Synthesis and reactivity of bridging and terminal hydrosulfido palladium and platinum complexes. Crystal structures of [NBU4]2[{PT(C6F5)2 (μ-SH)}2], [Pt(C6F5)2</s

Article abstract of DOI:10.1021/ic0013633

The reactions of the hydroxo complexes [M₂R₄(μ-OH)₂]^2- (M=Pd, R=C₆F₅, C₆Cl₅; M=Pt, R=C₆F₅), [{PdR(PPh₃)(μ-OH)}₂] (R=C₆

Full text of DOI:10.1021/ic0013633

5354
Inorg. Chem. 2001, 40, 5354-5360
Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum
Complexes. Crystal Structures of [NBu4]2[{Pt(C6F5)2(µ-SH)}2],
[Pt(C6F5)2(PPh3){S(H)AgPPh3}], and [Pt(C6F5)2(PPh3){S(AuPPh3)2}]
Jose´ Ruiz,* Venancio Rodr´ıguez, Consuelo Vicente, Jose´ M. Mart´ı, and Gregorio Lo´pez
Departamento de Qu´ımica Inorga´nica, Universidad de Murcia, 30071-Murcia, Spain
Jose´ Pe´rez
Departamento de Ingenier´ıa Minera, Geolo´gica y Cartogra´fica. AÄ rea de Qu´ımica Inorga´nica,
Universidad Polite´cnica de Cartagena, 30203, Cartagena, Spain
ReceiVed December 6, 2000
The reactions of the hydroxo complexes [M2R4(µ-OH)2]2- (M ) Pd, R ) C6F5, C6Cl5; M ) Pt, R ) C6F5),
[{PdR(PPh3)(µ-OH)}2] (R ) C6F5, C6Cl5), and [{Pt(C6F5)2}2(µ-OH)(µ-pz)]2- (pz ) pyrazolate) with H2S yield
the corresponding hydrosulfido complexes [M2(C6F5)4(µ-SH)2]2-, [{PdR(PPh3)(µ-SH)}2], and [{Pt(C6F5)2}2(µ-
SH)(µ-pz)]2-, respectively. The monomeric hydrosulfido complexes [M(C6F5)2(SH)(PPh3)]- (M ) Pd, Pt) have
been prepared by reactions of the corresponding binuclear hydrosulfido complexes [M2(C6F5)4(µ-SH)2]2- with
PPh3 in the molar ratio 1:2, and they can be used as metalloligands toward Ag(PPh3)+ to form the heterodinuclear
complex [(C6F5)2(PPh3){S(H)AgPPh3}], and toward Au(PPh3)+ yielding the heterotrinuclear complexes [M(C6F5)2-
(PPh3){S(AuPPh3)2}]. The crystal structures of [NBu4]2[{Pt(C6F5)2(µ-SH)}2], [Pt(C6F5)2(PPh3){S(H)AgPPh3}],
and [Pt(C6F5)2(PPh3){S(AuPPh3)2}] have been established by X-ray diffraction and show no short metal-metal
interactions between the metallic centers.
Introduction
The µ-hydroxo complexes of palladium and platinum of the
types [M2R4(µ-OH)2]2- (M ) Pd, R ) C6F5, C6Cl5; M ) Pt, R
) C6F5),12,13 [{PdR(PPh3)(µ-OH)}2] (R ) C6F5, C6Cl5; L )
PPh3),14 and [{Pt(C6F5)2}2(µ-OH)(µ-pz)]2- (pz ) pyrazolate)15
have been shown to be excellent precursors in synthetic
work.17-19 We report now their reactions with H2S gas to give
the first bridging hydrosulfido palladium and platinum com-
plexes. The mononuclear hydrosulfido complexes [M(C6F5)2(SH)-
(PPh3)]- (M ) Pd, Pt), prepared from the corresponding dimers
by addition of PPh3 in the molar ratio 1:2, can be used as
metalloligands toward M′(PPh3)+ (M′ ) Ag or Au), yielding
heterobinuclear or heterotrinuclear complexes. In the hetero-
trinuclear complexes [M(C6F5)2(PPh3){S(AuPPh3)2}], it is pos-
sible to envisage the isolobal analogy existing between the
hydrogen atom and the AuPR3 fragment. Some of these
There is much current interest in the chemistry of transition
metal hydrosulfido complexes, mainly because these are useful
in understanding many catalytic processes, such as hydrogena-
tion and hydrodesulfuration.1,2 However, these species are still
quite rare, and hydrosulfido palladium or platinum complexes
are very poorly represented. Only some terminal hydrosulfido
compounds of the types [ML2(SH)2] (M ) Pd or Pt; L2 ) 2
PPh3, 2 PEt3, 2 PiBu3, or diphos),3-5 [PtH(SH)L2] (L2 ) 2 PPh3,
2 PEt3),6,7 [PtH(SH)(triphos)],8 or [PtR(SH)(dcpe)] (dcpe ) Cy2-
PC2H4PCy2, R ) Me, Ph, CH2tBu)9 have been reported and, to
the best of our knowledge, no examples of bridging hydrosulfido
palladium or platinum are known so far. A tetranuclear
palladium cluster with sulfide ligands, [{Pd(η3-C4H7)}4S2],
synthesized from the reaction of [Pd(η3-C4H7)2] and H2S,10 has
been shown to serve as a homogeneous catalyst.11
(11) Bogdanovic, B.; Gottsch, P.; Rubach, M. J. Mol. Catal. 1981, 11,
135.
* To whom correspondence should be addressed. E-mail: jruiz@um.es.
(1) Angelici, R. J. Acc. Chem. Res. 1988, 21, 387, and references therein.
(2) Rakowski-Dubois, M. Chem. ReV. 1989, 89, 2, and references therein.
(3) Schmidt, M.; Hoffmann, G. G.; Ho¨ller, R. Inorg. Chim. Acta 1979,
32, L19.
(4) Shaver, A.; Lai, R. D.; Bird, P.; Wickramsasinghe, W. Can. J. Chem.
1985, 63, 2555.
(12) Lo´pez, G.; Ruiz, J.; Garc´ıa, G.; Vicente, C.; Casabo´, J.; Molins, E.;
Miravitlles, C. Inorg. Chem. 1991, 30, 2605.
(13) Lo´pez, G.; Ruiz, J.; Garc´ıa, G.; Mart´ı, J. M.; Sa´nchez, G.; Garc´ıa, J.
J. Organomet. Chem. 1991, 412, 435.
(14) Lo´pez, G.; Ruiz, J.; Garc´ıa, G.; Vicente, C.; Mart´ı, J. M.; Hermoso,
J. A.; Vegas, A.; Mart´ınez-Ripoll, M. J. Chem. Soc., Dalton Trans.
1992, 53.
(5) Ghillardi, C. A.; Midollini, S.; Nazzi, F.; Orlandini, A. Transition Met.
Chem. 1983, 8, 73.
(6) Ugo, R.; La Monica, G.; Cenini, S.; Segre, A.; Conti, F. J. Chem.
Soc. A 1971, 522.
(7) Garc´ıa, J. J.; Maitlis, P. M. J. Am. Chem. Soc. 1993, 115, 12200.
(8) Cecconi, F.; Innocenti, P.; Midollini, S.; Moneti, S.; Vacca, A.;
Ramirez, J. A. J. Chem. Soc., Dalton Trans. 1991, 1129.
(9) Morton, M. S.; Lachicotte, R. J.; Vicic, D. A.; Jones, W. D.
Organometallics 1999, 18, 227.
(15) Ruiz, J.; C. Vicente, C.; Mart´ı, J. M.; Cutillas, N., Garc´ıa, G.; Lo´pez,
G. J. Organomet. Chem. 1993, 460, 241.
(16) Lo´pez, G.; Ruiz, J.; Garc´ıa, G.; Vicente, C.; Rodr´ıguez, V.; Sa´nchez,
G.; Hermoso, J. A.; Mart´ınez-Ripoll, M. J. Chem. Soc., Dalton Trans.
1992, 1681.
(17) Ruiz, J.; M. T. Mart´ınez; Vicente, C.; Garc´ıa, G.; Lo´pez, G.; Chaloner,
P. A.; Hitchcock, P. B. Organometallics 1993, 12, 1594.
(18) Ruiz, J.; Rodr´ıguez, V.; Lo´pez, G.; Chaloner, P. A.; Hitchcock, P. B.
Organometallics 1996, 15, 1662.
(10) Bogdanovic, B.; Gottsch, P.; Rubach, M. Z. Naturforsch. B 1983, 38,
599.
(19) Ruiz, J.; Rodr´ıguez, V.; Lo´pez, G.; Casabo´, J.; Molins, E.; Miravitlles,
C. Organometallics 1999, 18, 1177.
10.1021/ic0013633 CCC: $20.00 © 2001 American Chemical Society
Published on Web 09/06/2001

Bridging and Terminal Hydrosulfido Pd and Pt Complexes
Inorganic Chemistry, Vol. 40, No. 21, 2001 5355
Scheme 1
Figure 1. ORTEP diagram of 3.
Table 1. Selected Distances (Å) and Bond Angles (deg) for
Complex 3a
Bond Distances
Bond Angles
C(11)-Pt(1)-C(21)
C(11)-Pt(1)-S(1)#1
polynuclear complexes have been characterized by X-ray
diffraction, and the crystal structure of a binuclear hydrosulfido
platinum complex is reported for the first time.
Pt(1)-C(11)
2.009 (5)
2.014(5)
90.4(2)
Pt(1)-C(21)
Pt(1)-S(1)#1
Pt(1)-S(1)
91.37(13)
2.3591(15) C(21)-Pt(1)-S(1)#1 178.22(15)
2.3577(15) C(11)-Pt(1)-S(1)
3.494(1)
175.72(15)
93.82(15)
84.43(6)
Pt(1)‚‚‚Pt(1)#
C(21)-Pt(1)-S(1)
S(1)#1-Pt(1)-S(1)
Results and Discussion
a Symmetry transformations used to generate equivalent atoms: # 1
- x + 1, -y + 1, -z.
µ-Hydrosulfido Palladium and Platinum Complexes [M2-
(C6F5)4(µ-SH)2]2-, [{Pd(R)(PPh3)(µ-SH)}2], and [{Pt(C6F5)2}2-
(µ-SH)(µ-pz)]2-. The di-µ-hydroxo palladium and platinum
complexes [NBu4]2[{M(R)2(µ-OH)}2] (M ) Pd, R ) C6F5, C6-
Cl5; M ) Pt, R ) C6F5) and [{Pd(R)(PPh3)(µ-OH)}2] (R )
C6F5, C6Cl5; L ) PPh3) react with H2S to yield the correspond-
ing binuclear di-µ-hydrosulfido complexes [NBu4]2[{M(R)2(µ-
OH)}2] and [{Pd(R)(PPh3)(µ-SH)}2] 1-5 (Scheme 1) with the
concomitant formation of H2O.
(for HOD). The 1H NMR spectra of 1-3 also show the signals
assigned to the protons of the NBu4 group. The resonance at δ
1
-1.19 ppm in the H NMR of complex 3 is flanked by 195Pt
satellites (I ) 1/2, natural abundance 33.8%; 2JPtH ) 37.2 Hz).
The 19F NMR data of complex 4 and the 31P{1H} NMR data of
complexes 4 and 5 show unambiguously that they exist in
1
chloroform solution as only one isomer. Since the H spectra
Complexes 1-5 have been characterized on the basis of
partial elemental analyses and spectroscopic data. The IR-active
band corresponding to the V(SH) mode, which usually appears
in the range 2300-2600 cm-1, is not observed; its weakness is
a common feature of most SH complexes. The IR spectra show
the bands attributed to the C6F5 (1630, 1490, 1460, 1050, and
of 4 and 5 exhibit a unique high-field resonance for the SH
groups, consisting of a doublet arising from coupling to 31P of
the phosphine trans to SH, it should exist as the anti isomer, as
it also occurs with the hydroxo precursor complex.11 The 19F
NMR spectrum of complex 4 shows two broad resonances in
the o-F region, together with one sharp triplet for the p-F atoms,
suggesting restricted rotation of the perfluorophenyl rings around
the Pd-C bond. The 19F NMR spectrum of 4 at -50 °C shows
two sharp doublets in the o-F region (δ -114.4, d, Jom ) 33.6
and δ -117.0, d, Jom ) 31.9). It is noteworthy that the dinuclear
palladium complex with bridging sulfide ligands [Pd2(dppe)2-
(µ-S)2] has been very recently successfully prepared from [Pd-
(dppe)Cl2] and an excess of Na2S‚9H2O, though it easily evolves
into the trimetallic species [Pd3(dppe)2(µ3-S)2]Cl2.25
The crystal structure of 3 has been established by X-ray
diffraction. A view of complex 3 is given in Figure 1. Selected
bond distances and angles are presented in Table 1. The complex
is a centrosymmetric dinuclear unit where two hydrosulfido
anions bridge two Pt(C6F5)2 fragments through the sulfur atoms.
Coordination at each of the platinum centers is essentially square
planar, the largest deviation from the best plane through the
atoms defining the coordination plane is 0.005(2) Å, and the
largest deviation from the ideal angles is for C(11)-Pt(1)-
S(1), which shows a value of 175.7(2)°. The Pt‚‚‚‚Pt distance
is 3.494(1) Å, showing no significant metal-metal interaction.
The two C6F5 rings on each Pt are planar and rotated 88.7(2)°
with respect to each other.
950 cm-1 20 or C6Cl5 (1315, 1285, 1220, and 670 cm-1 21
)
)
groups. Morever, a split absorption, located at ca. 800 cm-1 in
the spectra of the bis(pentafluorophenyl) derivatives or at ca.
830 cm-1 for the bis(pentachlorophenyl)derivatives, has been
previously used for structural elucidation.22 It is derived from
the so-called halogen-sensitive mode in C6F5 and C6Cl5 halogen
molecules, and in square-planar MR2L2 (R ) C6F5, C6Cl5)
complexes, it is related to the skeletal symmetry of the entire
molecule22 and behaves like a V(M-C) which is characteristic
of the cis-MR2 fragment (C2V symmetry). Complexes 1-3
behave as 1:2 electrolytes in acetone solution,23 in accordance
with the formulas given.
All the complexes exhibit a high field resonance (δ -2 to
-1.2) in their 1H NMR spectra due to the SH ligand. This SH
signal appears in most other late transition metal complexes in
the range δ -4 to +2.24 Upon addition of D2O to an NMR
sample of 1 in acetone-d6, the SH signal disappears from its
previous position (δ -2.03) and a new signal at δ 3.7 arises
(20) Long, D. A.; Steel, D. Spectrochim. Acta 1963, 19, 1955.
(21) Casabo´, J.; Coronas, J. M.; Sales, J. Inorg. Chim. Acta 1974, 11 , 5.
(22) E. Maslowski, Vibrational Spectra of Organometallic Compounds,
Wiley: New York, 1977; p 437.
(23) Geary, W. J. Coord. Chem. ReV. 1971, 7, 81.
(24) Tang, Z.; Nomura, Y.; Ishii, Y.; Mizobe, Y.; Hidai, M. Inorg. Chim.
Acta 1998, 267, 73, and references therein.
(25) Capdevila, M.; Clegg, W.; Coxall, R. A., Gonza´lez-Duarte, M., Hamidi,
M., Lledo´s, A., Ujaque, G. Inorg. Chem. Commun. 1998, 1, 466.

5356 Inorganic Chemistry, Vol. 40, No. 21, 2001
Ruiz et al.
Scheme 2
Scheme 4
Scheme 3
absorptions assignable to the X-sensitive mode of the C6F5
groups20 suggests that they are on cis positions.22 The absorp-
tions in the 500 cm-1 region due to the PPh3 ligand show the
typical pattern for this ligand bound to Pd or Pt.
The 19F NMR spectra of 7 and 8 show the presence of two
different sets of resonances, each with an intensity ratio 2:1:2
(2Fo:1Fp:2Fm), revealing the presence of two different pen-
tafluorophenyl groups, one trans to S and one trans to P (a
multiplet resonance for the o-F atoms being observed due to
coupling to 31P). A singlet resonance is observed in the 31P NMR
spectra of 7 and 8 at δ 28.7 and 22.0, respectively, flanked by
195Pt satellites (3JPtFo ) 2677 Hz) in complex 8. The H NMR
1
The mixed µ-hydroxo-µ-pyrazolate complex [{Pt(C6F5)2}2-
(µ-OH)(µ-pz)]2- reacts in methanol with H2S to yield the
heterobridged µ-hydrosulfido-µ-pyrazolate complex [{Pt(C6F5)2}2-
(µ-SH)(µ-pz)]2- 6 (Scheme 2). This reaction implies protonation
of the hydroxo group and replacement by µ-SH. The micro-
analytical data and molar conductance in acetone solution is in
agreement with the proposed formula.
spectra of 7 and 8 exhibit, in each case, a high field resonance
for the SH group consisting of a doublet at δ -2.26 and -2.03,
respectively, arising from coupling to 31P of the phosphine (3JPH
) 12.9 Hz), and flanked by 195Pt satellites (2JPtH ) 50.8 Hz) in
complex 8. This resonance is observed at a higher field than in
the corresponding dimeric precursors 1 and 3, respectively.
No reaction was observed when complex 4 was treated with
PPh3 (1:2 molar ratio) in refluxing acetone for 3 h (see
experimental).
1
The H NMR spectrum of 6 shows one resonance at δ 5.69
(H4) and one resonance at δ 6.99 (H3 and H5), with relative
intensities of 1:2, which is consistent with the presence of a
bridging pyrazolate ligand.12 It should be noted that the µ-SH
resonance at δ -1.19 in 3 moves to a lower field (δ -0.45
ppm) in the µ-hydrosulfido-µ-pyrazolate complex 6, a result
that can be attributed to the increased electron delocalization
in the bridging system when one µ-SH group is substituted by
the pyrazolate ligand.9,12 The 19F NMR spectrum of 6 is in
accordance with the presence of two pairs of nonequivalent C6F5
groups freely rotating around the Pt-C bonds, one trans to S
and one trans to N, with two resonances in the o-fluorine region
(flanked by 195Pt satellites; 2JPtH ) 40.6 Hz) and two resonances
both in the p- and m-fluorine regions.
[M(C6F5)2(PPh3){S(H)AgPPh3}] and [M(C6F5)2(PPh3)-
{S(AuPPh3)2}]. The recently reported reaction of the related
dimeric hydrosulfido gold complex NBu4[{Au(C6F5)3}2SH] with
[Au(OClO3)(PPh3)] or [Ag(O3SCF3)(PPh3)] in the presence of
Na2CO3 , yielding sulfur-centered gold complexes NBu4[{Au-
(C6F5)3}2SR] (R ) AuPPh3, AgPPh3),26 prompted us to try the
reaction of [M(C6F5)2(SH)(PPh3)]- 7 (M ) Pd) and 8 (M )
Pt) with the [M′PPh3]+ (M′ ) Ag or Au) moiety to check
whether they can behave as mononuclear metalloligands.
Complexes 7 and 8 react with [Ag(O3SCF3)(PPh3)] in a 1:1
ratio affording the heterobinuclear complexes [M(C6F5)2(PPh3)-
{S(H)AgPPh3}] 9 or 10 (Scheme 4). Both complexes are
nonconducting in acetone solution.
Monomeric Palladium and Platinum Complexes [M(C6F5)2-
(SH)(PPh3)]-. The di-µ-hydrosulfido complexes [M2(C6F5)4-
(µ-SH)2]2- 1 and 3 react with PPh3 (1:2 molar ratio) to yield
the corresponding hydrosulfido monomeric complexes [M(C6F5)2-
(SH)(PPh3)]- (M ) Pd 7, Pt 8) (Scheme 3). The microanalytical
data are in agreement with the proposed formulas. Measurements
of the molar conductivities in acetone indicate that complexes
7 and 8 behave as 1:1 electrolytes.23 The presence of two
The 19F NMR spectra of 9 and 10 are in accordance with the
presence of two pairs of non equivalent C6F5 groups freely
rotating around the M-C bonds (M ) Pd or Pt), one trans to
S and one trans to P. The 31P{1H} NMR spectra of 9 and 10
(26) Canales, F.; Canales, S.; Grespo, O.; Gimeno, M. C.; Jones, P. G.;
Laguna, A. Organometallics 1998, 17, 1617.

Bridging and Terminal Hydrosulfido Pd and Pt Complexes
Inorganic Chemistry, Vol. 40, No. 21, 2001 5357
Figure 3. ORTEP diagram of 12.
Figure 2. ORTEP diagram of 10.
175.71(9)°. The Pt(1)-S(1) distance in complex 10 (2.3617 (12)
Å) is very similar to that found in [Pt(C6F5)2(PPh3)(C5H4NS)-
AgPPh3].28 The Ag(1)‚‚‚‚Pt(1) distance (3.366(1) Å) is too long
to be considered a bonding interaction. The Pt(1)-S(1)-
Ag(1) angle is very small, showing a value of 89.64 (5)°.
Owing to the isolobal analogy between the hydrogen atom
and the AgPR3 fragment, we also tried the treatment of
complexes 7 or 8 with [Ag(O3SCF3)(PPh3)] in a 1:2 ratio in
order to get the trinuclear complexes [M(C6F5)2(PPh3)-
{S(AgPPh3)2}] (M ) Pd or Pt). However, we obtained the
mononuclear complex [Pd(C6F5)2(PPh3)2] (as shown by mi-
croanalysis and 31P NMR data)29 and Ag2S (for 7) or mixtures
containing the heterobinuclear complex [Pt(C6F5)2(PPh3){S(H)-
AgPPh3}] 10 together with [Pt(C6F5)2(PPh3)2] and Ag2S (for
8) (Scheme 4). As mentioned above, the reaction of the related
hydrosulfido gold complex NBu4[{Au(C6F5)3}2SH] with [Ag-
(O3SCF3)(PPh3)] yields the sulfur-centered heterotrinuclear
complex NBu4[{Au(C6F5)3}2S(AgPPh3)].26
Table 2. Selected Distances (Å) and Bond Angles (deg) for
Complex 10
Bond Distances
Bond Angles
P(2)-Ag(1)-S(1)
Pt(1)-C(7)
2.037 (5)
2.059(5)
167.05 (6)
89.06 (19)
92.96 (14)
176.72 (15)
176.73 (16)
89.35 (14)
88.76 (5)
Pt(1)-C(1)
Pt(1)-P(1)
Pt(1)-S(1)
Ag(1)-P(2)
S(1)-Ag(1)
Pt(1)‚‚‚Ag(1)
C(7)-Pt(1) -C(1)
C(7)-Pt(1)-P(1)
C(7)-Pt(1)-S(1)
C(1)-Pt(1)-P(1)
C(1)-Pt-S(1)
2.2860 (14)
2.3617 (12)
2.3869 (15)
2.4142 (14)
3.366(1)
P(1)-Pt(1)-S(1)
Pt(1)-S(1)-Ag(1)
89.64(5)
show the presence of two chemically nonequivalent phosphorus
atoms, with relative intensities of 1:1, one of which is bound to
palladium (for 9) or platinum (for 10), as revealed by the
presence for 10 of the characteristic 195Pt satellites (δ 16.5 ppm,
1JPtP ) 2467 Hz), and the other phosphorus atom is bound to
silver (δ 13.8 and 12.0 ppm for 9 and 10, respectively); its
resonance appears as a broad signal at room temperature that
sharpens at -50 °C into two doublets because of the coupling
with the silver nuclei 107Ag and 109Ag (1J (107Ag,31P) ) 570
Hz, 1J (109Ag,31P) ) 657 Hz). The broadening observed at room
temperature for this signal can be ascribed to an operative
dynamic process, possibly involving dissociation of the PPh3
ligand as is frequently observed in the coordination chemistry
On the other hand, treatment of complexes 7 or 8 with [Au-
(O3SCF3)(PPh3)] in a 1:2 ratio produces the heterotrinuclear
complexes [M(C6F5)2(PPh3){S(AuPPh3)2}] 11 or 12 (Scheme
4).
The 31P{1H} NMR spectra of the trinuclear complexes 11
and 12 show the presence of two different resonances, with
relative intensities of 1:2, one of which is assigned to the P
bound to palladium (for 11) or to platinum (for 12, 1JPtP ) 2518),
and the other resonance is assigned to the phosphorus atoms
bonded to the two gold metal centers, which is observed at
higher frequency.
1
of silver.27 The H NMR spectra of 9 and 10 exhibit, in each
case, a high field resonance for the SH group consisting of a
doublet at δ -1.05 and -0.84, respectively, arising from
coupling to 31P of the phosphine bound to Pd or Pt (3JPH
≈
12.6 Hz), and flanked by 195Pt satellites (2JPtH ) 42.4 Hz) in
complex 10.
The crystal structure of [Pt(C6F5)2(PPh3){S(AuPPh3)2}] has
been established by X-ray diffraction. A view of complex 12 is
given in Figure 3. Selected bond distances and bond angles are
presented in Table 3. Compound 12 is a heterotrinuclear species
in which the PtII and AuI centers are linked by the bridging S
atom of the hydridosulfido ligand, and 12 shows a distorted
trigonal-pyramidal geometry, with the sulfur at the vertex lying
1.033 Å out of the plane of the three metallic centers with no
short metal-metal interactions between them. Some polynuclear
gold complexes with bridging sulfido ligands show weak metal-
metal interactions between the closed-shell d10 metal centers,
termed aurophilic attractions,30 that cannot be explained in terms
The crystal structure of [Pt(C6F5)2(PPh3){S(H)AgPPh3}] 10
has been established by single-crystal X-ray diffraction. A view
of complex 10 is given in Figure 2 , and selected bond distances
and bond angles are presented in Table 2. Compound 10 is a
heterodinuclear species in which the PtII and AgI centers are
linked by the bridging S atom of the hydridosulfido ligand. The
Pt atom is in a nearly square-planar environment, whereas the
geometry around Ag deviates from linearity; the angle P(2)-
Ag(1)-S(1) is 167.05 (6)°. In the related complex [Pt(C6F5)2-
(PPh3)(C5H4NS)AgPPh3], in which the PtII and AgI centers are
linked by the bridging S atom of the pyridine-2-thiolato ligand,28
the geometry around Ag can be considered to be quasi-linear
(28) Falvello, R. L.; Fornie´s, J.; Fortun˜o, C.; Go´mez-Saso, M.; Menjo´n
B.; Rueda, A. J.; Toma´s, M. Inorg. Chim. Acta 1997, 264 , 219.
(29) Uso´n, R.; Fornie´s, J.; Espinet. P.; Mart´ınez, F.; Toma´s, M. J. Chem.
Soc., Dalton Trans. 1981, 463.
(27) Harris, R. K.; Man, B. E. NMR and the Periodic Table; Academic
Press: London, UK, 1978.

5358 Inorganic Chemistry, Vol. 40, No. 21, 2001
Ruiz et al.
1
Table 3. Selected Distances (Å) and Bond Angles (deg) for
Complex 12
ΛM: 178 S cm2 mol-1. IR (Nujol, cm-1) 825, 800 (Pd-C6Cl5). H
NMR (CDCl3) δ -1.85 (s, 2H, SH).
Preparation of Complex [NBu4]2[{Pt(C6F5)2(µ-SH)}2] (3). [NBu4]2-
[{Pt(C6F5)2(µ-OH)}2] (0.10 g, 0.063 mmol) in methanol (15 cm3) was
reacted with H2S at reflux temperature for 30 min. The solvent was
partially evaporated under reduced pressure. Addition of water caused
the precipitation of a brown solid, which was collected by filtration
and air dried.
Complex 3: Yield: 89%. Anal. Calcd for C56H74F20N2Pt2S2: C, 41.8;
H, 4.6; N, 1.7; S, 4.0. Found: C, 41.4; H, 4.6; N, 1.7; S, 4.3. Mp: 190
°C. Dec ΛM: 204 S cm2 mol-1. IR (Nujol, cm-1) 795, 785 (Pd-C6F5).
1H NMR (CDCl3) δ -1.19 (s, 2H, SH, JPtH ) 37.2).19F NMR (CDCl3)
δ -116.5 (d, 8Fo, JPtFo ) 469, Jom ) 25.9), -167.7 (m, 8Fm), -168.2
(t, 4Fp, Jmp ) 20.0).
Bond Distances
Pt(1)-C(7)
2.022(11)
2.045 (11)
2.278 (3)
2.371(3)
2.259(4)
2.314 (3)
2.256 (3)
2.304 (3)
3.883(1)
3.712(1)
3.164(1)
86.15 (4)
94.0 (3)
Pt(1)-C(1)
Pt(1)-P(1)
Pt(1)-S(1)
Au(1)-P(2)
S(1)-Au(1)
Au(2)-P(3)
S(1)-Au(2)
Pt(1)‚‚‚Au(1)
Pt(1)‚‚‚Au(2)
Au(1)‚‚‚Au(2)
Preparation of Complexes [{Pd(R)(PPh3)(µ-SH)}2] (R ) C6F5 4
and C6Cl5 5). H2S was bubbled, at room temperature, through a solution
of [{Pd(R)(PPh3)(µ-OH)}2] (R ) C6F5 or C6Cl5) (0.071 mmol) in
acetone (for 4) or dichloromethane (for 5) (15 cm3) for 15 min. The
solvent was removed under vacuum, and the residue was treated with
methanol. The brown solid was filtered off, washed with water then
hexane, and air dried.
of the classical theory of chemical bonding, but only in
theoretical studies when considered as a correlation effect,
strengthened by relativistic effects.31 The Pt atom is in a nearly
square-planar environment. The Pt(1)-S(1) distance (2.371(3)
Å) is very similar to that found in complex 10 and in other
related complexes.28 The coordination of the Au centers to the
S and P atoms can be considered as quasi-linear (P(3)-
Au(2)-S(1) ) 176.81 (12)° and P(2)-Au(1)-S(1) ) 170.55
(11)°).
Treatment of complexes 7 or 8 with [Au(O3SCF3)(PPh3)] in
a 1:1 ratio produces mixtures containing the heterotrinuclear
complexes [M(C6F5)2(PPh3){S(AuPPh3)2}] 11 or 12 and the
starting material, but the formation of the binuclear complexes
[M(C6F5)2(PPh3){S(H)AuPPh3}] was not observed.
Complex 4: Yield: 90%. Anal. Calcd for C48H32F10P2Pd2S2: C, 50.7;
H, 2.8; S, 5.6. Found: C, 51.0; H, 2.9; S, 5.4. Mp: 170 °C. Dec IR
1
(Nujol, cm-1) 780 (Pd-C6F5). H NMR (CDCl3) δ 7.3 (m, 30H, Ph),
-1.29 (d, 2H, SH, JPH ) 2.2).19F NMR (CDCl3) δ -114.9 (br, 2Fo),
-116.3 (br, 2Fo), -161.6 (t, 2Fp, Jmp ) 21.4), -161.3 (br, 4Fm). 31P
NMR (CDCl3) δ 25.5 (s). Complex 5: Yield: 74%. Anal. Calcd for
C48H32Cl10P2Pd2S2: C, 44.3; H, 2.5; S, 4.9. Found: C, 44.7; H, 2.9; S,
1
4.7. Mp: 186 °C. Dec IR (Nujol, cm-1) 830 (Pd-C6Cl5). H NMR
(CDCl3) δ 7.4 (m, 30H, Ph), -1.38 (d, 2H, SH, JPH ) 2.2). 31P NMR
(CDCl3) δ 24.9 (s).
Preparation of Complex [NBu4]2[{Pt(C6F5)2}2(µ-SH)(µ-pz)] (6).
[NBu4]2[{Pt(C6F5)2}2(µ-OH)(µ-pz)] (0.1 g, 0.061 mmol) in methanol
(15 cm3) was reacted with H2S at reflux temperature for 30 min. The
solvent was removed under reduced pressure, and the residue was
treated with 2-propanol. The greenish solid was filtered off and air
dried.
Complex 6: Yield: 73%. Anal. Calcd for C59H76F20N4Pt2S2: C, 43.1;
H, 4.7; N, 3.4; S, 2.0. Found: C, 42.8; H, 4.9; N, 3.4; S, 2.3. Mp: 248
°C. Dec ΛM: 224 S cm2 mol-1. IR (Nujol, cm-1) 795, 780 (Pt-C6F5).
1H NMR (CDCl3) δ 6.99 (br, 2H, 3- and 5-H of pz), 5.69 (br, 1H, 4-H
of pz), -0.45 (s, 1H, SH, JPtH ) 40.6).19F NMR (CDCl3) δ -115.7 (d,
4Fo, JPtFo ) 452, Jom ) 29.1), -116.1 (d, 4Fo, JPtFo ) 480, Jom ) 22.5),
-166.8 (m, 4Fm + 2Fp), -168.1 (m, 4Fm + 2Fp).
Preparation of Complex [NBu4][Pd(C6F5)2(SH)(PPh3)] (7). To a
solution of 1 (0.1 g, 0.069 mmol) in methanol (10 cm3) was added
PPh3 (0.139 mmol). The solution was stirred under reflux for 1 h. The
solvent was partially evaporated under reduced pressure. Addition of
water caused the precipitation of a brownish solid, which was collected
by filtration and air dried.
Experimental Section
Instrumental Measurements. C, H, and N analyses were performed
with a Carlo Erba model EA 1108 microanalyzer. Decomposition
temperatures were determined with a Mettler TG-50 thermobalance at
a heating rate of 5 °C min-1 and with the solid samples under nitrogen
flow (100 mL min-1). Molar conductivities were measured in acetone
solution (c ≈ 5 × 10-4 mol L-1) with a Crison 525 conductimeter.
The NMR spectra were recorded on a Bruker AC 200E or Varian Unity
300 spectrometer, using SiMe4 and CFCl3 as the standard, respectively.
In the 1H NMR spectra of the ionic compounds, the signal of the NBu4+
cation has been omitted. Infrared spectra were recorded on a Perkin-
Elmer 1430 spectrophotometer using Nujol mulls between polyethylene
sheets.
Materials. The starting complexes [NBu4]2[{M(R)2(µ-OH)}2] (M)
Pd, R ) C6F5 or C6Cl5; Pt, R ) C6F5),12-14 [{Pd(R)(PPh3)(µ-OH)}2]
(R ) C6F5 or C6Cl5),15 [NBu4]2[{Pt(C6F5)2}2(µ-OH)(µ-pz)],16 and [M′-
(O3SCF3)(PPh3)] (M′ ) Ag, Au)25 were prepared by procedures
described elsewhere. Solvents were dried by the usual methods. H2S
gas was generated by treating FeS with commercial 96% H2SO4.
CAUTION: H2S is extremely toxic, and all the preparations
inVolVing its use should be carried out in a well-Ventilated fume hood!
Preparation of Complexes [NBu4]2[{Pd(R)2(µ-SH)}2] (R ) C6F5
1 and C6Cl5 2). H2S was bubbled, at room temperature, through a
solution of [NBu4]2[{Pd(R)2(µ-OH)}2] (R ) C6F5 or C6Cl5) (0.071
mmol) in methanol (for 1) or acetone (for 2) (15 cm3) for 15 min. The
solvent was partially evaporated under reduced pressure. Addition of
water caused the precipitation of a brown solid, which was collected
by filtration, washed with water, and air dried.
Complex 7: Yield: 79%. Anal. Calcd for C46H52F10NPPdS: C, 56.5;
H, 5.4; N, 1.4; S, 3.3. Found: C, 56.8; H, 5.3; N, 1.3; S, 3.2. Mp: 230
°C. Dec ΛM: 97 S cm2 mol-1. IR (Nujol, cm-1) 775, 760 (Pd-C6F5),
1
530, 510, 494 (PPh3). H NMR (CDCl3) δ 7.72 (m, 6H, Ho of Ph),
7.34 (m, 9H, Hm and Hp of Ph), -2.26 (d, 1H, SH, JPH ) 12.9). 19F
NMR (CDCl3) δ -111.2 (m, 2Fo), -113.0 (d, 2Fo, Jom )30.8), -165.8
(m, 2Fm), -166.4 (m, 2Fm + 2Fp). 31P NMR (CDCl3) δ 28.7 (s).
Preparation of Complex [NBu4][Pt(C6F5)2(SH)(PPh3)] (8). To a
suspension of 3 (0.1 g, 0.062 mmol) in 2-propanol (10 cm3) was added
PPh3 (0.124 mmol). The suspension was stirred under reflux for 8 h.
The solvent was removed under reduced pressure, and the residue was
treated with dichloromethane/hexane. The brownish solid was filtered
off and air dried.
Complex 1: Yield: 90%. Anal. Calcd for C56H74F20N2Pd2S2: C,
47.0; H, 5.2; N, 2.0; S, 4.5. Found: C, 46.7; H, 5.4; N, 2.1; S, 4.8.
Mp: 148 °C. Dec ΛM: 240 S cm2 mol-1. IR (Nujol, cm-1) 780, 770
(Pd-C6F5). 1H NMR (CDCl3) δ -2.03 (s, 2H, SH). 19F NMR (CDCl3)
δ -111.1 (d, 8Fo, Jom) 27.4), -166.7 (m, 8Fm + 4Fp). Complex 2:
Yield: 68%. Anal. Calcd for C56H74Cl20N2Pd2S2: C, 38.2; H, 4.2; N,
1.6; S, 3.7. Found: C, 38.4; H, 4.2; N, 1.8; S, 3.9. Mp: 175 °C. Dec
Complex 8: Yield: 72%. Anal. Calcd for C46H52F10NPPtS: C, 51.8;
H, 4.9; N, 1.3; S, 3.0. Found: C, 51.6; H, 5.1; N, 1.3; S, 3.2. Mp: 204
°C. Dec ΛM: 97 S cm2 mol-1. IR (Nujol, cm-1) 790, 775 (Pt-C6F5)
1
524, 512, 492 (PPh3). H NMR (CDCl3) δ 7.74 (m, 6H, Ho of Ph),
7.32 (m, 9H, Hm and Hp of Ph), -2.03 (d, 1H, SH, JPH ) 12.9, JPtH
)
50.8). 19F NMR (CDCl3) δ -114.6 (m, 2Fo, JPtFo ) 395), -116.0 (d,
2Fo, JPtFo ) 395, Jom ) 30.8), -166.8 (m, 2Fm + 1Fp), -168.1 (m,
2Fm + 1Fp). 31P NMR (CDCl3) δ 22.0 (s, JPtFo ) 2677).
(30) Calhorda, M. J.; Canales, F.; Gimeno, M. C.; Jime´nez, J.; Jones, P.
G.; Laguna, A.; Veiros, L. F. Organometallics 1997, 17, 33837.
(31) Pyykko¨, P. Chem. ReV. 1997, 97, 597

Bridging and Terminal Hydrosulfido Pd and Pt Complexes
Inorganic Chemistry, Vol. 40, No. 21, 2001 5359
Table 4. Crystal Structure Determination Details
3
10
12
formula
fw
space group
a (Å)
b (Å)
c (Å)
C56H74F20N2Pt2S2
1609.47
P 2 (1)/c
12.7811(9)
12.4547(8)
19.558(2)
90
103.706(5)
90
3024.7(4)
2
C48H31AgF10P2PtS
1194.69
P1h
C66H45Au2F10P3PtS‚0.25CH2Cl2
1763.24
C 2/c
13.9502(2)
14.1938(2)
15.1239(2)
83.44
74.8860(10)
70.3330(10)
2721.24(7)
2
62.6035(9)
13.0329(2)
32.0828(5)
90
104.7030(10)
90
25319.3(7)
16
1.850
R (deg)
â (deg)
γ (deg)
V(Å3)
Z
D
calc (g cm-1
)
1.767
1.458
λ (Å)
0.71073
4.789
173(2)
0.71073
3.087
293(2)
0.71073
7.027
293(2)
µ(mm-1
)
temp (K)
data/restraints/parameters
5294/3/402
0.995
12865/0/568
0.759
22862/63/1524
1.081
GOFa
final R indices
0.0343, 0.0880
0.0412, 0.1106
0.0619, 0.1374
[I > 2σ(I)]: R1,b wR2c
R indices (all data):
R1,b wR2c
0.0430, 0.0927
0.0594, 0.1248
0.1079, 0.1594
a GOF ) [∑(w(Fo - Fc2)2)/(n - p)]1/2 where n is the reflections number and p the refined parameters number. b R1 ) ∑||Fo| - |Fc||/∑|Fo|.
2
c wR2 )[∑(w(Fo - Fc2)2)/∑(w(Fo )2)]1/2
.
2
2
Reaction of Complex 4 with PPh3. To a solution of 4 (0.08 g,
0.070 mmol) in acetone (10 cm3) was added PPh3 (0.140 mmol). The
reaction mixture was stirred under reflux for 3 h. The solvent was
partially evaporated under reduced pressure. The addition of water and
methanol caused the precipitation of a brown solid, which was filtered
off and air dried. NMR data showed that 4 was recovered unchanged.
Preparation of Complex [Pd(C6F5)2(PPh3){S(H)AgPPh3}] (9). To
a solution of 7 (0.12 g, 0.123 mmol) in CH2Cl2 (20 mL) was added
[Ag(O3SCF3)(PPh3)] (63.67 mg, 0.123 mmol). The mixture was stirred
at room temperature for 5 min and then filtered through a small column
packed with florisil. The solvent was partially evaporated under reduced
pressure. The addition of hexane caused the precipitation of a white
solid, which was collected by filtration and air dried. No analytically
pure sample was obtained because it contains a small portion of a
persistent impurity.
Complex 11: Yield: 59%. Anal. Calcd for C66H45Au2F10P3PdS: C,
47.9; H, 2.7; S, 1.9. Found: C, 47.7; H, 2.7; S, 1.8. Mp: 245 °C. Dec
IR (Nujol cm-1) 780-770 (Pd-C6F5). 1H NMR (CDCl3) δ 7.68-7.09
(m, 45H, Ph). 19F NMR (CDCl3) δ -111.1 (d, 2Fo, Jom ) 29.9), -115.6
(d, 2Fo, Jom ) 35.3), -163.2 (t, 1Fp, Jmp ) 19.7), -164.3 (m, 2Fm),
-165.2 (m, 1Fp + 2Fm). 31P NMR (CDCl3) δ 33.9 (s, 2P, Au-PPh3),
13.8 (s, 1P, Pd-PPh3).
Preparation of Complex [Pt(C6F5)2(PPh3){S(AuPPh3)2}] (12). To
a solution of 8 (0.12 g, 0.112 mmol) in CH2Cl2 (20 mL) was added
[Au(O3SCF3)(PPh3)] (136.8 mg, 0.224 mmol). The mixture was stirred
at room temperature for 3 h and then filtered through a small column
packed with florisil. The solvent was partially evaporated under reduced
pressure. The addition of hexane caused the precipitation of a white
solid, which was collected by filtration and air dried. Complex 12 was
recrystallized from dry toluene/CH2Cl2/hexane.
Complex 12: Yield: 57%. Anal. Calcd for C66H45Au2F10P3PtS: C,
45.5; H, 2.6; S, 1.8. Found: C, 45.3; H, 2.6; S, 1.6. Mp: 280 °C. Dec
IR (Nujol cm-1) 794-782 (Pt-C6F5). 1H NMR (CDCl3) δ 7.72-7.06
(m, 45H, Ph). 19F NMR (CDCl3) δ -114.6 (m, 2Fo, JPtFo ) 400),
-118.6 (d, 2Fo, Jom ) 31.0, JPtFo ) 427), -163.9 (t, 1Fp, Jmp ) 19.7),
-164.9 (m, 2Fm), -166.6 (t, 1Fp + 2Fm). 31P NMR (CDCl3) δ 33.2 (s,
2P, Au-PPh3), 12.0 (s, 1P, Pt-PPh3, JPtP ) 2518).
X-ray Structure Determination of 3, 10, and 12. Crystals suitable
for a diffraction study were grown from toluene/hexane (complexes 3
and 10) or dichloromethane-toluene-hexane (complex 12). Single
crystals of dimensions 0.60 × 0.50 × 0.50 for 3, 0.20 × 0.25 × 0.40
for 10, and 0.05 × 0.25 × 0.35 for 12 were mounted on a glass fiber
in a random orientation. Data collection for 10 and 12 was performed
at 25 °C on a Bruker Smart CCD diffractometer using graphite
monocromated Mo KR radiation (λ ) 0.71073 Α), with a nominal
crystal to detector distance of 4.5 cm. Diffraction data were colleted
based on a φ-ω scan run. A total of 1271 frames were collected at
0.3° intervals and 10 s per frame. The diffraction frames were integrated
using the SAINT package32 and corrected for absorption with SAD-
ABS.33 Data collection for 3 was performed at -100 °C on a Siemens
P4 diffractometer. The scan method was ω-2θ, and empirical ι-scan
mode absorption correction was made.
Complex 9: IR (Nujol cm-1) 782-772 (Pd-C6F5), 530, 522, 508,
1
490 (PPh3). H NMR (CDCl3) δ 7.58-7.12 (m, 30H, Ph), -1.05 (d,
1H, SH, JPH ) 12.6). 19F NMR (CDCl3) δ -111.6 (d, 2Fo, Jom ) 36.1),
-115.7 (d, 2Fo, Jom ) 29.6), -161.8 (t, 1Fp, Jmp ) 19.5), -163.1 (m,
2Fm), -166.6 (t, 1Fp, Jmp ) 19.8), -164.5 (m, 2Fm). 31P NMR (CDCl3)
δ 24.3 (s, 1P, Pd-PPh3), 13.8 (br, 1P, Ag-PPh3).
Preparation of Complex [Pt(C6F5)2(PPh3){S(H)AgPPh3}] (10). To
a solution of 8 (0.1 g, 0.094 mmol) in CH2Cl2 (20 mL) was added
[Ag(O3SCF3)(PPh3)] (48.66 mg, 0.094 mmol). The mixture was stirred
at room temperature for 3 h and then filtered through a small column
packed with florisil. The solvent was partially evaporated under reduced
pressure. The addition of hexane caused the precipitation of a white
solid, which was collected by filtration and air dried. Complex 10 was
recrystallized from dry toluene/hexane.
Complex 10: Yield: 67%. Anal. Calcd for C48H31F10AgP2PtS: C,
48.3; H, 2.6; S, 2.7. Found: C, 48.5; H, 2.8; S, 2.6. Mp: 161 °C. Dec
1
IR (Nujol cm-1) 798-784 (Pt-C6F5), 536, 524, 512, 492 (PPh3). H
NMR (CDCl3) δ 7.56-7.06 (m, 30H, Ph), -0.84 (d, 1H, SH, JPH
)
12.3, JPtH ) 42.4). 19F NMR (CDCl3) δ -114.9 (m, 2Fo, JPtFo ) 373),
-118.9 (d, 2Fo, Jom ) 27.6, JPtFo ) 424), -162.7 (t, 1Fp, Jmp ) 19.2),
-163.9 (m, 2Fm), -165.3 (t, 1Fp, Jmp ) 19.2), -165.9 (m, 2Fm). 31P
NMR (CDCl3) δ 16.5 (s, 1P, Pt-PPh3, JPtP ) 2467), 12.0 (br, 2P, Ag-
PPh3).
The structures were solved by heavy-atom methods34 and refined35
by full-matrix least-squares techniques using anisotropic thermal
Preparation of Complex [Pd(C6F5)2(PPh3){S(AuPPh3)2}] (11). To
a solution of 7 (0.12 g, 0.123 mmol) in CH2Cl2 (20 mL) was added
[Au(O3SCF3)(PPh3)] (149.2 mg, 0.246 mmol). The mixture was stirred
at room temperature for 30 min and then filtered through a small column
packed with florisil. The solvent was partially evaporated under reduced
pressure. The addition of hexane caused the precipitation of a white
solid, which was collected by filtration and air dried.
(32) SAINT, Version 4.0, Bruker Analytical X-ray Instruments Inc.,
Madison, Wisconsin, USA, 1996.
(33) Sheldrick, G. M. SADABS; University of Gottingen, 1996.
(34) Sheldrick, G. M. SHELXS-97; University of Gottingen, 1997.
(35) Sheldrick, G. M. SHELXL-97; University of Gottingen, 1997.

5360 Inorganic Chemistry, Vol. 40, No. 21, 2001
Ruiz et al.
parameters for non-H atoms. Hydrogen atoms were introduced in
calculated positions and refined during the last stages of the refinement.
The final R factors were 0.041 for 10, 0.0619 for 12, and 0.0343 for 3
over 9479, 15334, and 4583 observed reflections, respectively.
In complex 12 there are two molecules with bond lengths and angles
somewhat different in the asymmetric unit, which can justify the big
unit cell. The structure contains CH2Cl2 as solvate, and the largest
residual peaks appear near that molecule.
J.M.M. thank the Fundacio´n Se´neca (Comunidad Auto´noma de
la Regio´n de Murcia, Spain) and the Fundacio´n Organizacio´n
Nacional de Ciegos Espan˜oles (Spain), respectively, for research
grants.
Supporting Information Available: X-ray crystallographic files
in CIF format for the structure determination of compounds 3, 10, and
12. This material is available free of charge via the Internet at
http://pubs.acs.org.
Further details are given in Table 4.
Acknowledgment. Financial support from the DGES (project
PB97-1036), Spain, is gratefully acknowledged. V.R. and
IC0013633