Reactivity of C6F5S-P(C6H 5)2 with [M3(CO)12

Article abstract of DOI:10.1016/j.jorganchem.2005.02.046

The thiophosphinite C₆F₅S-P(C₆H ₅)₂ (1) was synthesized and its reactivity explored with transition metal clusters of group 8. The reaction of 1 with [M ₃(CO)₁₂] (M = Fe, Ru, Os)

Full text of DOI:10.1016/j.jorganchem.2005.02.046

Journal of Organometallic Chemistry 690 (2005) 2880–2887
www.elsevier.com/locate/jorganchem
Reactivity of C6F5S-P(C6H5)2 with [M3(CO)12] (M = Fe, Ru, Os).
The X-ray crystal structures of [Fe2(l-SC6F5)(l-PPh2)(CO)6],
[Ru4(l3-SPPh2)2(l-SC6F5)2(l-PPh2)2(SC6F5)2(CO)6]
and [Os3(g1-Ph2P-SC6F5)(CO)11]
´
´
Oscar Baldovino-Pantaleon, Gustavo Rıos-Moreno,
*
Ruben A. Toscano, David Morales-Morales
´ ´ ´ ´ ´ ´
Instituto de Quımica, Universidad Nacional Autonoma de Mexico, Cd. Universitaria, Circuito Exterior, Coyoacan, 04510 Mexico city, Mexico
Received 30 November 2004; revised 9 February 2005; accepted 10 February 2005
Available online 25 April 2005
Abstract
The thiophosphinite C6F5S-P(C6H5)2 (1) was synthesized and its reactivity explored with transition metal clusters of group 8. The
reaction of 1 with [M3(CO)12] (M = Fe, Ru, Os) afforded the complexes [Fe2(l-SC6F5)(l-PPh2)(CO)6] (2), [Ru4(l3-SPPh2)2(l-
SC6F5)2(l-PPh2)2(SC6F5)2(CO)6] (3) and [Os3(g1-Ph2P-SC6F5)(CO)11] (4) in good yields. Complex 2 was the result of the P–S bond
activation, while complex 3 resulted from the activation of P–S and C–S bonds. Simple ligand substitution occurs when C6F5S-
P(C6H5)2 (1) is reacted with Os3(CO)12.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: P–S ligand; Thiophosphinite; Cluster chemistry; Fluorinated thiolate complexes; Crystal structures
1. Introduction
conductors with low band gaps [4]. Therefore, following
our interest in the reactivity of fluorinated thiolates on
the one hand and the design and synthesis of robust
complexes for application as catalysts in industrially rel-
evant transformations [5], we have synthesized the thio-
phosphinite C6F5S-P(C6H5)2 (1). Our aim was to have a
convenient source of thiolate and secondary phosphines
and to explore its reactivity with a series of transition
metals clusters of group 8 [M3(CO)12] (M = Fe, Ru,
Os). The results are reported herein.
Transition metal carbonyl clusters containing chalc-
ogenides have important chemical and structural signif-
icance, since they can be regarded as discrete molecular
models of extended inorganic solids [1]. These com-
pounds have also been employed as homogeneous mod-
els to better understand the fundamental steps of the
catalytic HDS (hydrodesulfurization) process [2] in
which sulfur is removed from thiols and other organo-
sulfur compounds in fossil fuels [3]. On the other hand,
transition metal clusters containing phosphido ligands
have received considerable attention in recent years
due to the importance that these compounds may have
as homogeneous catalyst and for precursors for semi-
2. Experimental
2.1. Materials and methods
*
Unless stated otherwise, all reactions were car-
ried out under an atmosphere of dinitrogen using
Corresponding author. Tel.: +525556224514; fax: +525556162217.
E-mail address: damor@servidor.unam.mx (D. Morales-Morales).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.02.046

´
O. Baldovino-Pantaleon et al. / Journal of Organometallic Chemistry 690 (2005) 2880–2887
2881
conventional Schlenk glassware. Solvents were dried
2.3. General procedure for the preparation of SP-
transition metal clusters complexes
using standard procedures and distilled under
dinitrogen immediately prior to use. The IR spectra
were recorded on a Nicolet-Magna 750 FT-IR spec-
trometer as nujol mulls. The 1H NMR (300 MHz)
spectra were recorded on a JEOL GX300 spectrome-
ter. Chemical shifts are reported in ppm down field
of TMS using the residual solvent (CDCl3, d = 7.27)
as an internal standard. 31P{1H}NMR (121 MHz)
and 19F{1H}spectra were recorded with complete pro-
ton decoupling and are reported in ppm using 85%
H3PO4 and C6F6 as external standards, respectively.
Elemental analyses were determined on a Perkin–
Elmer 240. Positive-ion FAB mass spectra were re-
corded on a JEOL JMS-SX102A mass spectrometer
operated at an accelerating voltage of 10 kV. Samples
were desorbed from a nitrobenzyl alcohol (NOBA)
matrix using 3 keV xenon atoms. Mass measurements
in FAB are performed at a resolution of 3000 using
magnetic field scans and the matrix ions as the
reference material or, alternatively, by electric field
scans with the sample peak bracketed by two (poly-
ethylene glycol or cesium iodide) reference ions. Melt-
ing points were determined in a MEL-TEMP capillary
melting point apparatus and are reported without cor-
rection. GC–MS analyses were performed on a Agi-
Complexes 2–4 were obtained using identical experi-
mental procedures. As a representative example, the
synthesis of [Fe2(l-SC6F5)(l-PPh2)(CO)6] (2) is
described.
2.3.1. Synthesis of [Fe2(l-SC6F5)(l-PPh2)(CO)6] (2)
A
mixture of the metal carbonyl complex
[Fe3(CO)12] (21.85 mg, 4.34 mmol), (C6F5)S-P(C6H5)2
(50 mg, 13.02 mmol) and heptane ( 25 mL) was re-
fluxed for 4 h. The solvent was removed under vac-
uum, the residue redissolved in a minimal volume of
CH2Cl2, and filtered through a short plug of CeliteÒ.
Red crystals were grown by recrystallization from a
heptane/dichloromethane (2:8) mixture. A microcrys-
talline red solid was obtained (94%); m.p. 186–
187 °C. IR (CHCl3): mCO 2070.98(m), 2031.82(s),
2004.09(vs), 1981.69(vs) cmꢀ1
CDCl3): d 7.60(t, 4 H, Ho), 7.37(s, 2H, Hp), 7.29 (2,
4H, Hm); 13C{1H}NMR (75.5 MHz, CDCl3):
207.94 (CO), 147.37–144.05 (Co-F), 142.13–138.75
.
1H NMR (300 MHz,
d
(Cp-F), 139.53–136.50 (Cm-F), 136.24–135.71 (Cipso
-
P), 134.40 (d, 3J = 8.15 Hz, Co-H), 133.33 (d,
3J = 8.60 Hz, Co-H), 131.75-131.37 (Cipso-S), 130.58
(d, Cp-H), 130.30(d, Cp-H), 128.75 (d, 3J = 10.64 Hz,
lent 6890N GC with
a 30.0 m DB-5 capillary
column coupled to an Agilent 5973 Inert Mass Selec-
tive detector.
The HSC6F5, PPh2Cl were obtained commercially
from Aldrich Chem. Co. Compounds [Fe3(CO)12] [6],
[Ru3(CO)12] [7], and [Os3(CO)12] [8]; were synthesized
according to the published procedures.
Cm-H), 128.26 (d, 3J = 10.17 Hz, Cm-H); 19F{1H}-
3
NMR (282 MHz, CDCl3): d ꢀ124.13 (d,
J
¼
Fo–Fm
3
16.92 Hz, Fo), ꢀ151.94 (t,
J
¼ 19.74 Hz, Fp),
Fp–Fm
¼ 19.74; 16.92 Hz, Fm); 31P-
3
ꢀ159.79(m,
J
Fp–Fm;Fo–Fm
{1H}NMR (121 MHz, CDCl3): d 138.66. FAB+-MS
M+ = 664 m/z. Anal. Calc. for C24H10F5Fe2O6PS
(664.05): C, 43.41; H, 1.52. Found: C, 43.38, H, 1.55.
2.2. Synthesis of C6F5S-P(C6H5)2 (1)
2.3.2. Synthesis of [Ru4(l3-SPPh2)2(l-SC6F5)2-
(l-PPh2)2(SC6F5)2(CO)6] (3)
A red solid was obtained in 70% yield; m.p. 234–
A solution of toluene (50 mL), HSC6F5 (1.0 g,
0.66 mL, 4.99 mmol) and NEt3 (50 mg, 0.70 mL,
4.99 mmol) was stirred under N2 for 20 min. After this
time a (C6H5)2PCl (1.102 g, 0.89 mL, 4.99 mmol) and
toluene (20 mL) were added. Immediate formation of
a white precipitated was noted. The mixture was stirred
overnight, filtered and concentrated under reduced pres-
sure. A microcrystalline white solid was obtained (92%).
1H NMR (300 MHz, CDCl3): d 7.65 (m, 4H, Ho), 7.43
(m, 6H, Hm,p). 13C{1H}NMR (75.5 MHz, CDCl3): d
149.70–146.43(Co-F), 143.26–139.29(Cp-F), 139.71–
135.99 (Cm-F), 132.95(Co-H), 132.66(Co-H), 129.96(Cp-
H), 128.86(Cm-H), 128.78(Cm-H). 19F{1H}NMR
1
236 °C. IR (CHCl3): mCO 2045(vs), 1979(vs) cmꢀ1. H
NMR (300 MHz, CDCl3): d 7.94–7.47(m, 40 H); 13C
NMR (75.5 MHz, CDCl3): d 133.65, 132.43, 131.56,
130.52, 129.783, 128.89, 128.26; 19F{1H}NMR (282
3
MHz, CDCl3): d ꢀ124.92 and 128.92 (m, JF –F
¼
o
m
3
16.92, Fo), ꢀ144.43 and ꢀ146.73 (m, JF –F ¼ 22.56,
p
m
3
Fp), ꢀ154.74 and ꢀ158.36 (m, JF –F
¼ 22.56;
m;Fo–Fm
p
16.92 Hz, Fm); 31P{1H}NMR (121 MHz, CDCl3) d
106 (s), 145(s). FAB+-MS M+ = 2174 m/z. Anal. Calc.
for C78H40F20Ru4O6P4S6 (2173.62): C, 43.10; H, 1.85.
Found: C, 43.08; H, 1.86.
3
(282 MHz, CDCl3): d ꢀ128.96 (m, JF –F ¼ 16.92 Hz,
o
m
3
Fo), ꢀ151.06 (t, JF –F ¼ 22.56 Hz, Fp), ꢀ159.36 (m,
p
m
3JF –F
¼ 22.56; 16.92 Hz, Fm). 31P{1H}NMR
m;Fo–Fm
p
4
(121 MHz, CDCl3): d 45.29 (t, J = 18.16 Hz). EI-MS:
385 (M+, 89%), Anal. Calc. for C18H10F5PS; C, 56.26;
H, 2.62. Found C, 56.22; H, 2.59.
2.3.3. Synthesis of [Os3(g1-Ph2P-SC6F5)(CO)11] (4)
A microcrystalline pale yellow solid was obtained in
65% yield. Single crystal for X-ray diffraction study

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O. Baldovino-Pantaleon et al. / Journal of Organometallic Chemistry 690 (2005) 2880–2887
2882
was obtained from heptane–dichloromethane at room
temperature; m.p. 218–220 °C. IR (CHCl3): mCO
of 4.837 cm from the crystals in all cases. A total of
1800 frames were collected with a scan width of 0.3° in
x and an exposure time of 10 s/frame. The frames were
integrated with the Bruker SAINT software package [9]
using a narrow-frame integration algorithm. The inte-
gration of the data was done using a triclinic unit cell
in all cases except for complex 2 were a monoclinic unit
cell was used to yield a total of 20030, 42663 and 32023
reflections for 2, 3 and 4, respectively, to a maximum
2068(m), 2027(vs), 1949(vs) cmꢀ1
.
1H NMR
(300 MHz, CDCl3) d 7.59–7.44 (m, 10H); 13C NMR
(75.5 MHz, CDCl3) d 186.38 (CO), 134.22–133.31
(Co-F), 134.01–133.40 (Cp-F), 133.10 (Cm-F), 132.40
(d,3JC-P = 12.45 Hz, Co-H), 132.19 (s, Cp-H) 131.55
3
(d,3JC-P = 12.19 Hz, Cipso-P), 130.37 (d, JC-P = 12.19
3
Hz, Cipso-S),128.78 (d, JC-P = 11.40 Hz, Cm-H); 19F-
{1H}NMR (282 MHz, CDCl3) d-127.12 (d, JF –F
¼
2h angle of 50.00° (0.93 A resolution), of which 4409
3
˚
o
m
3
19.74 Hz, Fo), ꢀ148.20 (t, JF –F ¼ 19.74 Hz, Fp),
(2), 14466 (3) and 11567(4) were independent. Analysis
of the data showed in all cases negligible decays during
data collections. The structures were solved by Patterson
method using SHELXS-97 [10] program. The remaining
atoms were located via a few cycles of least squares
refinements and difference Fourier maps, using the space
p
m
ꢀ159.30 (m, JF –F ¼ 19.74 Hz, Fm); 31P{1H}NMR
3
p
m
(121 MHz, CDCl3) d 70.35. FAB+-MS M+ = 1263.
Anal. Calc. for C29H10F5O11Os3PS (1263.1): C, 27.58;
H, 0.80. Found: C, 27.55; H, 0.79.
ꢀ
ꢀ
2.4. Data collection and refinement for [Fe2(l-SC6F5)-
(l-PPh2)(CO)6] (2), [Ru4(l3-SPPh2)2(l-SC6F5)2-
(l-PPh2)2(SC6F5)2(CO)6] (3), [Os3(g1-Ph2P-SC6F5)-
(CO)11] (4)
group P21/c with Z = 4 for 2, P1 with Z = 1 for 3 and P1
with Z = 2 for 4. Hydrogen atoms were input at calcu-
lated positions, and allowed to ride on the atoms to
which they are attached. Thermal parameters were re-
fined for hydrogen atoms on the phenyl groups using a
˚
Crystalline red, red-orange and yellow prisms for 2, 3
and 4, respectively, were grown independently by slow
diffusion of CH2Cl2/heptane solvent systems. Each crys-
tal was mounted on a glass fiber. In all cases, the X-ray
intensity data were measured at 293 or 291 K on a Bru-
ker SMART APEX CCD-based X-ray diffractometer
system equipped with a Mo-target X-ray tube (k =
Ueq = 1.2 A to precedent atom in all cases. For all com-
plexes, the final cycle of refinement was carried out on all
non-zero data using SHELXL-97 [10] and anisotropic ther-
mal parameters for all non-hydrogen atoms. The details
of the structure determinations are given in Table 1 and
selected bond lengths (A) and angles (°) are given in Ta-
bles 2–4, respectively. The numbering of the atoms is
shown in Figs. 1–3, respectively (ORTEP) [11].
˚
˚
0.71073 A). The detector was placed at a distance
Table 1
Summary of crystal structure data for: [Fe2(l-SC6F5)(l-PPh2)(CO)6] (2), [Ru4(l 3-SPPh2)2(l-SC6F5)2(l-PPh2)2(SC6F5)2(CO)6] (3), [Os3(g1-Ph2P-
SC6F5)(CO)11] (4)
Compound
Formula
2
3
4
C
664.05
24H10F5Fe2O6PS
C78H40F20Ru4O6P4S6
2173.62
Triclinic
C29H10F5O11Os3PS
1263.00
Triclinic
Formula weight
Crystal system
Space group
Monoclinic
P21/c
ꢀ
ꢀ
P1
P1
˚
a (A)
14.5431(9)
10.8230(6)
15.9483(9)
90
12.524(3)
14.753(4)
16.075(4)
90
8.1154(4)
13.4111(7)
16.5814(9)
108.80(1)
90.718(1)
106.581(1)
1626.4(2)
2
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
93.3170(10)
90
112.18(1)
90
3
˚
V (A )
2506.1(3)
4
1.760
2470.4(11)
1
1.461
Z
qcalc (g cmꢀ3
)
2.579
11.891
l (mmꢀ1
Reflections collected
Independent reflections
)
1.320
20,030
0.872
42,663
32,023
11567
4409
[Rint = 0.0377]
1.008a
14466
[Rint = 0.0942]
1.011a
[Rint = 0.0651]
1.002a
GOF on F2
R(I>2r(I))
R1 = 0.0360,
wR2 = 0.0758a
R1 = 0.0440,
wR2 = 0.0791b
R1 = 0.0683,
wR2 = 0.2017a
R1 = 0.02122,
wR2 = 0.02270b
R1 = 0.0429,
wR2 = 0.0704a
R1 = 0.0730,
wR2 = 0.0931b
R indices (all data)
a
S = [(w(Fo)2 ꢀ(Fc)2)2/(nꢀp)]1/2, where n = number of reflections and p = total number of parameters.
b
R1 = |Fo ꢀFc|/|Fo|, wR2 = [w((Fo)2 ꢀ(Fc)2)2/w(Fo)2]1/2
.

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2883
Table 2
Selected bond lengths and angles for [Fe2(l-SC6F5)(l-PPh2)(CO)6] (2)
Table 3
Selected bond lengths and angles for [Ru4(l3-SPPh2)2(l-SC6F5)2(l-
PPh2)2(SC6F5)2(CO)6] (3)
˚
Bond lengths (A)
Angles (°)
˚
Bond lengths (A)
Angles (°)
Fe(1)–C(3)
Fe(1)–C(2)
Fe(1)–C(1)
Fe(1)–P(1)
Fe(1)–S(1)
Fe(1)–Fe(2)
Fe(2)–C(4)
Fe(1)–C(5)
Fe(2)–C(6)
Fe(2)–P(1)
Fe(2)–S(1)
O(1)–C(1)
O(2)–C(2)
O(3)–C(3)
O(4)–C(4)
O(5)–C(6)
O(6)–C(5)
1.780(3)
1.792(3)
1.814(3)
2.2281(8)
2.2781(7)
2.5394(5)
1.786(3)
1.792(3)
1.809(3)
2.2298(8)
2.2853(7)
1.127(3)
1.133(3)
1.135(3)
1.130(3)
1.129(3)
1.135(3)
C(3)–Fe(1)–C(2)
C(3)–Fe(1)–C(1)
C(2)–Fe(1)–C(1)
C(3)–Fe(1)–P(1)
C(2)–Fe(1)–P(1)
C(1)–Fe(1)–P(1)
C(3)–Fe(1)–S(1)
C(2)–Fe(1)–S(1)
C(1)–Fe(1)–S(1)
P(1)–Fe(1)–S(1)
C(3)–Fe(1)–Fe(2)
C(2)–Fe(1)–Fe(2)
C(1)–Fe(1)–Fe(2)
P(1)–Fe(1)–Fe(2)
S(1)–Fe(1)–Fe(2)
C(4)–Fe(2)–C(5)
C(4)–Fe(2)–C(6)
C(5)–Fe(2)–C(6)
C(4)–Fe(2)–P(1)
C(5)–Fe(2)–P(1)
C(6)–Fe(2)–P(1)
C(4)–Fe(2)–S(1)
C(5)–Fe(2)–S(1)
C(6)–Fe(2)–S(1)
P(1)–Fe(2)–S(1)
C(4)–Fe(2)–Fe(1)
C(5)–Fe(2)–Fe(1)
C(6)–Fe(2)–Fe(1)
P(1)–Fe(2)–Fe(1)
S(1)–Fe(2)–Fe(1)
C(7)–S(1)–Fe(1)
C(7)–S(1)–Fe(2)
Fe(1)–S(1)–Fe(2)
Fe(1)–P(1)–Fe(2)
O(1)–C(1)–Fe(1)
O(2)–C(2)–Fe(1)
O(3)–C(3)–Fe(1)
O(4)–C(4)–Fe(2)
O(6)–C(5)–Fe(2)
O(5)–C(6)–Fe(2)
100.34(13)
88.83(12)
100.63(12)
90.95(9)
100.85(9)
158.20(9)
153.13(9)
105.06(9)
94.89(9)
75.94(3)
96.91(9)
150.82(9)
103.09(8)
55.30(2)
56.32(2)
98.16(13)
91.05(12)
99.42(13)
94.84(9)
107.10(10)
152.85(9)
156.75(9)
103.88(10)
92.57(9)
75.76(3)
100.70(9)
154.08(10)
97.85(9)
55.24(2)
56.05(2)
117.30(9)
114.54(9)
67.62(2)
69.45(2)
177.7(3)
177.5(3)
177.0(3)
178.2(3)
177.7(3)
179.0(3)
Ru(1)–C(38)
Ru(1)–C(39)
Ru(1)–P(1)
Ru(1)–S(1)
Ru(1)–S(2)
Ru(1)–S(2)#1
Ru(2)–C(37)
Ru(2)–P(2)
Ru(2)–P(1)
Ru(2)–S(3)
Ru(2)–S(1)
S(1)–C(1)
1.888(11)
1.912(11)
2.357(3)
2.465(3)
2.494(3)
2.522(3)
1.877(10)
2.275(3)
2.307(3)
2.335(3)
2.449(3)
1.739(11)
2.125(4)
2.522(3)
1.759(14)
1.123(11)
1.120(10)
1.125(11)
C(38)–Ru(1)–C(39)
C(38)–Ru(1)–P(1)
C(39)–Ru(1)–P(1)
C(38)–Ru(1)–S(1)
C(39)–Ru(1)–S(1)
P(1)–Ru(1)–S(1)
C(38)–Ru(1)–S(2)
C(39)–Ru(1)–S(2)
P(1)–Ru(1)–S(2)
S(1)–Ru(1)–S(2)
C(38)–Ru(1)–S(2)#1
C(39)–Ru(1)–S(2)#1
P(1)–Ru(1)–S(2)#1
S(1)–Ru(1)–S(2)#1
S(2)–Ru(1)–S(2)#1
C(37)–Ru(2)–P(2)
C(37)–Ru(2)–P(1)
P(2)–Ru(2)–P(1)
C(37)–Ru(2)–S(3)
P(2)–Ru(2)–S(3)
P(1)–Ru(2)–S(3)
C(37)–Ru(2)–S(1)
P(2)–Ru(2)–S(1)
P(1)–Ru(2)–S(1)
S(3)–Ru(2)–S(1)
Ru(2)–S(1)–Ru(1)
P(2)–S(2)–Ru(1)
P(2)–S(2)–Ru(1)#1
Ru(1)–S(2)–Ru(1)#1
Ru(2)–P(1)–Ru(1)
S(2)–P(2)–Ru(2)
O(1)–C(37)–Ru(2)
O(2)–C(38)–Ru(1)
O(3)–C(39)–Ru(1)
89.1(4)
94.0(3)
95.5(3)
94.9(3)
176.0(3)
83.82(10)
176.2(3)
94.6(3)
86.49(9)
81.43(9)
96.1(3)
100.3(3)
161.29(10)
79.68(9)
82.40(8)
95.1(3)
S(2)–P(2)
S(2)–Ru(1)#1
S(3)–C(7)
O(1)–C(37)
O(2)–C(38)
O(3)–C(39)
94.5(3)
86.35(10)
93.9(3)
139.55(12)
132.07(12)
177.1(3)
82.04(9)
85.25(9)
88.41(10)
90.73(9)
101.13(13)
123.43(13)
97.60(8)
97.14(10)
112.56(13)
177.4(10)
177.8(10)
174.2(10)
ꢀ128.96 ppm is observed for the fluorines in the ortho
position, a triplet centered at ꢀ151.06 ppm, correspond-
ing to the fluorine in the para position and a multiplet at
ꢀ159.36 ppm due to the presence of the fluorines in the
meta position.
3. Results and discussion
The reactivity of this compound was explored with
transition metal carbonyl clusters. Thus, the reaction
of three equivalents of compound 1 with one equivalent
of [Fe3(CO)12] under reflux conditions in heptane, af-
fords complex [Fe2(l-SC6F5)(l-PPh2)(CO)6] (2) in good
yield. This compound resulted from cleavage of the S–P
bond. The infrared analysis for this compound reveals
signals corresponding to the presence of the carbonyls
between 1981 and 2070 cmꢀ1. Analysis of this complex
The thiophosphinite C6F5S-P(C6H5)2 (1) has been
conveniently synthesized from the reaction of stoichiom-
etric amounts of pentafluorothiophenol (HSC6F5) and
diphenylchlorophosphine (PPh2PCl) in the presence of
triethylamine (NEt3) as base. This compound was ob-
tained as a microcrystalline white solid. Analysis by
1H NMR reveal the presence of the aromatic groups
at 7.20–7.50 ppm. The analysis by 31P{1H}NMR spectra
were more informative, showing a unique signal at
45.29 ppm as a triplet, the multiplicity being the result
of the P–F coupling (4J = 18.2 Hz). The 19F{1H}NMR
spectrum of this compound reveal the fluorinated thio-
lates to be present, with typical splitting patterns for
the ligand ꢀSC6F5. Thus a multiplet centered at
1
by H NMR shows signals in the usual region for aro-
matic protons. The 31P NMR spectrum of this complex
is more informative exhibiting a singlet at 138.66 ppm
that accounts for a single phosphorus in the molecule,
the chemical shift observed agrees well with the presence
of a bridging phosphide ligand. The 19F{1H}NMR spec-
tra for this complex indicates the presence of the thiolate

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O. Baldovino-Pantaleon et al. / Journal of Organometallic Chemistry 690 (2005) 2880–2887
2884
Table 4
Selected bond lengths and angles for [Os3(g1-Ph2P-SC6F5)(CO)11] (4)
˚
Bond lengths (A)
Angles (°)
Os(1)–C(1)
Os(1)–C(2)
Os(1)–C(3)
Os(1)–P(1)
Os(1)–Os(2)
Os(1)–Os(3)
Os(2)–C(4)
Os(2)–C(5)
Os(2)–C(7)
Os(2)–C(6)
Os(2)–Os(3)
Os(3)–C(8)
Os(3)–C(9)
Os(3)–C(11)
Os(3)–C(10)
P(1)–S(1)
1.893(7)
1.939(7)
1.942(7)
2.3179(18)
2.8831(4)
2.9008(4)
1.882(9)
1.922(8)
1.941(7)
1.942(8)
2.8846(4)
1.918(8)
1.919(8)
1.950(8)
1.954(8)
2.142(2)
1.137(7)
1.135(8)
1.133(8)
1.147(9)
1.127(8)
1.140(9)
1.135(8)
1.128(9)
1.128(9)
1.130(8)
1.128(8)
C(1)–Os(1)–C(2)
C(1)–Os(1)–C(3)
C(2)–Os(1)–C(3)
C(1)–Os(1)–P(1)
C(2)–Os(1)–P(1)
C(3)–Os(1)–P(1)
C(1)–Os(1)–Os(2)
C(2)–Os(1)–Os(2)
C(3)–Os(1)–Os(2)
P(1)–Os(1)–Os(2)
C(1)–Os(1)–Os(3)
C(2)–Os(1)–Os(3)
C(3)–Os(1)–Os(3)
P(1)–Os(1)–Os(3)
Os(2)–Os(1)–Os(3)
C(4)–Os(2)–C(5)
C(4)–Os(2)–C(7)
C(5)–Os(2)–C(7)
C(4)–Os(2)–C(6)
C(5)–Os(2)–C(6)
C(7)–Os(2)–C(6)
C(4)–Os(2)–Os(1)
C(5)–Os(2)–Os(1)
C(7)–Os(2)–Os(1)
C(6)–Os(2)–Os(1)
C(4)–Os(2)–Os(3)
C(5)–Os(2)–Os(3)
C(7)–Os(2)–Os(3)
C(6)–Os(2)–Os(3)
Os(1)–Os(2)–Os(3)
C(8)–Os(3)–C(9)
C(8)–Os(3)–C(11)
C(9)–Os(3)–C(11)
C(8)–Os(3)–C(10)
C(9)–Os(3)–C(10)
C(11)–Os(3)–C(10)
C(8)–Os(3)–Os(2)
C(9)–Os(3)–Os(2)
C(11)–Os(3)–Os(2)
C(10)–Os(3)–Os(2)
C(8)–Os(3)–Os(1)
C(9)–Os(3)–Os(1)
C(11)–Os(3)–Os(1)
C(10)–Os(3)–Os(1)
Os(2)–Os(3)–Os(1)
C(18)–P(1)–C(12)
C(18)–P(1)–S(1)
C(12)–P(1)–S(1)
C(18)–P(1)–Os(1)
C(12)–P(1)–Os(1)
S(1)–P(1)–Os(1)
C(24)–S(1)–P(1)
91.8(3)
90.0(3)
178.2(3)
100.1(2)
87.8(2)
91.8(2)
97.2(2)
84.5(2)
95.3(2)
161.32(4)
156.2(2)
92.01(19)
86.4(2)
Fig. 1. An ORTEP representation of the structure of [Fe2(l-SC6F5)(l-
PPh2)(CO)6] (2) at 50% probability showing the atom labeling scheme.
103.58(4)
59.831(10)
101.9(4)
91.2(3)
O(1)–C(1)
O(2)–C(2)
O(3)–C(3)
O(4)–C(4)
O(5)–C(5)
O(6)–C(6)
O(7)–C(7)
O(8)–C(8)
O(9)–C(9)
O(10)–C(10)
O(11)–C(11)
91.6(3)
90.1(3)
89.4(3)
178.2(3)
160.1(3)
97.7(2)
84.7(2)
93.7(2)
100.3(3)
157.5(2)
91.2(2)
87.3(2)
60.390(9)
101.0(3)
91.0(3)
90.3(3)
91.2(3)
91.1(3)
177.1(3)
98.6(2)
Fig. 2. An ORTEP representation of the structure of [Ru4(l3-
SPPh2)2(l-SC6F5)2(l-PPh2)2(SC6F5)2(CO)6] (3) at 50% probability
showing the atom labeling scheme.
160.2(2)
86.7(2)
91.1(2)
158.0(2)
100.8(2)
91.6(2)
85.59(19)
59.779(9)
101.6(3)
107.2(2)
103.0(2)
118.5(2)
118.8(2)
106.35(9)
107.6(2)
moiety in the molecule with signals at ꢀ124.13 (Fo),
ꢀ151.94 (Fp) and ꢀ159.79 (Fm) ppm with typical split-
ting patterns for the ligand ꢀSC6F5. Further analysis
of this complex by LSIMS exhibits the molecular ion
for the complex [M+] = 664 m/z.
Fig. 3. An ORTEP representation of the structure of [Os3(g1-Ph2P-
SC6F5)(CO)11] (4) at 50% probability showing the atom labeling
scheme.

´
O. Baldovino-Pantaleon et al. / Journal of Organometallic Chemistry 690 (2005) 2880–2887
2885
F
from the reaction mixture was taken and analyzed by
GC–MS, the results reveal the presence of
P(C6F5)(C6H5)2 in the solution, this compound is indeed
the result of the C–S activation process and probably
also consequence of a partial decomposition of the li-
gand C6F5S-P(C6H5)2 (1) during the reaction.
Ph2P
S
F
F
F
Fe
Fe
F
Crystals suitable for X-ray diffraction analysis of
complex 2 were obtained from a heptane/dichlorometh-
ane solvent system. Analysis of the red crystals revealed
a dinuclear structure bridged by ꢀPPh2 and ꢀSC6F5
moieties generating a butterfly like structure, which re-
sulted from P–S bond cleavage of compound 1 (Fig.
1). The two iron centers have a distorted geometry octa-
hedral. The coordination sphere is completed by six ter-
minal carbonyl ligands, three for each iron fragment. In
all other respects the bond distances and angles are with-
in the expected values (Table 2).
F
F
F
F
P
F
Ruthenium compounds and particularly, [Ru3-
(CO)12] has been recognized and used as a model
for HDS processes in homogeneous catalysis [12]. Thus
it is not surprising that the reaction of C6F5S-P(C6H5)2
(1) with [Ru3(CO)12] affords a product that goes be-
yond the mere activation of the P–S bond, affording
Slow diffusion of heptane into a saturated solution of
[Ru4(l3-SPPh2)2(l-SC6F5)2(l-PPh2)2(SC6F5)2(CO)6] (3)
in CH2Cl2 at room temperature, afforded red-orange
crystals. X-ray diffraction analysis revealed a tetrameric
structure consisting of two different ruthenium centers.
One is in a distorted trigonal bipyramidal (TBP) envi-
ronment, and the other having a slightly distorted octa-
hedral geometry bridged by l3-SPPh2, l-SC6F5 and
l-PPh2 moieties. The coordination spheres are com-
pleted by one terminal ꢀSC6F5 and one carbonyl ligand
for the TBP center, while the octahedron is completed
by two terminal carbonyl ligands and the sulfur of an-
other l3-SPPh2 moiety. The bond distances and angles
are comparable to those found in complexes
such as [Ru3(l-Se)(l-PPh2)(l-pyth)(CO)6{P(pyth)Ph2}]-
pyth = 5-(2-pyridyl)-2-thienyl [13]. [Ru3(CO)6(l3-CO)-
complex [Ru4(l -SPPh2)2(l-SC6F5)2(l-PPh2)2(SC6F5)2-
3
(CO)6] (3), which is the result of the P–S bond cleavage
and the activation of the C–S bond of the fluorinated
thiolate moiety. As a result of the presence of sulfur
in the molecule the structure is more complicated than
expected. Infrared analysis reveals absorptions due to
the presence of the carbonyl ligands between 1979
and 2045 cmꢀ1. The presence of the aromatic protons
were detected in the region 7.94–7.47 ppm. The
31P{1H}NMR spectrum is more instructive since it
shows signals at 145 and 106 ppm. The signal at
145 ppm is due to the phosphorus moiety bridging
the two ruthenium centers and the other bridges be-
tween one ruthenium center and one sulfur (vide infra).
The analysis by 19F NMR exhibits signals with typical
splitting patterns for ꢀSC6F5, the sets of signals are
duplicated (d ꢀ124.92 (d) and ꢀ128.92 (t) Fo,
ꢀ144.43 (d) and ꢀ146.73 (t) Fp, ꢀ154.74 (d) and
ꢀ158.36 (t) Fm) due to the presence of two different
types of thiolates, one bridging and one terminal.
FAB+-MS analysis identified the molecular ion
[M+] = 2174 m/z.
(l3-Se)(l-dppm)(g1-Ph2PCH2P(=O)Ph2)]
[14]
and
[Ru3(l-H){l-P(C4H2S)Ph2}(CO)8{P(C4H3S)Ph2}] [15].
In all other respects the bond distances and angles are
within the expected values (Table 3).
Finally, the reaction of C6F5S-P(C6H5)2 (1) with
[Os3(CO)12] seems to be the milder of all three processes,
since under reflux in heptane it afforded [Os3(g1-PPh2-
SC6F5)(CO)11] (4) as the sole product. Complex 4 resulted
from P-coordination to one of the osmium centers of the
cluster.
Infrared analysis of this complex reveals the presence
of the carbonyl ligands exhibiting absorptions between
1949 and 2068 cmꢀ1. As in the previous case, 1H
NMR of this complex exhibits signals corresponding
to the presence of the protons on the phenyl moiety at
7.59–7.44 ppm. Similarly, analysis by 19F NMR exhibits
signals at ꢀ127.12 (Fo), ꢀ148.20 (Fp) and ꢀ159.30 (Fm)
ppm with the typical splitting patterns for the ligand
ꢀSC6F5. Analysis by FAB+-MS as in the previous cases
exhibits the molecular ion for complex 3, [M+] = 1263
m/z.
C6F5
S
P
SC6F5
Ru
Ru
Ph2
PPh2
S
S
Ph2P
Ru
Ph2
P
Ru
SC6F5
SC6F5
In order to know the faith of the C6F5 group lost
from the thiolate moiety, some of the mother liquor

´
O. Baldovino-Pantaleon et al. / Journal of Organometallic Chemistry 690 (2005) 2880–2887
2886
In all cases, elemental analysis for the complexes
agreed with the proposed formulations.
Appendix A. Supplementary material
Supplementary data for complexes 2, 3 and 4 have
been deposited at the Cambridge Crystallographic Data
Centre. Copies of this information are available free of
charge on request from The Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (fax: +44 1223
336033; e-mail deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk) quoting the deposition
numbers CCDC 257187 trough 257189. Supplementary
data associated with this article can be found, in the on-
line version at doi:10.1016/j.jorganchem.2005.02.046.
F
S
F
Os
Os
F
F
P
Ph2
Os
F
Recrystalization of complex 4 from a CH2Cl2/hep-
tane solvent system afford pale yellow crystals. Analysis
of this compound by single crystal X-ray diffraction
analysis, revealed a compound where the starting mate-
rial [Os3(CO)12] had lost one carbonyl, which was substi-
tuted by the compound C6F5S-P(C6H5)2 (1). In this case,
the structure of the P–S ligand remains intact after the
reaction. The bond distances and angles are similar to
those observed for the starting material [Os3(CO)12]
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