The synthesis and structural characterization of [Et4N]2[Ti(SPh)6] and trimeric [Ti3O(SPh)3Cl4(CH3CN)5] · CH3CN · (C2H5)2O complexes

Article abstract of DOI:10.1016/S0277-5387(00)00374-0

The reaction of TiCl₄ with 6 equiv. of NaSPh in the presence of organic cations such as Et₄N⁺ or PPh₄⁺ proceeds to yield a novel homoleptic arylthiolate Ti(IV) complex, [Ti(SPh)₆]^2-. The Et₄N salt of [Ti(SPh)₆]^2- has been structurally determined. The coordination geometry around the metal ion is a regular octahedron in which the central titanium ion is located on the crystallographic inversion center. The infrared (IR) spectrum of compound I exhibits the characteristic Ti-S bond stretching vibrations of thiophenolate ligands at 480 and 430 cm^-1, and the ¹H NMR spectrum in CD₃CN displays characteristic Et₄N⁺ resonance peaks and six thiophenolate resonance peaks which are consistent with the solid state structure. The reaction of TiCl₄ with 3 or 4 equiv. of NaSPh in CH₃CN yields the unexpected mixture of dark purple [TiCl₃(CH₃CN)₃] and dark red [Ti₃O(SPh)₃Cl₄(CH₃CN)₅] · CH₃CN · (C₂H₅)₂O (II) complexes. Complex II has been structurally determined by single X-ray crystallography. The IR spectrum of complex II exhibits a μ₃-O stretching vibration at 600 cm^-1 and Ti-S vibrations of the thiophenolate ligand at 481 and 429 cm^-1. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0277-5387(00)00374-0

www.elsevier.nl/locate/poly
Polyhedron 19 (2000) 1139–1143
The synthesis and structural characterization of [Et4N]2[Ti(SPh)6] and
trimeric [Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP(C2H5)2O complexes
*
Jun Tae Kim, Jung Woo Park, Sang Man Koo
Department of Industrial Chemistry and Ceramic Processing Research Center, College of Engineering, Hanyang University, Seoul 133-791, South Korea
Received 5 January 2000; accepted 20 March 2000
Abstract
q
The reaction of TiCl4 with 6 equiv. of NaSPh in the presence of organic cations such as Et4Nq or PPh4 proceeds to yield a novel
homoleptic arylthiolate Ti(IV) complex, [Ti(SPh)6]2y. The Et4N salt of [Ti(SPh)6]2y has been structurally determined. The coordination
geometry around the metal ion is a regular octahedron in which the central titanium ion is located on the crystallographic inversion center.
The infrared (IR) spectrum of compound I exhibits the characteristic Ti–S bond stretching vibrations of thiophenolate ligands at 480 and 430
cmy1, and the 1H NMR spectrum in CD3CN displays characteristic Et4Nq resonance peaks and six thiophenolate resonance peaks which are
consistent with the solid state structure. The reaction of TiCl4 with 3 or 4 equiv. of NaSPh in CH3CN yields the unexpected mixture of dark
purple [TiCl3(CH3CN)3] and dark red [Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP(C2H5)2O (II) complexes. Complex II has been structurally
determined by single X-ray crystallography. The IR spectrum of complex II exhibits a m3–O stretching vibration at 600 cmy1 and Ti–S
vibrations of the thiophenolate ligand at 481 and 429 cmy1
.
q2000 Elsevier Science Ltd All rights reserved.
Keywords: Oxo ligands; Thiolates; Titanium; Trimers
1. Introduction
Reports on titanium complexes with thiolate ligands are
limited to
a few complexes, including Ti(S-2,4,6-
iPr3C6H2)4y, Ti(S-2,4,6-tBu3C6H2)4 [23] and dithiolate
complexes of titanium [20,21]. Recently. Giolando et al.
reported on the synthesis and structural characterization of
dimeric Ti2(SMe)9y, trimeric Ti3(SMe)12 complexeswhich
were obtained from the reaction of Ti(NR2)4 with RSH
(RsMe, Et) [24].
y
There has been an enormous study of the transition metal
complexes with aliphatic or aromatic thiolate ligands,
because they exhibit a variety of structural types with various
nuclearities [1–9], and certain complexes can be used as
precursors for corresponding transition metal sulfide com-
plexes [10–15]. Among the transition metal thiolate com-
plexes, mononuclear species with homolepticthiolateligands
are fundamental types that can be used to derive cluster and
cage types of molecules or correspondingthiometalates.Such
early transition metal complexes with homoleptic thiolate
We are interested in obtaining Ti(IV) homoleptic mono-
dentate thiolate complexes, potential starting materials for
corresponding thiotitanates. Here, we report the synthesisand
structural characterization of the homoleptic arylthiolate
titanium complex [Ti(SPh)6]2y (I) and the trimeric
[Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP(C2H5)2O (II).
ligands have been reported extensively in the last few
ny
years. For example, M(SPh)6
[16], M(SPh)4
(ns1, 2; MsNb, Ta)
2y
(MsMn, Fe, Co, Ni) [17,18] and
M(S2C2H4)3y (MsNb, Ta) [19], M(S2C2H4)3ny (ns1,
2; MsTi, Co, Cr) [20,21] have been synthesized and fully
characterized. In contrast to the other groups, the types and
structural pattern of group IV metal thiolate complexes have
not been fully studied. Recently, Tatsumi et al. reported
Zr(tBuS)5y and Zr(tBuS)62y complexes [22].
2. Experimental
All manipulations were performed using standard Schlenk
line techniques under dinitrogen atmosphere. Diethyl ether
was distilled after being refluxed with sodium–benzophe-
none. Acetonitrile was distilled after being refluxed over
CaH2 before use. TiCl4, Et4NBr and PPh4Cl were purchased
from Aldrich and used as received. Sodium thiophenolate
* Corresponding author. Tel.: q82-2-2290 0527; fax: q82-2-2281 4800;
e-mail: sangman@email.hanyang.ac.kr
0277-5387/00/$ - see front matter q2000 Elsevier Science Ltd All rights reserved.
PII S0277-5387(00)00374-0
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J.T. Kim et al. / Polyhedron 19 (2000) 1139–1143
(NaSPh) was prepared from the reaction of sodium and thio-
phenol in diethyl ether.
solution was stood at ambient temperature. Finally, a dark
red powder of [Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP
(C2H5)2O was obtained in 74% yield.
2.1. [Et4N]2[Ti(SPh)6] (I)
Calc. for Ti3S3O2N6Cl4C34H43: C, 43.03; H, 4.53; N, 8.85;
S, 10.14. Found: C, 43.24; H, 4.24; N, 8.76; S, 12.01%. FT-
IR (cmy1): n(Ti–O), 600.5; n(CH3CN), 2310.3, 2280;
A 250-ml Schlenk flask was charged with 2.26 g (17.23
mmol) of NaSPh, 1.10 g (5.30 mmol) of Et4NBr and a
stirring bar. To this mixture was added 50 ml of CH3CN via
a cannula with stirring at ambient temperature and 0.29 ml
(2.65 mmol) of TiCl4 was injected using a syringe. The color
of the solution turned to dark red immediately. After 2 h, the
solution was filtered through a fine porosity fritted funnel; to
the dark red filtrate, 50 ml of diethyl ether was added and the
resulting solution was left to stand at ambient temperature.
Finally, dark red crystalline materials were obtained in 80%
yield. Calc. for TiS6N2C52H70: C, 64.83; H, 7.27; N, 2.92; S,
19.97. Found: C, 64.91; H, 7.34; N, 3.01; S, 21.52%. FT-IR
1
n(Ti–SPh), 481, 429. H NMR in DMF-d7: d (CH3 in
CH3CN ligand and free CH3CN); 1.92–1.97 (m, 18H), d
(CH2 in Et2O); 3.28 (q, 4H), d (CH3 in Et2O); 1.06 (t, 6H),
d (C6H5 in SPh ligand); 7.252–7.285 (m, 15H).
2.3. X-ray crystallography
Single X-ray diffraction data forboth crystalsarepresented
in Table 1. Diffraction data were collected at ambient tem-
perature on a Bruker P4 four circle diffractometer using
Mo Ka radiation. Intensity data were collected by using a u–
2u step scan technique and for all data sets the condition of
the crystal was monitored by measuring 2 standard reflec-
tions. The solutions of both structures were carried out by a
combination of heavy atom Patterson techniques, direct
methods and Fourier techniques. The refinement of the struc-
tures by full-matrix least-squares methods was based on 2640
unique reflections (2us458, I)2s) for compound I, and
4361 unique reflections (2us22.58, I)2s) for compound
II. Anisotropic temperature factors were used for all non-
hydrogen atoms in compounds I and II, except solvent mol-
ecules packed in the lattice for compound II. At the current
stage of refinement on 312 parameters for compound I and
459 parameters for compound II with all atoms present in the
asymmetric units, Rs0.0383, Rws0.0989 for compound I
and Rs0.0715, Rws0.1982 for compound II.
(cmy1): n(Ti–SPh); 480, 430. H NMR in acetonitrile-d3:
1
d (CH3 in Et4Nq); 1.18 (t, 24H), d (CH2 in Et4Nq); 3.21
(q, 16H), d (C6H5 in SPh ligand); 6.97–7.42 (m, 30H). The
Ph4Pq salt was also obtained by a similar syntheticprocedure
in 80% yield. Calc. for TiS6P2C84H70: C, 73.05; H, 5.07.
Found: C, 73.23; H, 5.12%. IR (KBr disc) (cmy1): n(Ti–
SPh), 480 and 420.
2.2. [Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP(C2H5)2O (II)
2.2.1. Method A
A 250-ml Schlenk flask was charged with 1.39 g (10.60
mmol) of NaSPh and a stirring bar. To this flask 30 ml of
CH3CN was added via a cannula with stirring at ambient
temperature, and 0.29 ml (2.65 mmol) of TiCl4 was injected
using a syringe. The color of the solution turned to dark red.
After 2 h, the solution was filtered through a fine porosity
fritted funnel. To the red filtrate 100 ml of diethyl ether was
added and the resulting solution was stood at ambient tem-
perature. Dark purple crystals and dark red crystals were
isolated and dried under vacuum. Finally, a 1:1 mixture of
dark purple crystals of TiCl3(CH3CN)3 and dark red crystals
of [Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP(C2H5)2O were
obtained (see below). The total yield was approximately
70% (based on Ti). 1H NMR in DMF-d7: d (CH2 in CH3CN
in ligand and free CH3CN); 1.95 (br, 27H), d (CH3 in Et2O);
3.382 (q, 4H), d (CH3 in Et2O); 1.068 (t, 6H), d (C6H5 in
SPh ligand); 7.126–7.277 (m, 15H).
Table 1
Crystallographic data for [Et4N]2[Ti(SPh)6] (I) and [Ti3O(SPh)3Cl4-
(CH3CN)5]PCH3CNP(C2H5)2O (II)
I
II
Formula
FW
TiS6N2C52H70
963.36
Ti3S3O2N6Cl4C34H43
948.96
Crystal system
Space group
triclinic
P1 (no. 2)
monoclinic
P21/c (no. 14)
13.139(1)
8.653(1)
38.544(3)
¯
˚
a (A)
11.113(2)
11.414(2)
13.075(2)
112.89(1)
92.29(1)
118.77(1)
2
1285.2(4)
20
0.71073
1.245
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
90.94(1)
2.2.2. Method B
Z
4
TiCl4, 0.18 ml (1.68 mmol), was injected using a syringe
into a 250-ml Schlenk flask containing 20 ml of CH3CN. To
this solution 0.01 ml (0.56 mmol) of H2O diluted in 10 ml
of CH3CN was added and the solution was stirred at ambient
temperature for 10 min. The solution was transferred via a
cannula to a 250-ml schlenk flask charged with 0.88 g (6.72
mmol) of NaSPh and 20 ml of CH3CN. After 2 h, the solution
was filtered through a fine porosity fritted funnel; then to the
red filtrate 100 ml of diethyl ether was added and the resulting
3
˚
V (A )
4381.5(7)
20
0.71073
1.439
9.58
T (8C)
3
˚
l (A )
rcalc (g cmy3
)
m (cmy1
R a
)
4.46
0.0383
0.0989
0.0715
0.1982
Rw b
a RsSNNFoNyNFcNN/SNFoN.
b Rws[Sw(NFoNyNFcN)2/Sw(NFoN )]1/2, where ws1/s2(NFoN).
2
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1141
2.4. Other physical measurements
1H NMR spectra (300 MHz) were obtained with a Varian
Gemini 300 spectrometer. IR spectra were measured with a
Nicolet Magna IR-760 spectrophotometer. C, H and N anal-
yses were obtained with a Thermoquest EA-1110 CHNS
analyzer.
3. Results and discussion
3.1. Synthesis and spectroscopic results
The reactions between titanium tetrachloride and sodium
thiophenolate were investigated in CH3CN at room temper-
ature with different stoichiometries. The Et4Nq salts of com-
pound I could be obtained from the reaction of TiCl4 with
6 equiv. of NaSPh in CH3CN solution in the presence of
Et4NBr. Upon the addition of solvent, the solution of the
reaction mixture immediately turned to a deep red color, and
was stirred for 2 h at ambient temperature under N2 atmos-
phere. The solution was then filtered and dark red crystals of
Et4Nq ‘salts’ were isolated with 80% yield by the slow dif-
fusion of diethyl ether into the filtrate solution. The Ph4Pq
‘salts’ were also obtained in 70% yield using a similar
method. The red crystals of compound I were very sensitive
to air and moisture and even decomposed in a dry N2 glove
box within several days. The reaction of TiCl4 with 4 equiv.
of NaSPh in CH3CN at ambient temperature produced a 1:1
Scheme 1.
The IR spectrum of [Et4N]2[Ti(SPh)6] exhibited the
characteristic thiophenolate ligand Ti–S bond stretching
vibrations at 480 and 430 cmy1, which is typical of most
metal thiolate complexes. The 1H NMR spectrum in CD3CN
displayed the characteristic Et4Nq resonance peaks and six
thiophenolate resonance peaks, which is consistent with the
solid state structure. In the IR spectra the m3–O stretching
vibration in the [Ti3O(SPh)3Cl4(CH3CN)5]PCH3CNP
(C2H5)2O (II) complex was observed at 600 cmy1, and
doublet peaks at 2310 and 2280 cmy1 were assigned to the
C^N vibrations in the CH3CN ligand. Also the Ti–S vibra-
tions in the thiophenolate ligand were observed at 481 and
429 cmy1. The 1H NMR spectrum in DMF-d7 displayed the
characteristic CH2 (d 3.382) and CH3 (d 1.608) resonance
peaks from one diethyl ether molecule and three thiopheno-
late resonancepeaks(d7.126–7.277). Inthe1HNMRspectra
of the product, which was prepared by method A, a broad
single resonance peak at d 1.95 due to five coordinated
CH3CN, freeCH3CNmoleculeincomplexIIandcoordinated
CH3CN in TiCl3(CH3CN)3 were observed. The integralratio
of those peaks compared to the thiophenolate ligands sug-
gested that TiCl3(CH3CN)3 and complex II existed as a 1:1
mixture. However, the 1H NMR spectra for the product pre-
pared by method B suggested that only complex II was pro-
duced by this method.
1
mixture (as evidenced by H NMR spectroscopy) of dark
purple [TiCl3(CH3CN)3] and dark red [Ti3O(SPh)3Cl4-
(CH3CN)5]PCH3CNP(C2H5)2O complexes. Both com-
plexes were identified by single crystal X-ray analysis.
The synthesis of compound I was accomplished by the
simple ligand exchange reaction of chloride by thiophenolate
group (Scheme 1). The precipitation of NaCl facilitated the
completion of the reaction. This method afforded a simple
and convenient route to obtain the monomeric titanium thiol-
ate complex in high yield. When the reaction stoichiometry
of 1:4 (Ti:PhSy) was used to obtain the cluster type Ti–
thiolate complex, the hydrolyzed complex II was inadver-
tently produced. In this reaction, titanium was reduced to
q3 oxidation state with the concomitant oxidation of PhSy
to 1/2PhSSPh. This kind of reduction mechanism was
reported earlier in the synthesis of [Ph4P]2[Nb(SPh)6]
[16]. The oxygen in complex II presumably came from a
trace of water in the CH3CN solution. In fact, complex II
could be obtained in excellent yield (74%) when the stoi-
chiometric amount of water (3:1 molar ratio with TiCl4 and
H2O) was added to the reaction medium. A similar reaction
3.2. X-ray structures
The structures of compounds I and II were determined;
the ORTEP diagrams of the anion in complex I and complex
II are shown in Figs. 1 and 2.
¨
was reported by Muller’s group [26] in which the reaction
The selected bond distances and angles of anion in com-
plex I are presented and compared with those of the
[Ti(S2C2H4)3]2y anion [21] in Table 2. The coordination
geometry around the metal ion is a regular octahedron in
which the central titanium ion is located on the crystallo-
system 3TiCl4:6S(SiMe3)2:3/2O2 led to a [Ti3O(S2)6-
Cl6]2y complex in which the oxygen atom came from the
inert gas containing small amounts of O2. Further study will
verify a more detailed reaction mechanism.
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J.T. Kim et al. / Polyhedron 19 (2000) 1139–1143
Fig. 1. Structure and labeling of the anion I in the [Et4N]2[Ti(SPh)6]
complex. Thermal ellipsoids as drawn by ORTEP represent the 40% prob-
ability surfaces. Symmetry-generated atoms have the suffix ‘A’.
Fig. 2. Structure and labeling of complex II. Thermal ellipsoids as drawn by
ORTEP represent the 40% probability surfaces.
Table 2
graphic inversion center. The titanium–sulfurdistancesrange
from 2.424 to 2.443 A, which are typical for metal–sulfur
˚
Selected bond lengths (A) and angles (8) for anion in complex I and
˚
[Ti(edt)3]2y
bonds in transition metal thiolate complexes. The slightly
I
[Ti(edt)3]2y a
˚
longer Ti–S distance (mean 2.432 A) than that of
[Ti(S2C2H4)3]2y (mean 2.428 A) is mainly due to the che-
˚
M–S(1)
M–S(2)
M–S(3)
S–C
2.4240(8) b
2.4283(9)
2.4434(8)
1.777(3)
1.765(3)
1.767(3)
84.05(3) b
95.51(3)
84.44(3)
range 2.419(2)–2.438(2)
mean 2.428
lating effect of dithiolate ligands in the [Ti(S2C2H4)3]2y
complex. The S–M–S angles are 84.05, 84.44 and 95.518,
respectively.
range 1.789(7)–1.820(7)
mean 1.81
The selected bond distances and angles of complex II are
presented in Table 3. In complex II, the oxygen atom bridges
three Ti atoms with m3-mode and all four atoms exist nearly
S–M–S (neighbored)
range 82.8(1)–89.1(1)
˚
in the plane. The distance of Ti–O (1.922 A) is comparable
˚
to that of (CpTi)6(m3-S)4(m3-O)4 (1.97 A) [25]. The bond
a From [21].
b The numbers in parentheses represent the individual standard deviations.
angles of Ti–O–Ti (119.878) and the three nearly identical
distances of three Ti–O bonds suggest that the oxygen atom
Table 3
˚
Selected bond lengths (A) and angles (8) for complex II
Ti(1)–O
Ti(2)–O
Ti(3)–O
Ti(1)–S(1)
Ti(1)–S(3)
Ti(2)–S(2)
Ti(2)–S(1)
Ti(3)–S(2)
Ti(3)–S(3)
1.934(7) a
1.914(6)
1.917(7)
2.574(3)
2.576(3)
2.560(3)
2.585(3)
2.553(3)
2.571(3)
Ti(1)–Cl(1)
2.369(3)
2.396(3)
2.323(3)
2.333(3)
3.323(2)
3.332(2)
3.322(2)
2.166
Ti(1)–Cl(2)
Ti(2)–Cl(3)
Ti(3)–Cl(4)
Ti(1)–Ti(3)
Ti(1)–Ti(2)
Ti(2)–Ti(3)
Ti–N (mean)
O–Ti–N(mean)
O–Ti(1)–Cl(1)
O–Ti(1)–Cl(2)
O–Ti(2)–Cl(3)
90.68
Ti–Ti–Ti (mean)
Ti–Ob–Ti (mean)
59.99
119.87
97.8(2) a
170.6(2)
179.0(2)
177.0(2)
176.0(3)
84.7(2)
87.8(3)
88.1(3)
90.0(3)
87.0(3)
80.64
N(1)–Ti(1)–S(1), S(3)
N(2)–Ti(2)–S(1), S(2)
N(3)–Ti(2)–S(1), S(2)
N(4)–Ti(3)–S(2), S(3)
N(5)–Ti(3)–S(2), S(3)
Cl(1)–Ti(1)–S(1), S(3)
Cl(2)–Ti(1)–S(1), S(3)
Cl(3)–Ti(2)–S(1), S(2)
Cl(4)–Ti(3)–S(2), S(3)
Cl(1)–Ti(1)–Cl(2)
90.0(2), 92.1(2)
84.6(3), 96.6(3)
90.2(3), 90.2(3)
97.2(3), 83.2(3)
90.6(2), 90.1(3)
89.24(10), 90.03(10)
100.30(12), 100.37(11)
101.17(13), 99.97(13)
98.40(12), 102.03(12)
91.57(11)
O–Ti(3)–Cl(4)
N(1)–Ti(1)–Cl(1)
N(1)–Ti(1)–Cl(2)
N(3)–Ti(2)–Cl(3)
N(2)–Ti(2)–Cl(3)
N(4)–Ti(3)–Cl(4)
N(5)–Ti(3)–Cl(4)
Ti–Sb–Ti(mean)
a The numbers in parentheses represent the individual standard deviations.
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J.T. Kim et al. / Polyhedron 19 (2000) 1139–1143
1143
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is located at the center of triangular geometry formed by three
titanium atoms. Each titanium is contained within a pseudo-
octahedral geometry in which two sulfur atoms, a chloride
atom and an oxygen atom form the equatorial plane. All
CH3CN ligands are located in the axial position (O–Ti–N
90.688) and all Cl ligands are located in the equatorial posi-
tion (O–Ti–Cl 175.58), except Cl(1) which is in the axial
position (O–Ti(1)–Cl(1) 97.88). The Ti–Ti distances in
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˚
complex II, which range from 3.322 to 3.332 A, are slightly
longer than those in [Ti3O(S2)6Cl6]2y (3.14–3.18 A) [26].
˚
¨
[8] A. Muller, G. Henkel, Chem. Commun. (1996) 1005.
The reactivity characteristics of the anion in complex I and
its conversion to titanium sulfide complexes as a precursor
are currently under investigation in our laboratory.
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103 (1981) 3011.
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´
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Cambridge Crystallographic Data Center, 12 Union Road,
Cambridge CB2 IEZ, UK (fax: q44-1223-336033; e-mail:
deposit@ccdc.cam.ac.uk) on request, quoting the deposition
numbers 136711 (I) and 136712 (II).
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The support of this work by a grant from the Korean Min-
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