Synthesis and characterization of oxo- and thiophosphorylcyclopentadienyl Ti(IV) thiolate complexes.

Article abstract of DOI:10.1016/S0022-328X(98)00496-3

New titanium (IV) complexes containing diphenyloxo- or diphenylthiophosphorylcyclopentadienyl ligands are obtained by reaction of diphenylphosphinocyclopentadienyl derivatives with the appropriate oxidizer (S₈ or H₂O₂). The crystal structures of [(η⁵-C₅H₄P(S)Ph₂)(η⁵-C₅H₄SiMe₃)TiCl₂] 3 and [(η⁵-C₅H₄P(S)Ph₂)₂Ti( SPh)₂]·C₄H₁₀O 7 indicate in both cases, a pseudo-tetrahedral arrangement around the titanium atom. The two SPh ligands in compound 7 are orientated in opposite sites of the TiS₂ plane, which suggests an anti conformation for this molecule.

Full text of DOI:10.1016/S0022-328X(98)00496-3

Journal of Organometallic Chemistry 560 (1998) 27–33
Synthesis and characterization of oxo- and
thiophosphorylcyclopentadienyl Ti(IV) thiolate complexes. Crystal
structures of [(p5-C5H4P(S)Ph2)(p5-C5H4SiMe3)TiCl2] and
[(p5-C5H4P(S)Ph2)2Ti(SPh)2]·C4H10O
Esther Delgado a,*, M. Angeles Garc´ıa a, Elisa Herna´ndez a, Noelia Mansilla a,
L. Alfonso Mart´ınez-Cruz b, Jesu´s Tornero c, Rosario Torres c
a Departamento de Qu´ımica Inorga´nica, Facultad de Ciencias, Uni6ersidad Auto´noma de Madrid, 20249 Madrid, Spain
b Instituto de Qu´ımica-F´ısica Rocasolano, Departamento de Cristalograf´ıa, CSIC, 28006 Madrid, Spain
c Ser6icio Interdepartamental de In6estigacio´n (Rayos X), Uni6ersidad Auto´noma de Madrid, 28049 Madrid, Spain
Received 16 July 1997
Abstract
New titanium (IV) complexes containing diphenyloxo- or diphenylthiophosphorylcyclopentadienyl ligands are obtained by
reaction of diphenylphosphinocyclopentadienyl derivatives with the appropriate oxidizer (S8 or H2O2). The crystal structures of
[(p5-C5H4P(S)Ph2)(p5-C5H4SiMe3)TiCl2] 3 and [(p5-C5H4P(S)Ph2)2Ti(SPh)2]·C4H10O 7 indicate in both cases, a pseudo-tetrahedral
arrangement around the titanium atom. The two SPh ligands in compound 7 are orientated in opposite sites of the TiS2 plane,
which suggests an anti conformation for this molecule. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Titanium; Thiolate; Cyclopentadienyl
induce changes in the reactivity and stability of these
complexes when compared with those bearing unsubsti-
1. Introduction
tuted rings [5]. But although many compounds of for-
Organotransition metal compounds with ligands con-
taining sulfur atoms have been a subject of considerable
interest in recent years on view of their importance to
t
mula [(p5-C5H4R)(p5-C5H5)TiX2] (R=Me, Bu, SiMe3,
CHꢀCH2, etc.) have been reported [6], data on
analogous species with mixed monosubstituted Cp lig-
biological systems [1] and catalytic processes [2]. The
ands are scarce. Derivatives of these type containing a
chemistry of cyclopentadienyl (Cp) Ti(IV) thiolate
donor-substituent group might undoubtedly prove an
derivatives is being also explored due to the ability of
useful way to bond to other metal fragments. In this
these species to act as metalloligands towards different
context recently Jutzi et al. [7] have synthesized the new
metal fragments [3]. In addition, structural studies car-
ried out on bent metallocene thiolates have pointed out
the conformational preferences exhibited by these com-
plexes depending on the S–M–S angle [4].
complex
Cl2].
[(p5-C5H4CH2CH2NiPr2)(p5-C5H4SiMe3)Ti-
By the other hand, the coordination chemistry of the
phosphine oxides and sulphides has been a subject of
numerous studies over the years [8], however little work
has been done on related oxo- and thiophosphorylcy-
clopentadienyl ligands with the exception of ferrocene
systems containing these ligands [9].
The presence of substituted Cp ligands is known to
* Corresponding author. Fax: +34
1 3974833; e-mail: es-
ther.delgado@uam.es
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00496-3

28
E. Delgado et al. / Journal of Organometallic Chemistry 560 (1998) 27–33
In connection with our current studies on thiolate
of signals due to the presence of two different mono-
substituted Cp rings in the same molecule. The reso-
nances corresponding to C5H4SiMe3 and C5H4PPh2
appear as two triplets and two multiplets respectively.
The assignation of these signals was confirmed on the
titanium (IV) derivatives, we report the syntheses and
characterization of compounds [(p5-C5H4PPh2)(p5-
C5H4SiMe3)TiX2] (X=Cl 1; X=SPh 2) and the new
diphenyloxo- and diphenylthiophosphorylcyclopentadi-
enyl complexes of formula [(p5-C5H4P(E)Ph2)(p5-
C5H4SiMe3)TiX2] (E=S, X=Cl 3; E=O, X=SPh 4;
E=S, X=SPh 5) and [(p5-C5H4P(E)Ph2)2TiX2] (E=S,
X=Cl 6; E=S, X=SPh 7; E=O, X=SPh 8).
For compounds [(p5-C5H4P(S)Ph2)(p5-C5H4SiMe3)-
TiCl2] 3 and [(p5-C5H4P(S)Ph2)2Ti(SPh)2]·C4H10O 7 X-
ray diffraction studies have been carried out.
1
basis of 31P decoupling in the H-NMR spectra of the
complexes. The 31P{1H}-NMR spectra exhibit one sin-
glet at −14.0 ppm for compound 1 and −15.7 ppm
for compound 2, which are in the same range that
related species [(p5-C5H4PPh2)2TiX2] [11] (X=Cl, SPh).
It is well documented that the P atom in monoter-
tiary phosphines can easily be oxidized to give the
corresponding phosphine chalcogenides R3PꢀE (E=O,
S, Se), whose coordination chemistry has been widely
explored [8]. A few reports have described the use of
1,1-bis(diphenylphosphoryl)ferrocene as chelate ligand
towards Cu, Ag and Au [9]. But as far as we know,
nothing has been published on thio- or oxophosphoryl-
cyclopentadienyl titanium complexes. To gain insight
into this field we were interested in the synthesis of new
2. Results and discussion
The ability of the thiolate titanocene species to act as
metalloligands in the synthesis of heteronuclear com-
pounds has been studied by Stephan et al. among
others [3]. It is clear that the presence of a donor group
as substituent in the Cp rings of these titanocene
derivatives could also facilitate coordination to other
metal fragments through these ligands. Nevertheless
since Poilblanc et al. [10] reported the synthesis of
compounds (p5-C5H4(CH2)nPPh2)2MCl2 (M=Ti, Zr)
no much chemistry has been developed in this direction.
Very recently we have studied ([3]b, [11]) the coordina-
tive competition between P and S atoms towards Mo,
Pt and Pd fragments in complexes bis[(diphenylphos-
phino)cyclopentadienyl] bis(chloride) or bis(thiolate)
Ti(IV). Our experience with these derivatives reveals
their unstability in solution. In contrast the presence in
the Cp rings of no donor groups, such as SiMe3, seems
to improve the stability and to enhance the solubility of
the complexes [12].
mononuclear
titanium
(IV)
complexes
using
diphenylthio- and diphenyloxophosphorylcyclopentadi-
enyl ligands able to act as precursors to obtain heter-
obi- or heteropolynuclear compounds.
We
have
prepared
the
compounds
[(p5-
C5H4P(E)Ph2)(p5-C5H4SiMe3)TiX2] (E=S, X=Cl 3;
E=O, X=SPh 4; E=S, X=SPh 5) and [(p5-
C5H4P(E)Ph2)2TiX2] (E=S, X=Cl 6; E=S, X=SPh
7; E=O, X=SPh 8) by reaction of [(p5-C5H4PPh2)(p5-
C5H4SiMe3)TiX2] or [(p5-C5H4PPh2)2TiX2] (X=Cl,
SPh) with the appropriate oxidizer (S8 or H2O2) at 0°C
and using toluene or THF as solvent. Orange–red
solutions are characteristic of dichloride derivatives 3
and 6, whereas for the phenylthiolate derivatives 4, 5, 7
and 8 deep emerald-green solutions are obtained in all
the cases.
In addition, data on mixed substituted Cp derivatives
of Ti(IV) being one of them a donor-substituent group
are scarce. Jutzi et al. [7] have just recently reported the
synthesis and characterization of the compound [(p5-
C5H4CH2CH2NiPr2)(p5-C5H4SiMe3)TiCl2].
When toluene solutions of 3 and 6 are treated with
the stoichometric amount of HSC6H5 and NEt3 com-
pounds 5 and 7 are also isolated, nevertheless these
reactions have proved to proceed in a much lower yield.
All the efforts we made to prepare the analogous
bis(chloride) derivatives containing the diphenylox-
ophosphorylcyclopentadienyl ligand failed (Scheme 1).
Keeping on mind all these ideas and following our
current studies on the chemistry of Cp derivatives of
Ti(IV) as precursors for the synthesis of heteronuclear
compounds, initially we attempted the preparation of
[(p5-C5H4PPh2)(p5-C5H4SiMe3)TiCl2] 1. Treatment of a
solution of [(p5-C5H4SiMe3)TiCl3] in toluene with
Tl[C5H4PPh2] yielded a 65% of 1 as a brown solid.
Further substitution of chloride ligands is achieved
upon reaction of 1 with the stoichometric amount of
HSPh and slight excess of Et3N in toluene. Under these
conditions the phenylthiolate derivative [(p5-
C5H4PPh2)(p5-C5H4SiMe3)Ti(SPh)2] 2 is obtained. As
expected, the new compounds 1 and 2 exhibit higher
stability in solution when compared with related deriva-
tives [(p5-C5H4PPh2)2TiX2] (X=Cl, SPh) [11].
1
The H-NMR spectra of these compounds in the Cp
region exhibit two sets of signals for each different
substituted Cp ring, with the exception of compound 6
1
which shows only one quartet signal. Again H-NMR
spectra decoupled from 31P were recorded in order to
assign unambiguosly the signals corresponding to the
protons of the rings. The presence of Ph2PꢀE (E=O,
S), a relatively more electronegative group than Ph2P,
may cause a higher deshielding in the Cp ring and
consequently provoke a downfield shift for these pro-
tons. Furthermore, as we mentioned before the lower
electronegativity of SPh comparing to that of chloride
The 1H-NMR spectra show in the Cp region four sets

E. Delgado et al. / Journal of Organometallic Chemistry 560 (1998) 27–33
29
Scheme 1. Synthetic route to complexes 2–8. a Taken from ref. [11].
ligand should shift the resonances of Cp protons to
upfield. The H-NMR spectra recorded point out that
both effects are taking place.
and the two centroids of the diphenylthiophosphoryl-
and trimethylsilylcyclopentadienyl ligands. The Ti–Cl
distances [2.350(1) and 2.318(1) A] and Cl–Ti–Cl angle
1
˚
Upon
oxidation
or
sulfurization
of
the
[95.74(5)°] are similar to those found in related com-
(diphenylphosphino)cyclopentadienyl group the 31P
chemical shifts of compounds 3–8 move to downfield,
as expected, consistent with a change from P(III) to
P(V).
pounds [(p5-C5H5)(p5-C5Ph5)TiCl2] [14] and [(p5-
C5H4CH2CH2NiPr2)(p5-C5H4SiMe3)TiCl2]
[7].
As
expected for this type of compound, the two substituted
Cp rings adopt a ‘staggered’ conformation being posi-
tioned the bulky substituents as far as possible. The
In the IR spectra the stretching vibration frequencies
of PꢀE (E=O, S) appear in the normal range for these
groups [13]. The mass spectra show the molecular ion
peaks. Fragments attributable to [M+ −X] and [M+
−2X] (X=Cl, SPh) are prominent in all the cases.
˚
PꢀS distance [1.944(2) A] for the thiophosphorylcy-
clopentadienyl ligand is in agreement with values previ-
ously reported ([8]a, [9]).
2.2. Crystal structure of
2.1. Crystal structure of
[(p5-C5H4P(S)Ph2)2Ti(SPh)2] ·C4H10O (7)
[(p5-C5H4P(S)Ph2)(p5-C5H4SiMe3)TiCl2] (3)
An ORTEP illustration of the molecular structure
and atom labeling scheme for compound 7 is shown in
Fig. 2. Selected bond lengths and angles for 7 are given
in Table 3. Theoretical studies and X-ray data [4] found
in the literature on relationship between the S(1)–Ti–
S(2) angle value and the type of conformer that the
thiolate derivatives of biscyclopentadienyl Ti(IV) show
The molecular structure showing the atom number-
ing scheme is presented in Fig. 1. Crystal data for
complexes 3 and 7 are given in Table 1, while selected
bond lengths and angles for 3 are listed in Table 2. The
complex shows a distorted tetrahedral arrangement
about the titanium atom made up of the two chlorides

30
E. Delgado et al. / Journal of Organometallic Chemistry 560 (1998) 27–33
AMX-300 and Varian Unity 500 Plus. Chemical shifts
are reported in parts per million relative to external
standards (TMS for 1H and 85% H3PO4 for 31P).
Elemental analyses for C and H were performed with a
Perkin-Elmer 2400. FAB positive ion mass spectra were
measured on a VG Autospec spectrometer.
3.1. [(p5-C5H4PPh2)(p5-C5H4SiMe3)TiCl2] (1)
Tl[C5H4PPh2] (1.0 g, 2.2 mmol) was added to a
solution of [(p5-C5H4SiMe3)TiCl3] (0.40 g, 1.4 mmol) in
toluene (20 cm3). After 1 h stirring at room temperature
(r.t.) the resultant solution was evaporated to dryness.
The solid obtained was extracted with 2×5 cm3 por-
tions of dichloromethane and filtered through a plug of
Celite. Removal of the solvent yielded the product as a
brown solid. Recrystallization in dichloromethane–hex-
ane (1:2.5) at −20oC afforded analytical pure samples
(0.46 g, 65%). Anal. Found:
C25H27Cl2PSiTi requires: C 59.42, H 5.39%. H-NMR
(CDCl3): 7.42–7.34 (10H, m, PPh), 6.78 (2H, t,
C 59.05, H 5.34.
1
C5H4
6
SiMe3), 6.57 (2H, m, C5H4
PPh2), 6.40 (2H, t, C5H4SiMe3), 0.27 (9H, s, SiMe)
Ph) ppm.
6 PPh2), 6.55 (2H, m,
C5H4
6
6
ppm. 31P{1H}-NMR (CDCl3): −14.0 (s, P
6
MS: m/z 505 (M+), 469 (M+ −Cl).
Fig. 1. X-ray structure of compound 3.
Table 1
is in agreement with the value of S(1)–Ti–S(2) angle
[99.26(7)°] and the endo (anti) conformation exhibited
by the new compound [(p5-C5H4P(S)Ph2)2Ti(SPh)2].
Previously we reported [12] a similar behavior for the
complex [(p5-C5H4SiMe3)2Ti(SC6F5)2]. The geometry at
the titanium atom is pseudo-tetrahedral; the Ti–S dis-
Crystallographic data for complexes 3 and 7
3
7
Empirical formula
C25H25Cl2PSSiTi
C46H38P2S4Ti·C4H10O
MW
535.37
902.96
˚
tances [2.410(2) and 2.423(2) A] and S(1)–Ti–S(2)
Crystal size (mm)
Crystal system
Space group
Lattice parameters
0.24×0.18×0.20
Triclinic
P1
0.05×0.275×0.35
Monoclinic
P21/c
[99.26(7)°] are similar to those observed in analogous
derivatives [12,15]. A projection of the Cp rings onto
the plane formed by the titanium and the two sulfur
atoms reveals a ‘staggered’ conformation for them. The
˚
a (A)
10.504(3)
11.023(5)
12.155(5)
72.10(3)
80.35(1)
72.44(1)
1272.5(9)
2
1.397
552
6.674
60
13.341(1)
14.055(1)
25.256(1)
˚
b (A)
˚
distances of 1.944(2) and 1.942(2) A for P(1)–S(3) and
˚
c (A)
P(2)–S(4) bonds are comparable to that of compound
3.
h (°)
i (°)
99.931(4)
k (°)
3
˚
V (A )
4664.7(3)
4
1.286
1888
4.148
90
−1–12, −12–12,
−22–23
8476
Z
Dcalc. (g cm−3
F(000)
)
3. Experimental
v (mm−1
2qmax (°)
)
All the reactions were carried out under argon using
Schlenk techniques [16]. Solvents were purified accord-
ing to standard procedures [17]. The starting materials
Tl[C5H4PPh2] [18], [(p5-C5H4SiMe3)TiCl3] [19], [(p5-
C5H4PPh2)2TiCl2] [11] and [(p5-C5H4PPh2)2Ti(SC6H5)2]
[11] were prepared as previously described. All the
other reagents are commercially available and were
used as purchased. IR spectra were recorded on a
Perkin Elmer 1650 FT spectrophotometer using KBr
hkl Ranges
0–11, −11–12,
−13–13
3777
Reflections measured
Reflections observed
[(I\2|(I)]
3667
3693
No. variables
280
490
Goodness of fit on F2 1.027
1.037
0.068
0.178
Final R
Final weighted R
0.0475
0.1368
1
pellets. H- and 31P-NMR were recorded on a Bruker

E. Delgado et al. / Journal of Organometallic Chemistry 560 (1998) 27–33
31
Table 2
Selected bond lengths (A) and angles (°) for complex 3
red–orange crystals (0.57 g, 63%) suitable for X-ray
diffraction study. Anal. Found: C 55.32, H 5.02.
C25H27Cl2PSSiTi requires: C 55.88, H 5.06%. IR: wmax
˚
˚
Bond lengths (A)
(cm−1
)
657 (PꢀS). 1H-NMR (CDCl3): 7.65–7.43
Ti(1)–Cl(2)
Ti(1)–Cl(1)
S(1)–P(1)
2.318(1) Ti–Cp(1)
2.350(1) Ti–Cp(2)
1.944(2) Mean Si–C (methyl
groups)
2.102(1)
2.072(1)
1.867
(10H, m, PPh), 7.17 (2H, q, C5H4
(4H, m, C5H4SiMe3), 6.62 (2H, q, C5H4
0.25 (9H, s, SiMe) ppm. 31P{1H}-NMR (CDCl3):
35.4 (s, P
(S)Ph) ppm. MS: m/z 536 (M+), 501 (M+
−Cl).
6
P(S)Ph2), 6.83
6
6
P(S)Ph2),
P(1)–C(1)
P(1)–C(6)
P(1)–C(12)
1.797(3) Mean C–C [Cp(1)]
1.805(3) Mean C–C [Cp(2)]
1.809(3) Mean C–C (benzene
rings)
1.404
1.406
1.378
6
3.4. [(p5-C5H4P(O)Ph2)(p5-C5H4SiMe3)Ti(SPh)2] (4)
Bond angles (°)
Cl(2)–Ti(1)–Cl(1)
C(1)–P(1)–C(6)
C(1)–P(1)–C(12)
C(6)–P(1)–C(12)
C(1)–P(1)–S(1)
C(6)–P(1)–S(1)
C(12)–P(1)–S(1)
95.74(5) C(24)–Si(1)–C(23)
107.15(14) C(25)–Si(1)–C(23)
105.33(14) C(24)–Si(1)–C(18)
110.1(2)
An ice-cooled solution of [(p5-C5H4PPh2)(p5-
C5H4SiMe3)Ti(SPh)2] (0.35 g, 0.53 mmol) in THF (30
cm3) was treated with 30% H2O2 (0.04 cm3, 0.53
mmol) and the mixture stirred for 1.5 h. The solvent
was removed in vacuo and the solid obtained was
purified by chromatography on a silica column using
toluene–THF (20:1) as eluent to gave a violet–green
band of 4. Recrystallization from diethyl ether solu-
tion at −20°C afforded a deep-green crystalline solid
109.0(2)
109.5(2)
111.3(2)
105.5(2)
132.00
103.3(2)
C(25)–Si(1)–C(18)
113.83(11) C(23)–Si(1)–C(18)
114.29(13) Cp(1)–Ti–Cp(2)
112.05(12) Mean C–C–C (Cp
rings)
108.0
C(24)–Si(1)–C(25) 111.2(2)
Mean C–C–C (ben- 120.2
zene rings)
Cp(1) refers to the centroid of the ring formed by C1, C2, C3, C4 and
C5.
Cp(2) refers to the centroid of the ring formed by C18, C19, C20, C21
and C22.
(0.26 g, 75%). Anal. Found:
C 66.49, H 5.63.
C37H37OPS2SiTi requires: C 66.45, H 5.58%. IR: wmax
(cm−1) 1181 (PꢀO). 1H-NMR (CDCl3): 7.57–7.07
(20H, m, PPh, SPh); 6.83 (2H, t, C5H4
(4H, br d, C5H4P(S)Ph2); 6.23 (2H, br s, C5H4
0.21 (9H, s, SiMe) ppm. 31P{1H}-NMR (CDCl3): 23.3
6
SiMe3); 6.32
6
6
SiMe3);
3.2. [(p5-C5H4PPh2)(p5-C5H4SiMe3)Ti(SPh)2] (2)
(s, P6 −
(O)Ph) ppm. MS: m/z 668 (M+), 559 (M+
SPh), 450 (M+ −2SPh).
To a solution of [(p5-C5H4PPh2)(p5-C5H4SiMe3)-
TiCl2] (0.30 g, 0.7 mmol) in toluene (30 cm3), HSPh
(0.14 cm3, 1.4 mmol) and NEt3 (0.27 cm3, 1.6 mmol)
were added. After stirring for 3.5 h at r.t., the resul-
tant violet solution was evaporated to dryness. Fur-
3.5. [(p5-C5H4P(S)Ph2)(p5-C5H4SiMe3)Ti(SPh)2] (5)
Complex 5 was prepared following the same proce-
dure than 4 but using sulfur. Elution from the silica
column with hexane–toluene (1:2) and further recrys-
tallization from diethyl ether–hexane (1:1) at −20°C
afforded a deep-green crystalline solid (81%). Anal.
Found: C 65.10, H 5.65. C37H37PS3SiTi requires: C
ther purification by chromatography on
a silica
column, using hexane–toluene (1:4) as eluent, gave a
violet band of 2. Recrystallization from diethyl ether–
pentane (1:1.5) at −20°C afforded a violet crystalline
solid (0.20 g, 45%). Anal. Found: C 68.43, H 5.76.
C37H37PS2SiTi requires: C 68.08, H 5.71%. H-NMR
(CDCl3): 7.45–7.07 (20H, m, PPh, SPh), 6.28 (2H, t,
1
64.89, H 5.45%. IR: wmax (cm−1) 656 (PꢀS). H-NMR
1
(CDCl3): 7.62–7.08 (20H, m, PPh, SPh), 6.73 (2H, t,
C5H4
s, C5H4
(9H, s, SiMe) ppm. 31P{1H}-NMR (CDCl3): 35.7 (s,
6
SiMe3), 6.46 (2H, q, C5H4
6
P(S)Ph2), 6.36 (2H, br
C5H4
6
SiMe3), 6.25 (2H, m, C5H4
PPh2), 5.99 (2H, t, C5H4
6
PPh2), 6.19 (2H, m,
6 SiMe3), 0.20 (9H, s,
6
P(S)Ph2), 5.92 (2H, br s, C5H4
6
SiMe3), 0.23
C5H4
6
SiMe) ppm. 31P{1H}-NMR (CDCl3): −15.7 (s, P
6
Ph)
P6
(S)Ph) ppm. MS: m/z 683 (M+), 575 (M+ −SPh),
ppm. MS: m/z 652 (M+), 543 (M+ −SPh), 434 (M+
−2SPh).
466 (M+ −2SPh).
3.6. [(p5-C5H4P(S)Ph2)2TiCl2] (6)
3.3. [(p5-C5H4P(S)Ph2)(p5-C5H4SiMe3)TiCl2] (3)
An ice-cooled solution of [(p5-C5H4PPh2)(p5-
C5H4SiMe3)TiCl2] (0.90 g, 1.77 mmol) in toluene (30
cm3) was treated with sulfur (0.114 g, 3.54 mmol) and
the mixture stirred for 1.5 h. The resultant solution
was filtered through a plug of celite and the solvent
This compound was obtained following the same
procedure as 3 with 55% yield. Anal. Found: C 59.64,
H 4.16. C34H28Cl2P2S2Ti requires: C 59.93, H 4.14%.
1
IR: wmax (cm−1) 654 (PꢀS). H-NMR (CDCl3): 7.64–
7.39 (20H, m, PPh), 6.79 (8H, q, C5H4
31P{1H}-NMR (CDCl3): 35.0 (s, P
m/z 681 (M+), 646 (M+ −Cl).
6
P(S)Ph2) ppm.
6
(S)Ph) ppm. MS:
removed
in
vacuo.
Recrystallization
from
dichloromethane–hexane (1:1) at −20°C afforded

32
E. Delgado et al. / Journal of Organometallic Chemistry 560 (1998) 27–33
Fig. 2. X-ray structure of compound 7.
3.7. [(p5-C5H4P(S)Ph2)2Ti(SPh)2] (7)
MS: m/z 719 (M+), 687 (M+ −SPh), 578 (M+
−
2SPh).
An ice-cooled solution of [(p5-C5H4PPh2)2Ti(SPh)2]
(0.41 g, 0.53 mmol) in THF (30 cm3) was treated with
sulfur (0.034 g, 1.06 mmol) and the mixture stirred for
1.5 h. The solvent was removed in vacuo and the solid
obtained washed with hexane leaving the product as a
green solid. Recrystallization from diethyl ether solu-
tion at −20°C gave deep-green crystals of 7 (80%)
suitable for X-ray diffraction study. Anal. Found: C
66.45, H 4.70. C46H38P2S4Ti requires: C 66.66, H
3.9. Crystal structure of complex (3)
Suitable crystals for X-ray studies of compound
C25H25Cl2PSSiTi were obtained from dichloromethane/
n-hexane at −20°C. A red crystal was mounted in a
glass capillary and data were collected on an Enraf-No-
nius CAD4 diffractometer, using graphite monochro-
mated Cu–Kh radiation. Crystal data are given in
Table 1. No extinction correction was applied. Absorp-
tion was corrected using c-scan data [20], 1.171 and
0.781 being the maximum and minimum corrections.
The structure was solved by direct methods using
SIR92 [21] and was refined by LS analysis using
SHELX93 [22] with anisotropic parameters for non-H
atoms. The positions of the H atoms were refined using
the riding model on the corresponding C atoms.
1
4.62%. IR: wmax (cm−1) 654 (PꢀS). H-NMR (CDCl3):
7.59–7.03 (30H, m, PPh, SPh), 6.80 (4H, m,
C5H4
6
P(S)Ph2), 6.38 (4H, m, C5H4
6
P(S)Ph2) ppm.
31P{1H}-NMR (CDCl3): 35.5 (s, P
6 (S)Ph) ppm. MS: m/z
828 (M+), 719 (M+ −SPh), 610 (M+ −2SPh).
3.8. [(p5-C5H4P(O)Ph2)2Ti(SPh)2] (8)
This compound was obtained following the same
procedure as compound 7 but using 30% H2O2 (75%).
Anal. Found: C 69.07, H 4.76. C46H38P2O2S2Ti re-
quires: C 69.34, H 4.81%. IR: wmax (cm−1) 1167 (PꢀO).
1H-NMR (CDCl3): 7.58–6.97 (30H, m, PPh, SPh), 6.85
3.10. Crystal structure of complex (7) ·C4H10O
Single crystals of compound C46H38P2S4Ti·C4H10O
were grown by cooling a saturated solution of the
complex at −20°C. A deep green crystal was selected
and mounted on a Siemens P4R diffractometer. Data
(4H, m, C5H4
6
P(O)Ph2), 6.53 (4H, br s, C5H6 4P(O)Ph2)
ppm. 31P{1H}-NMR (CDCl3): 22.4 (s, P
6
(O)Ph) ppm.

E. Delgado et al. / Journal of Organometallic Chemistry 560 (1998) 27–33
33
Table 3
Selected bond lengths (A) and angles (°) for complex 7
[2] (a) B.C. Wiegand, C.M. Friend, Chem. Rev. 22 (1992) 22 491
and refs. therein. (b) R.J. Angelici, Acc. Chem. Res. 21 (1988)
387. (c) J.T. Roberts, C.M. Friend, J. Am. Chem. Soc. 108
(1986) 7204. (d) C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, P.
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115 (1993) 2731. (e) C. Bianchini, P. Frediani, V. Herrera, M.V.
Jime´nez, A. Meli, L. Rinco´n, R. Sa´nchez-Delgado, F. Vizza, J.
Am. Chem. Soc. 117 (1995) 4333. (e) D.A. Vicic, W.D. Jones,
Organometallics 16 (1997) 1912.
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Lalinde, M.T. Moreno, Inorg. Chem. 34 (1995) 5279. (b) I. Ara,
E. Delgado, J. Fornie´s, E. Herna´ndez, E. Lalinde, N. Mansilla,
M.T. Moreno, J. Chem. Soc. Dalton Trans. (1996) 3201. (c)
D.W. Stephan, T.T. Nadashi, Coord. Chem. Rev. 147 (1996)
147.
[4] M.Y. Darensbourg, M. Pala, S.A. Houliston, K.P. Kidwell, D.
Spencer, S.S. Chojnacki, J.H. Reibenspies, Inorg. Chem. 31
(1992) 1487.
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Catal. 60 (1990) 19. (b) P. Jutzi, T. Redeker, Organometallics 16
(1997) 1343.
[6] M. Bochmann, in: E.W. Abel, F.G.A. Stone, G. Wilkinson
(Eds.), Comprehensive Organometallic Chemistry II, vol. 4,
[M.F. Lappert (Vol. Ed.)], Pergamon, Oxford, 1995, ch. 5.
[7] P. Jutzi, T. Redeker, B. Neumann, H.G. Stammler, Chem. Ber.
129 (1996) 1509.
˚
˚
Bond lengths (A)
Ti(1)–S(1)
Ti(1)–S(2)
S(1)–C(11)
S(2)–C(17)
P(1)–S(3)
P(2)–S(4)
P(1)–C(9)
P(1)–C(35)
2.410(2) P(1)–C(41)
2.423(2) P(2)–C(4)
1.765(7) P(2)–C(23)
1.766(7) P(2)–C(29)
1.944(2) Ti–Cp(1)
1.821(6)
1.803(6)
1.808(7)
1.805(7)
2.092
2.084
1.402
1.371
1.942(2) Ti–Cp(2)
1.819(6) Mean C–C (Cp rings)
1.801(7) Mean C–C (benzene
rings)
Bond angles (°)
S(1)–Ti–S(2)
99.26(7) S(4)–P(2)–C(4)
117.3(2)
Ti(1)–S(1)–C(11) 116.2(2)
Ti(1)–S(2)–C(17) 112.3(2)
S(4)–P(2)–C(23)
S(4)–P(2)–C(29)
C(4)–P(2)–C(23)
C(4)–P(2)–C(29)
C(23)–P(2)–C(29)
Cp(1)–Ti–Cp(2)
Mean C–C–C (Cp
rings)
112.8(2)
112.0(2)
100.9(3)
106.3(3)
106.6(3)
135.1
S(3)–P(1)–C(9)
112.7(2)
S(3)–P(1)–C(35) 114.2(3)
S(3)–P(1)–C(41) 112.4(2)
C(9)–P(1)–C(35) 108.1(3)
C(9)–P(1)–C(41) 104.5(3)
108.0
C(35)–P(1)–C(41) 104.2(3)
Mean C–C–C (benzene 120.0
rings)
[8] (a) S.E. Livingstone, P.L. Goggin, in: G. Wilkinson, R.D.
Gillard, J.A. McCleverty (Eds.), Comprehensive Coordination
Chemistry, vol. 2, Pergamon, Oxford, 1987, ch. 16.6, 15.8. (b)
T.S. Lobana, Prog. Inorg. Chem. 37 (1989) 495 and refs. therein.
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Bandoli, B. Corain, J. Chem. Soc. Dalton Trans. (1997) 819.
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rier, F. Mathey, J. Organomet. Chem. 231 (1982) C43.
[11] E. Delgado, J. Fornie´s, E. Herna´ndez, E. Lalinde, N. Mansilla,
M.T. Moreno, J. Organomet. Chem. 494 (1995) 261.
[12] E. Delgado, E. Herna´ndez, A. Hedayat, J. Tornero, R. Torres, J.
Organomet. Chem. 466 (1994) 119.
Cp(1) refers to the centroid of the ring formed by C1, C2, C3, C4 and
C5.
Cp(2) refers to the centroid of the ring formed by C6, C7, C8, C9 and
C10.
were collected using Cu–Kh radiation by the ꢀ/2q
technique. Crystal data are given in Table 1. No extinc-
tion correction was applied. The structure was solved
by direct methods and refined by full matrix least
squares technique using the program SHELXTL ver-
sion 5 [23]. All ring-carbon atoms were founded by
differential synthesis but refined as ‘rigid groups’ with
the H atoms located by geometric calculations. The rest
of the atoms were refined anisotropically. This com-
pound crystallizes with a disordered diethyl ether
molecule.
[13] N.B. Colthup, L.H. Daly, S.E. Wiberley, Introduction to In-
frared and Raman Spectroscopy, Academic Press, New York,
1964.
[14] U. Thewalt, G. Schmid, J. Organomet. Chem. 412 (1991) 343.
[15] (a) E.G. Muller, S.F. Watking, L.F. Dahl, J. Organomet. Chem.
111 (1976) 73. (b) M.A.A. de C.T. Carrondo, G.A. Jeffrey, Acta.
Crystallogr. Sec. C. 42 (1983) C39. (c) M.J. Calhorda, M.A.A. de
C.T. Carrondo, A.R. Dias, C.F. Frazao, M.B. Hursthouse, J.A.
Martinho Simoes, C. Texeira, Inorg. Chem. 27 (1988) 2513.
[16] D.F. Shriver, M.A. Drezdon, The Manipulation of Air Sensitive
Compounds, 2nd ed., Wiley, New York, 1986.
Acknowledgements
[17] D.D. Perrin, W.L.F. Armarengo, D.R. Perrin, Purification of
Laboratory Chemicals, 2nd edn, Pergamon, Oxford, 1980.
[18] M.D. Rausch, B.H. Edwards, R.D. Rogers, J.L. Atwood, J. Am.
Chem. Soc. 105 (1983) 3882.
[19] A.M. Cardoso, R.J.H. Clark, S. Moorhouse, J. Chem. Soc.
Dalton Trans. (1980) 1157.
Financial support was generously provided by the
Direccio´n General de Investigacio´n Cient´ıfica y Te´c-
nica, Spain (Project PB93-0250). The authors wish to
thank M. Galakhov, Universidad de Alcala´, Madrid,
for helpful NMR measurements.
[20] A.C.T. North, D.C. Phillips, F.S. Mathews, Acta Crystallogr.
Sec. A 24 (1968) 351.
[21] A. Altomare, M.C. Burla, M. Camalli, G. Cascarano, C. Giaco-
vazzo, G. Polidori, SIR92, J. Appl. Crystallogr. 27 (1994) 435.
[22] (a) G.M. Sheldrick, Acta. Crystallogr. Sec. A 46 (1990) 467. (b)
G.M. Sheldrick, SHELX93, 1993, University of Go¨ttingen, Ger-
many.
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