The orange-red
complex from band 3 is trans-[W(CO)4(PPh3)2] (5). Yield: 0.16 g, 20%.
IR (KBr, cm-1): ν(CO) 1873 (s). 31P{1H} NMR (81 MHz, CDCl3,
298 K): δ 27.7 (1JW-P ) 281.3 Hz, PPh3). 1H NMR (200 MHz, CDCl3,
298 K): δ 7.4-7.6 (m, 30H, Ph). 13C{1H} NMR (50 MHz, CDCl3,
298 K): δ 127-134 (m, C of Ph). MS (FAB, NBA, m/z): 819 [M+].
Anal. Calcd for C40H30O4P2W: C, 58.55; H, 3.69. Found: C, 58.85;
H, 3.53.
[[(Ph3P)Pd[µ-η1,η2-(CS2Me)PPh2]]2] (6) and [W(CO)5(PPh3)] (7).
A CHCl3 (10 mL) solution of 3 (0.123 g, 0.1 mmol) was stirred at
room temperature for 1 h, and the 31P{1H} NMR spectrum indicated
that the reaction was complete. The solvent was removed, and
recrystallization from 2/1 n-hexane/CH2Cl2 gave the yellow crystalline
product [[(Ph3P)Pd[µ-η1,η2-(CS2Me)PPh2]]2] (6). Yield: 0.04 g, 31%.
31P{1H} NMR (81 MHz, CDCl3, 298 K): δ 22.2 (s, PPh3), 53.7 (s,
PPh2CS2Me). 1H NMR (200 MHz, CDCl3, 298 K): δ 2.18 (s, 6H,
SCH3), 7.0-7.4 (m, 50H, Ph). 13C{1H} NMR (50 MHz, CDCl3, 298
1
K): δ 19.7 (s, SCH3), 127-134 (m, C of Ph), 198.1 (d, JP-C ) 26.5
Experimental Section
Hz, PCS2). MS (FAB, NBA, m/z): 1243 [M+ - SCH3], 981 [M+
-
SCH3-PPh3]. Anal. Calcd for C64H56P4Pd2S4: C, 59.58; H, 4.38.
Found: C, 59.24; H, 4.60. Another yellow complex, [W(CO)5(PPh3)]
(7), was isolated from the reaction in 40% yield. IR (KBr, cm-1): ν-
(CO) 2060 (m), 1914 (vs), 1887 (s). 31P{1H} NMR (81 MHz, CDCl3,
298 K): δ -10.2 (1JW-P ) 257.2 Hz, PPh3). 1H NMR (200 MHz,
CDCl3, 298 K): δ 7.0-7.4 (m, 15H, Ph). 13C{1H} NMR (50 MHz,
CDCl3, 298 K): δ 127-134 (m, C of Ph), 213.6, 214.9 (s, CO). MS
(FAB, NBA, m/z): 586 [M+], 558 [M+ - CO].
All manipulations were performed under nitrogen using vacuum-
line, drybox, and standard Schlenk techniques. NMR spectra were
recorded on a Bruker AM-200 or a Bruker AM-300 WB FT-NMR
spectrometer and are reported in units of parts per million with residual
protons in the solvent as an internal standard (CDCl3, δ 7.24; CD3CN,
δ 1.93; C6D6, δ 7.15; CD3COCD3, δ 2.04). IR spectra were measured
on a Perkin-Elmer 983 instrument and referenced to a polystyrene
standard, using cells equipped with calcium fluoride windows. Mass
spectra were recorded on a JEOL SX-102A spectrometer. Solvents were
dried and deoxygenated by refluxing over the appropriate reagents
before use. n-Hexane, diethyl ether, THF, and benzene were distilled
from sodium-benzophenone. Acetonitrile and dichloromethane were
distilled from calcium hydride, and methanol was distilled from
magnesium. All other solvents and reagents were of reagent grade and
were used as received. The compounds [W(CO)5[PPh2(CS2R)]]29 (R
) CH3, C2H5, C3H5, C2H4OH, CH2CN, CH2CH2CN, CH2CH2CH2CN)
and [Pd(PPh3)4]36 were prepared according to the literature methods.
syn-[(Ph3P)2Pd[µ-η1,η2-(CS2CH2CN)PPh2]W(CO)5] (9a). A CH2-
Cl2 (10 mL) solution of 8a (0.313 g, 0.5 mmol) was added to a
suspension of [Pd(PPh3)4] (0.576 g, 0.5 mmol) in 10 mL of n-hexane.
After the mixture was stirred for 3 min, the orange-yellow solution
was evaporated to dryness. The residue was washed five times with
n-hexane (each 10 mL) to give a yellow precipitate, which was collected
by filtration (G4) and dried in vacuo. Crystals of 9a were obtained
from CH2Cl2/n-hexane by slow diffusion. The complex syn-[(Ph3P)2-
Pd[µ-η1,η2-(CS2CH2CN)PPh2]W(CO)5] (9a) as a yellow microcrystal-
line solid was isolated in 85% yield. IR (KBr, cm-1): ν(CO) 2064 (s),
1973 (m), 1910 (vs). 31P{1H} NMR (81 MHz, CDCl3, 298 K): δ 22.5
(35) Diehl, P.; Fluck, E.; Kosfeld, R. 31P and 13C NMR of Transition Metal
Phosphine Complexes; Springer-Verlag: Berlin, 1979.
(36) Malatesta, L.; Angeoletta, M. J. Chem. Soc. 1957, 1186.
3
2
2
(dd, JP-P ) 10.0 Hz, JP-P ) 37.1 Hz, PPh3), 24.7 (d, JP-P ) 37.1
Hz, PPh3), 54.2 (d, 1JW-P ) 255.0 Hz, 3JP-P ) 10.0 Hz, PPh2CS2). 1H

Isomers of Tungsten-Palladium Complexes
Inorganic Chemistry, Vol. 39, No. 12, 2000 2451
2
NMR (200 MHz, CDCl3, 298 K): δ 2.81 (d, JH-H ) 16.4 Hz, 1H,
CH2CH2CH2CN)PPh2]W(CO)5] (11d) was isolated in 92% yield. IR
(THF, cm-1): ν(CO) 2065 (m), 1926 (vs). 31P{1H} NMR (81 MHz,
2
SCH2), 3.19 (d, JH-H ) 16.4 Hz, 1H, SCH2), 7.0-7.4 (m, 40H, Ph).
13C{1H} NMR (50 MHz, CDCl3, 298 K): δ 20.1 (s, SCH2), 117.7 (s,
CN), 127-137 (m, C of Ph), 198.6 (d, 2JP-C ) 6.7 Hz, cis-CO), 200.6
CDCl3, 298 K): δ 23.3 (s, PPh3), 54.5 (br, JW-P ) 252.9 Hz, PPh2-
1
1
CS2). H NMR (200 MHz, CDCl3, 298 K): δ 1.80 (m, 2H, CH2CH2-
(s, CS2). MS (FAB, NBA, m/z): 1216 [M+ - CH2CN], 1160 [M+
-
CN), 2.16 (t, JH-H ) 8.1 Hz, 2H, CH2CN), 2.83 (t, JH-H ) 8.1 Hz,
2H, SCH2), 7.0-7.4 (m, 40H, Ph). 13C{1H} NMR (50 MHz, CDCl3,
298 K): δ 16.0 (s, CH2CH2CN), 24.7 (s, CH2CN), 34.7 (s, SCH2),
3
3
CH2CN - 2CO], 1076 [M+ - CH2CN - 5CO], 630 [M+ - CH2CN
- 5CO - WPPh2CS2]. Anal. Calcd for C56H42NO5P3PdS2W: C, 53.54;
H, 3.37; N, 1.12. Found: C, 53.32; H, 3.62; N, 1.54.
2
119.3 (s, CN), 127-137 (m, C of Ph), 198.6 (d, JP-C ) 6.9 Hz, cis
syn-[(Ph3P)2Pd[µ-η1,η2-(CS2CH2CH2CN)PPh2]W(CO)5] (9b). The
procedures for synthesis and workup were similar to those for 9a. The
yellow, microcrystalline complex syn-[(Ph3P)2Pd[µ-η1,η2-(CS2CH2CH2-
CN)PPh2]W(CO)5] (9b) was isolated in 90% yield. IR (THF, cm-1):
ν(CO) 2072 (m), 1972 (vs). 31P{1H} NMR (81 MHz, CDCl3, 298 K):
CO), 212.5 (s, CS2), 220.4 (s, trans CO). MS (FAB, NBA, m/z): 1284
[M+], 1216 [M+ - CH2CN - CO], 630 [M+ - CH2CN - W(CO)5PPh2-
CS2CH2CH2]. Anal. Calcd for C58H46NO5P3PdS2W: C, 54.24; H, 3.61;
N, 1.09. Found: C, 54.62; H, 3.20; N, 0.98.
Single-Crystal X-ray Diffraction Analyses of 3, 6, 9a, and 11d.
Single crystals of 3, 6, 9a, and 11d suitable for X-ray diffraction
analyses were grown by recrystallization from 20/1 n-hexane/CH2Cl2.
The diffraction data were collected at room temperature on an Enraf-
Nonius CAD4 diffractometer equipped with graphite-monochromated
Mo KR (λ ) 0.710 73 Å) radiation. The raw intensity data were
converted to structure factor amplitudes and their esd’s after correction
for scan speed, background, Lorentz, and polarization effects. An
empirical absorption correction, based on the azimuthal scan data, was
applied to the data. Crystallographic computations were carried out on
a Microvax III computer using the NRCC-SDP-VAX structure deter-
mination package.37
A suitable single crystal of 3 was mounted on the top of a glass
fiber with glue. Initial lattice parameters were determined from 24
accurately centered reflections with 2θ values in the range from 18.86
to 30.22°. Cell constants and other pertinent data were collected and
are recorded in Table 1. Reflection data were collected using the θ/2θ
scan method. The final scan speed for each reflection was determined
from the net intensity gathered during an initial prescan and ranged
from 2.06 to 8.24° min-1. The θ scan angle was determined for each
reflection according to the expression 0.85 ( 0.35 tan θ. Three check
reflections were measured every 30 min throughout the data collection
and showed no apparent decay. The merging of equivalent and duplicate
reflections gave a total of 6742 unique measured data, of which 4777
reflections with I > 2σ(I) were considered observed. The first step of
the structure solution used the heavy-atom method (Patterson synthesis),
which revealed the positions of the metal atoms. The remaining atoms
were found in a series of alternating difference Fourier maps and least-
squares refinements. The quantity minimized by the least-squares
program was w(|Fo| - |Fc|)2, where w is the weight of a given operation.
The analytical forms of the scattering factor tables for the neutral atoms
were used.38,39 The non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included in the structure factor calculations in
their expected positions on the basis of idealized bonding geometry
but were not refined in least squares. All hydrogens were assigned
isotropic thermal parameters 1-2 Å2 larger than the equivalent Biso
values of the atoms to which they were bonded. The final residuals of
this refinement were R ) 0.040 and Rw ) 0.042.
3
2
2
δ 23.4 (dd, JP-P ) 7.9 Hz, JP-P ) 33.5 Hz, PPh3), 24.2 (d, JP-P
)
33.5 Hz, PPh3), 55.7 (br, 1JW-P ) 258.4 Hz, PPh2CS2). 1H NMR (200
MHz, CDCl3, 298 K): δ 2.90 (t, JH-H ) 6.7 Hz, 2H, SCH2), 3.44 (t,
JH-H ) 6.7 Hz, 2H, CH2CN), 7.0-7.4 (m, 40H, Ph). 13C{1H} NMR
(50 MHz, CDCl3, 298 K): δ 15.2 (s, SCH2), 21.7 (s, CH2CN), 117.1
2
(s, CH2CN), 127-137 (m, C of Ph), 198.6 (d, JP-C ) 6.9 Hz, cis
CO), 200.6 (s, CS2), 210.2 (s, trans CO). MS (FAB, NBA, m/z): 1216
[M+ - C2H4CN], 1076 [M+ - C2H4CN - 5CO], 630 [M+ - C2H4CN
- 5CO - WPPh2CS2]. Anal. Calcd for C57H44NO5P3PdS2W: C, 53.89;
H, 3.49; N, 1.10. Found: C, 53.95; H, 3.60; N, 1.01.
syn-[(Ph3P)2Pd[µ-η1,η2-(CS2C2H5)PPh2]W(CO)5] (11a). CH2Cl2
(10 mL) was added to a flask (50 mL) containing 10a (0.307 g, 0.5
mmol) and [Pd(PPh3)4] (0.577 g, 0.5 mmol). The color of the solution
turned from red to yellow in 3 min. The solution was then evaporated
to dryness. The yellow residue was stirred with 30 mL of n-hexane/
diethyl ether (2/1) to yield a yellow precipitate, which was crystallized
from CH2Cl2/n-hexane by slow diffusion. The yellow crystals were
collected and dried in vacuo to give the complex syn-[(Ph3P)2Pd[µ-
η1,η2-(CS2C2H5)PPh2]W(CO)5] (11a) in 82% yield. IR (THF, cm-1):
ν(CO) 2072 (m), 1933 (vs). 31P{1H} NMR (81 MHz, CDCl3, 298 K):
δ 22.7 (s, PPh3), 52.6 (1JW-P ) 249.0 Hz, PPh2CS2). H NMR (200
1
MHz, CDCl3, 298 K): δ 1.29 (t, JH-H ) 7.4 Hz, 3H, CH3), 3.30 (q,
JH-H ) 7.4 Hz, 2H, SCH2), 7.0-7.4 (m, 40H, Ph). 13C{1H} NMR (50
MHz, CDCl3, 298 K): δ 12.7 (s, CH3), 30.6 (s, SCH2), 127-137 (m,
2
C of Ph), 197.0 (d, JP-C ) 8.3 Hz, cis CO). MS (FAB, NBA, m/z):
1245 [M+], 1217 [M+ - CO], 630 [M+ - W(CO)5PPh2CS2C2H5]. Anal.
Calcd for C56H45O5P3PdS2W: C, 54.01; H, 3.64. Found: C, 54.31; H,
3.80.
syn-[(Ph3P)2Pd[µ-η1,η2-(CS2C3H5)PPh2]W(CO)5] (11b). The pro-
cedures for synthesis and workup were similar to those for complex
11a. The yellow, microcrystalline complex syn-[(Ph3P)2Pd[µ-η1,η2-
(CS2C3H5)PPh2]W(CO)5] (11b) was isolated in 88% yield. IR (THF,
cm-1): ν(CO) 2068 (m), 1928 (vs). 31P{1H} NMR (81 MHz, CDCl3,
298 K): δ 22.7 (s, PPh3), 53.1 (1JW-P ) 252.6 Hz, PPh2CS2). 1H NMR
3
(200 MHz, CDCl3, 298 K): δ 3.42 (d, JH-H ) 6.6 Hz, 2H, SCH2),
4.93 (m, 2H, CHCH2), 5.66 (m, 1H, CHCH2), 7.0-7.4 (m, 40H, Ph).
13C{1H} NMR (50 MHz, CDCl3, 298 K): δ 40.1 (s, SCH2), 117.1 (s,
HCd), 117.6 (s, dCH2), 127-137 (m, C of Ph), 198.8 (d, 2JP-C ) 6.9
Hz, cis CO). MS (FAB, NBA, m/z): 1257 [M+], 1216 [M+ - C3H5],
630 [M+ - C3H5 - W(CO)5PPh2CS2]. Anal. Calcd for C57H45O5P3-
PdS2W: C, 54.45; H, 3.61. Found: C, 54.60; H, 3.82.
The procedures for 6, 9a, and 11d were similar to those for 3. The
final residuals of the refinements were R ) 0.034 and Rw ) 0.037 for
6, R ) 0.047 and Rw ) 0.044 for 9a, and R ) 0.038 and Rw ) 0.041
for 11d.
syn-[(Ph3P)2Pd[µ-η1,η2-(CS2C2H4OH)PPh2]W(CO)5] (11c). The
procedures for synthesis and workup were similar to those for complex
11a. The yellow, microcrystalline complex syn-[(Ph3P)2Pd[µ-η1,η2-
(CS2C2H4OH)PPh2]W(CO)5] (11c) was isolated in 80% yield. IR (THF,
cm-1): ν(CO) 2071 (m), 1932 (vs). 31P{1H} NMR (81 MHz, CDCl3,
298 K): δ 23.6 (s, PPh3), 55.3 (1JW-P ) 255.8 Hz, PPh2CS2). 1H NMR
(200 MHz, CDCl3, 298 K): δ 3.52 (m, 2H, SCH2), 3.78 (m, 2H, CH2O),
7.0-7.4 (m, 40H, Ph). 13C{1H} NMR (50 MHz, CDCl3, 298 K): δ
39.4 (s, SCH2), 60.8 (s, CH2OH), 127-137 (m, C of Ph), 197.1 (d,
2JP-C ) 8.3 Hz, cis CO). MS (FAB, NBA, m/z): 1261 [M+], 1216
[M+ - CH2CH2OH], 630 [M+ - C2H5OH - W(CO)5PPh2CS2]. Anal.
Calcd for C56H45O6P3PdS2W: C, 53.32; H, 3.60. Found: C, 53.75; H,
3.87.
Acknowledgment. We thank the National Science Council
of Taiwan, Republic of China, for support.
Supporting Information Available: X-ray crystallographic files,
in CIF format, for the structures of complexes 3, 6, 9a, and 11d‚CHCl3.
This material is available free of charge via the Internet at http://
pubs.acs.org.
IC9904438
(37) Gabe, E. J.; Lee, F. L.; Lepage, Y. In Crystallographic Computing 3;
Sheldrick, G. M., Kruger, C., Goddard, R., Eds.; Clarendon Press:
Oxford, England, 1985; p 167.
(38) International Tables for X-ray Crystallography; Reidel: Dordrecht.
Boston, 1974; Vol. IV.
syn-[(Ph3P)2Pd[µ-η1,η2-(CS2C3H6CN)PPh2]W(CO)5] (11d). The
procedures for synthesis and workup were similar to those for complex
11a. The yellow, microcrystalline complex syn-[(Ph3P)2Pd[µ-η1,η2-(CS2-
(39) LePage, Y.; Gabe, E. J. Appl. Crystallogr. 1990, 23, 406.