C-ansa-zirconocene complexes with O/S donor ligands: Novel homoleptic six coordinate 4-mercaptophenolate complex of Zr(IV)

Article abstract of DOI:10.1016/j.ica.2010.07.003

New C-ansa-zirconocene complexes containing methoxythiophenolate and mercaptophenolate ligands have been synthesized and characterized. The reaction of (HSC₆H₄-n-OMe) (n = 2, 3 or 4) with [Zr{(t-Bu)HC(η⁵-C₅Me₄)(η⁵- C₅H₄)}Me₂] (1) led to the formation of monosubstituted complexes [Zr{(t-Bu)HC(η⁵-C₅Me ₄)(η⁵-C₅H₄)}Me(κ,S-SC ₆H₄-n-OMe)] (n = 2 (2); n = 3 (3)) and the disubstituted complex [Zr{(t-Bu)HC(η⁵-C₅Me₄) (η⁵-C₅H₄)}(κ,S-SC₆H ₄-4-OMe)₂] (4). The complexes [Zr{(R)HC(η⁵- C₅Me₄)(η⁵-C₅H ₄)}(κ,O-OC₆H₄-4-SH)₂] (R = t-Bu (6); R = CH₂CHCH₂ (7)) and [Zr(η⁵- C₅H₄)₂(OC₆H₄-n-SH) ₂] (n = 3 (9); n = 4 (10)) have been synthesized using the corresponding dimethyl zirconocene and mercaptophenol. However, the reaction of [Zr{(t-Bu)HC(η⁵-C₅Me₄)(η⁵- C₅H₄)}Cl₂] (11) with 4-mercaptophenol in the presence of NEt₃ led to the formation of the first example of a homoleptic six-coordinate mercaptophenolate complex of zirconium, namely [HNEt₃]₂[Zr(κ,O-OC₆H₄-4-SH) ₆] (12). Complex 12 can be obtained in higher yield by the reaction of ZrCl₄ with six equivalents of 4-mercaptophenol and NEt _3. The reaction of 12 with [Zr(η⁵-C₅H ₄)₂Cl₂] gave the unexpected disubstituted complex [Zr(η⁵-C₅H₄)₂(OC ₆H₄-4-SH)₂] (10). The molecular structures of 4 and 12 have been determined by single-crystal X-ray diffraction studies.

Full text of DOI:10.1016/j.ica.2010.07.003

Inorganica Chimica Acta 363 (2010) 3489–3497
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Inorganica Chimica Acta
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C-ansa-zirconocene complexes with O/S donor ligands: Novel homoleptic six
coordinate 4-mercaptophenolate complex of Zr(IV)
a
a
a
a
Antonio Antiñolo a, , Rafael Fernández-Galán , Noelia Molina , Antonio Otero , Iván Rivilla ,
*
Ana M. Rodríguez b
a Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Química, Universidad de Castilla-La Mancha, 13071 Ciudad Real, Spain
b ETS Ingenieros Industriales, Universidad de Castilla-La Mancha, 13071 Ciudad Real, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
New C-ansa-zirconocene complexes containing methoxythiophenolate and mercaptophenolate
ligands have been synthesized and characterized. The reaction of (HSC6H4-n-OMe) (n = 2, 3 or 4) with
Received 11 March 2010
Received in revised form 23 June 2010
Accepted 1 July 2010
[Zr{(t-Bu)HC(
HC(
5-C5Me4)(
Bu)HC(
5-C5Me4)(
OC6H4-4-SH)2] (R = t-Bu (6); R = CH2CH@CH2 (7)) and [Zr(
have been synthesized using the corresponding dimethyl zirconocene and mercaptophenol. However, the
reaction of [Zr{(t-Bu)HC(
5-C5Me4)( 5-C5H4)}Cl2] (11) with 4-mercaptophenol in the presence of NEt3 led
to the formation of the first example of a homoleptic six-coordinate mercaptophenolate complex of zirco-
nium, namely [HNEt3]2[Zr( ,O-OC6H4-4-SH)6] (12). Complex 12 can be obtained in higher yield by the reac-
tion of ZrCl4 with six equivalents of 4-mercaptophenol and NEt3. The reaction of 12 with [Zr(
5-C5H4)2Cl2]
gave the unexpected disubstituted complex [Zr(
5-C5H4)2(OC6H4-4-SH)2] (10). The molecular structures of 4
and 12 have been determined by single-crystal X-ray diffraction studies.
g
5-C5Me4)(
5-C5H4)}Me(
5-C5H4)}(
g
5-C5H4)}Me2] (1) led to the formation of monosubstituted complexes [Zr{(t-Bu)
g
g
j
j
,S-SC6H4-n-OMe)] (n = 2 (2); n = 3 (3)) and the disubstituted complex [Zr{(t-
,S-SC6H4-4-OMe)2] (4). The complexes [Zr{(R)HC( ,O-
5-C5Me4)( 5-C5H4)}(
5-C5H4)2(OC6H4-n-SH)2] (n = 3 (9); n = 4 (10))
Available online 13 July 2010
g
g
g
g
j
g
Keywords:
Zirconium
Metallocene
Thiolate
Phenolate
Homoleptic
g
g
j
g
g
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
mono- and bis(cyclopentadienyl) complexes of group 4 and 5 tran-
sition metals has been carried out by our research group in recent
years [9].
There is a great deal of interest in the role of alkoxide complexes
[1] in several stoichiometric and catalytic processes [2] and also as
molecular models for catalyst–substrate surface interactions [3].
On the other hand, thiolate complexes are of particular interest
in the field of bioinorganic chemistry due to their relevance to
the structure, bonding and function of biologically active reaction
centres such as nitrogenase or metallothioneins [4]. More specifi-
cally, the alcoholate and thiolate complexes of group 4 have been
studied extensively [5] – including systems with diol and dithiol li-
gands – by Stephan and co-workers [6].
The study of ligand systems with two different donor atoms are
attracting increasing interest in the chemistry of metal complexes
due to the possible coordination of the remaining donor atom to
the metal centre [7] and the stabilization of heterometallic com-
plexes. In this sense, several mono- and disusbtituted zirconocene
and titanocene complexes that bear functionalised mercapto-
alkoxide ligands have been reported. These ligands contain a hard
donor and a soft donor atom at each end and are coordinated in a
monodentate fashion [8]. A systematic study of the chemistry of
We previously reported the preparation of the synthon
(C5Me4)@CH({C5H4}K) for the facile synthesis of C-ansa-metallo-
cene precursors with variable substitution at the bridging atom
[10] and, more recently, we described the synthesis, characteriza-
tion and reactivity of chiral ansa-metallocenes with an alkyl- or
aryl-substituted ansa methylene bridge [10c]. We also reported
the development of new ansa-metallocene complexes of group 4
that have vinyl or allyl substituents at the silicon ansa bridge or
at the cyclopentadinyl rings [11]. Herein we report the reactivity
studies of some of these chiral C-ansa-metallocenes of group 4
complexes with polyfunctional organic molecules contain a hard
donor and a soft donor atom at each end. We have chose for our
study chiral ansa-metallocenes containing a terc butyl group in
the bridge in order to increase the lipophility of the new complexes
an also to introduce
characterization.
a group easily followed in the NMR
We report the synthesis and characterization of several
mono- and disubstituted C-ansa zirconocene thiolate complexes
containing SC6H4OMe ligands, the reactivity of dichloro or
dimethyl zirconocene complexes with HOC6H4-4-SH and the
* Corresponding author.
synthesis and reactivity of
a new unexpected homoleptic
E-mail address: antonio.antinolo@uclm.es (A. Antiñolo).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.07.003

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A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
hexa-mercaptophenolate zirconium complex. In this field few
homoleptic six-coordinate mononuclear zirconium complexes
with alkoxide ligands are known, with [Zr{OCH(CF3)2}6]2À being
the first such complex to be completely characterized [12]. Prior
to the synthesis and characterization of the homoleptic zirco-
nium complexes with six phenolate ligands, [Zr(OC6H4-R)6]2À
by Giolando and co-workers [13], had only been characterized
heteroleptics six coordinate complexes with one, two or three
phenolate groups [14].
room temperature in all cases led to the evolution of methane.
The reaction with HSC6H4-2-OMe and HSC6H4-3-OMe only gave
the monothiolate complexes [Zr{(t-Bu)HC(
g
5-C5Me4)(
5-C5Me4)(
g
g
5-C5H4)}
5-C5H4)}
Me(
j
,S-SC6H4-2-OMe)] (2) and [Zr{(t-Bu)HC(
g
Me(j,S-SC6H4-3-OMe)] (3), respectively, even in the presence of a
large excess of ligand. This finding could be due to the steric hin-
drance caused by the ortho or meta methoxy-substituent of the
thiophenolate moiety [16]. The new complexes 2 and 3 have two
chiral centres – one at the zirconium atom and the other already
existing at the carbon bridge atom of the ansa ligand. This situation
gives rise to new isomers, two of which A and B (50:50 ratio) were
observed in the NMR studies (Scheme 1). On the other hand, when
two equivalents of the reagent HSC6H4-4-OMe were used the dithi-
2. Result and discussion
2.1. Synthesis and characterization
olate compound [Zr{(t-Bu)HC(g g j,S-SC6H4-4-
5-C5Me4)( 5-C5H4)}(
The most widely used methods for the synthesis of alkoxide or
thiolate derivatives of early transition metals are (a) the reaction of
appropriate metal halide precursors with alcohols or thiols in the
presence of an amine such as NEt3, which promotes the elimina-
tion of XÀ by formation of the corresponding ammonium salts
R3NHX, and (b) the reaction of alkyl complexes with alcohol or
thiol derivatives to yield the corresponding alkane derivative and
the alkoxide or thiolate complex [15].
These methods were used to synthesize several asymmetric C-
ansa biscyclopentadienyl complexes of group 4 with different alkyl
or aryl substituents at the carbon ansa bridge. The disubstituted
complexes have a chiral centre at the carbon bridge atom and this
chirality makes the other two ligands diastereotopic, as evidenced
by the NMR spectra, whereas the monosubstituted C-ansa com-
plexes have an additional chiral centre at the zirconium atom
and this generates a wide variety of geometries [10].
OMe)2] (4) was isolated as a white solid. Nevertheless when the
stoichiometry used was lower than 1:2, a mixture of 4 and the
starting material 1 was obtained. Complexes 2–4 were character-
ized by 1H and 13C{1H} NMR spectroscopy (see Section 4).
The 1H and 13C{1H} NMR spectroscopic and analytical data for 2
and 3 are consistent with the proposed structure and the presence
of two isomers is clearly evident in the NMR spectra. For example,
the 1H NMR spectrum of 2 shows signals for the two isomers, a sin-
glet at À0.05 ppm integrates as six protons for the methyl groups
bonded to the zirconium atom, two singlets at 1.15 and 1.17 ppm
corresponding to the tert-butyl ligand, eight singlets at 1.57–2.06
for the methyl groups of the tetramethylcyclopentadienyl ring,
two singlets at 3.18 and 3.19 ppm for the methoxy groups, two
singlets at 3.52 and 3.82 ppm for the proton ansa-CH bridge and
eight signals between 4.98 and 6.41 ppm for the unsubstituted
cyclopentadienyl ring.
In view of these results we focused our attention on the prepa-
ration of new thiolate and alkoxide zirconocene and chiral C-ansa
In contrast to the above, the 1H and 13C{1H} NMR spectra of 4 do
not show any resonances for the metal-bonded methyl groups and
the spectra therefore correspond to a single product with a singlet
observed for the tert-butyl group of the ansa-biscyclopentadienyl
moiety at 1.09 ppm, four singlets at 1.79–1.92 ppm for the four
zirconocene complexes. Reaction of [Zr{(t-Bu)HC(g -
5-C5Me4)(g5
C5H4)}Me2] (1) [10b] with the methoxythiophenol derivatives
HSC6H4-n-OMe, (n = 2, 3 or 4) in toluene in a 1:1 and 1:2 ratio at
Scheme 1. Different observable isomers in NMR studies for the monothiometoxyphenolate complexes 2 and 3.

A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
3491
methyl groups of the tetramethylcyclopentadienyl fragment, one
singlet corresponding to the proton of the ansa-CH bridge at
3.59 ppm and four multiplets at 5.01–6.20 due to the unsubstitut-
ed cyclopentadienyl ring. The signals observed are consistent with
the presence of only one chiral centre at the ansa-CH bridge and
the enantiomers are not distinguishable by the NMR spectra. How-
ever, the chirality of the complex makes the two 4-methoxythio-
phenol ligands diastereotopic and four multiplets were observed
at 7.23, 7.40, 7.63 and 7.73 ppm for the aromatic protons (one mul-
tiplet for the ortho protons and the other for the meta protons of
each methoxythiophenolate ligand in each isomer) and one singlet
at 3.24 ppm, integrating as six protons, corresponding to the two
methoxy groups.
diphenolate complexes. The Zr(1)–S(1)–C(1) and Zr(1)–S(2)–C(8)
angles are 115.0(1)° and 111.0(1)°, respectively, while the S(1)–
Zr(1)–S(2) angle has a value of 105.64(3)°. These parameters are
within the range expected for similar dithiophenolate complexes
[18].
Compound 4 has a torsion angle, defined by C1–S1–S2–C8, of
1.02° and such a low value has not been reported previously in
the literature [19]. On the other hand, the two aromatic rings of
the methoxythiophenolate groups are arranged with a dihedral an-
gle of 63.04° between them and these lie as far as possible from the
C5Me4 ring (see Fig. 1). The two Ph groups participate in intra- and
intermolecular C–H/p interactions with the H16 and H17 protons
of the unsubstituted cyclopentadienyl ring but not with the tetra-
This situation was confirmed by X-ray diffraction studies. The
X-ray crystal structure of 4 is depicted in Fig. 1. Selected bond
lengths and angles for 4 are given in Table 1.
methylcyclopentadienyl ring (see Fig. 2).
The H16–(centroid of C1–C6) distance is 2.652 Å and the H16
atom is 2.651 Å from the plane containing the (C1–C6) ring. The
H17–(centroid of C8–C13) distance is 3.140 Å and the H17 atom
is 2.734 Å out of plane of the (C8–C13) ring.
ꢀ
Compound 4 crystallizes in the P1 space group as a racemic
mixture. The structure of 4 has the typical bent metallocene con-
formation observed in zirconocene complexes with a pseudo-tetra-
hedral geometry around the zirconium atom. The ansa ligand
chelates the zirconium atom and both C5 rings are bound to the
metal in a g5 mode. The pseudo-tetrahedral environment of the
zirconium atom is completed by the two S atoms of the methoxy-
thiophenolate groups. The centroid of the cyclopentadienyl rings
forms an angle with the zirconium atom of 117.53°, which is typ-
ical for carbon atom-bridged ansa-zirconocene complexes [10,17].
The most characteristic bond distances of this compound corre-
spond to Zr(1)–S(1) (2.5167(9) Å) and Zr(1)–S(2) (2.511(1) Å). Both
distances are within the normal range for similar zirconium
The intermolecular C–H/
of the Cp ring and the (C1–C6) Ph ring leads to the formation of
chains (Fig. 3). These chains are joined by means of the C5–H5/
p interaction between the H16 proton
p
interaction with the Ph ring (C8–C13) and this in turn leads to
the formation of a laminar structure (Fig. 4).
The reactivity of complexes
1 and [Zr{(CH2@CHCH2)HC
(g
5-C5Me4)( 5-C5H4)}Me2] (5) with 4-mercaptophenol, HOC6H4-4-
g
SH, was considered. In this case the reagent has a hard oxygen
donor and a soft sulfur donor and it is able to behave as a monoden-
tate ligand through coordination of the oxygen atom or the sulfur
atom to the metal centre. In addition, the atom that remains free
could give rise to homo- or heterobimetallic complexes. Reaction of
a solution of 1 or 5 in toluene with 2 equivalents of HOC6H4-4-SH
yielded the complex [Zr{(R)HC(g g j-O-OC6H4-
5-C5Me4)( 5-C5H4)}(
4-SH)2] (R = t-Bu (6), CH2@CHCH2 (7)) and these were character-
ized by 1H and 13C{1H} NMR and IR spectroscopy. Complexes 6
and 7 have the same symmetry properties as complex 4. The
NMR spectra contain a similar number of signals to the spectrum
of complex 4, with evidence for two diastereotopic mercaptophen-
olate ligands and two singlets at 3.10 and 3.11 ppm corresponding
to the inequivalent SH protons. The
j-oxygen-coordination mode
of the mercaptophenolate ligands is proposed on the basis of the
IR spectra, which show the characteristic stretching vibrations at
ca.
m
SH = 2553 cmÀ1 and
m
ZrO = 459 cmÀ1
.
Fig. 1. ORTEP drawing of complex [Zr{(t-Bu)HC(g g j S-SC6H4-4-
5-C5Me4)( 5-C5H4)}(
OMe)2] (4) with the atomic labelling scheme. Hydrogen atoms are omitted for
clarity. Thermal ellipsoids are at the 30% level of probability.
Table 1
Selected bond lengths (Å) and angles (°) for 4.
Zr(1)–Ct(1)
Zr(1)–Ct(2)
Zr(1)–C(19)
Zr(1)–S(2)
Zr(1)–S(1)
S(1)–C(1)
2.1983
2.2103
Ct(1)–Zr(1)–S(2)
Ct(1)–Zr(1)–S(1)
Ct(2)–Zr(1)–S(2)
Ct(2)–Zr(1)–S(1)
Ct(1)–Zr(1)–Zt(2)
S(2)–Zr(1)–S(1)
C(1)–S(1)–Zr(1)
C(8)–S(2)–Zr(1)
C(4)–O(1)–C(7)
C(11)–O(2)–C(14)
C(15)–C(29)–C(20)
111.94
113.61
103.84
102.83
2.460(3)
2.511(1)
2.5167(9)
1.780(3)
1.776(3)
1.381(3)
1.430(4)
1.380(4)
1.412(4)
1.537(6)
1.588(6)
117.53
105.64(3)
115.0(1)
111.0(1)
117.0(3)
117.5(3)
99.4(4)
S(2)–C(8)
O(1)–C(4)
O(1)–C(7)
O(2)–C(11)
O(2)–C(14)
C(15)–C(29)
C(20)–C(29)
Ct(1) is the centroid of the cyclopentadienyl ring and Ct(2) is the centroid of the
teramethylcyclpentadienyl ring.
Fig. 2. Intra and intermolecular C–H/
the C16(H16) and C17(H17) protons of the not substituted cyclopentadienyl ring.
p
interactions of the phenylenic groups with

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A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
Fig. 3. Chains forming along b due to the intermolecular C16–H16/p interaction of Cp group and phenylenic ring. View down a axis.
triplet at 0.57 ppm (3JH–H = 7.1 Hz) and a quartet at 2.08 ppm with
the same coupling constant. These signals correspond to the pro-
tons of the ethyl group of the [HNEt3]+ cation, the acid proton of
which appears as a broad signal at 11.24 ppm. A very broad reso-
nance is also observed at 4.50 ppm and this corresponds to the pro-
ton of the SH groups. The aromatic region contains two doublets at
3
6.85 and 7.24 ppm with JH–H = 8.4 Hz for the ortho and meta
phenylenic ring protons, respectively. It is worth noting that reso-
nances corresponding to the C-ansa-biscyclopentadienyl ligand are
not observed. The 13C{1H} NMR spectrum contains only one signal
for each of the groups evidenced in the 1H NMR spectrum. The IR
spectrum shows stretching vibrations at
mSH = 2512 and mZrO = 498,
which are characteristic of the -oxygen-coordination mode of
j
mercaptophenolate ligands. Monocrystals of 12 suitable for study
by X-ray diffraction were obtained. The ORTEP diagram and atom
numbering scheme are shown in Fig. 5 and a selection bond
lengths and angles are given in Table 2.
Fig. 4. Laminar structure forming due to the juntion of chains in 4. View down b
axis. The H5–(centroid of C8–C13) distance is a value of 3.172 Å and the H5 atom is
a 3.057 Å of plane defined by (C8–C13) ring.
The complex [HNEt3]2[Zr(j,O-OC6H4-4-SH)6] (12) crystallized
in the orthorhombic space group Pbca with two C6D6 molecules.
The asymmetric unit contains half a molecule of complex 12, with
the zirconium atom located on a crystallographic inversion centre,
In the same way, we also explored the reactivity of [Zr(g5
-
C5H4)2Me2] (8) towards mercaptophenol ligands. Reaction of 8
with n-mercaptophenol (n = 3, 4) in a 1:2 M ratio afforded the
complexes [Zr(
C5H4)2( -O-OC6H4-4-SH)2] (10). Both complexes were character-
g j -
5-C5H4)2( -O-OC6H4-3-SH)2] (9) and [Zr(g5
j
ized by the usual spectroscopic techniques. As an example, the
1H NMR spectrum of 10 in C6D6 presents a broad signal at
3.21 ppm, corresponding to the protons of two equivalent SH
groups, one singlet at 5.84 ppm due to the protons of the two
cyclopentadienyl rings and two doublets at 6.48 ppm and
3
7.17 ppm with a coupling constant JH–H = 8.5 Hz assigned to the
ortho and meta protons of two phenylenic rings. These compounds
were fully characterized by 13C{1H} NMR spectroscopy and the IR
spectra provide supplementary information, with the characteris-
tic stretching vibration
m m(S–H) at ca.
(Zr–O) at ca. 512 cmÀ1 and
2538 cmÀ1
.
2.2. Synthesis and crystal structure of complex 12
We attempted to synthesize complex 6 by a metathesis reaction
between [Zr{(t-Bu)(
5-C5H4)( 5-C5Me4)}Cl2] (11) [10a] and
g
g
4-mercaptophenol in the presence of NEt3 in a 1:2:2 ratio. How-
ever, only a small amount of the desired product 6 was obtained.
In order to increase the yield of the reaction the stoichiometric
amounts of 4-mercaptophenol and NEt3 were increased (to a
1:6:6 ratio) and, after the appropriate work up, a new crystalline
product 12 was obtained. The 1H NMR spectrum of 12 contains a
Fig. 5. ORTEP drawing of [Zr(j
,O-OC6H4-4-SH)6]2À dianionic complex with the
atomic labelling scheme. Hydrogen atoms are omitted for clarity. Thermal ellipsoids
are at the 30% level of probability.

A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
3493
Table 2
Selected bond lengths (å) and angles (°) for 12 Á 2C6D6.
Zr(1)–O(1)
Zr(1)–O(2)
Zr(1)–O(3)
O(1)–C(1)
O(2)–C(7)
O(3)–C(13)
S(1)–C(4)
2.048(2)
2.006(2)
2.117(2)
1.332(3)
1.332(3)
1.350(3)
1.774(3)
1.777(3)
1.775(3)
O(1)–Zr(1)–O(2)
88.97(7)
91.06(7)
180.0
90.50(7)
91.03(7)
89.50(7)
180.0
O(1)–Zr(1)–O(3)
O(1)–Zr(1)–O(1)a
O(2)–Zr(1)–O(3)
O(2)–Zr(1)–O(1)a
O(2)–Zr(1)–O(3)a
O(2)–Zr(1)–O(2)a
O(3)a–Zr(1)–O(3)
O(1)–Zr(1)–O(3)a
C(1)–O(1)–Zr(1)
C(7)–O(2)–Zr(1)
C(13)–O(3)–Zr(1)
S(2)–C(10)
S(3)–C(16)
180.0
88.94(7)
146.1(2)
178.7(2)
126.6(1)
a
Symmetry transformations used to generate equivalent atoms: Àx, Ày, Àz + 1.
and one molecule of C6D6. Structural analysis of 12 by X-ray crys-
tallography revealed the presence of a dianionic complex consist-
ing of a zirconium centre coordinated by six oxygen atoms of six
4-mercaptophenolate ligands in an octahedral geometry, thus cor-
roborating the assignment of the 1H NMR and IR spectra.
It is interesting to note that the Zr–O bond lengths are not equal
and the distances between the oxygen atoms and the Zr centre are
as follows: Zr(1)–O(3), 2.117(2) Å; Zr(1)–O(1), 2.048(2) Å; Zr(1)–
O(2), 2.006(2) Å. These values are in agreement with three differ-
ent coordination modes of the oxygen atoms. This situation is
related with the Zr–O–C(Ph) bond angles, for which three different
values are observed: Zr(1)–O(3)–C(13) 126.6(1)°; Zr(1)–O(1)–C(1)
146.1(2)°; Zr(1)–O(2)–C(7) 178.7(2)°.
Fig. 6. View of the intermolecular S–H/
p
and C–H/
p
interactions in [Zr(
j
,O-OC6H4-
4-SH)6]2À dianionic complex of 12. The hydrogen atoms are omitted for clarity.
the dianionic complex: the O(3) atom is involved in an intermolec-
ular hydrogen bond with the H(1) atom of the [HNEt3]+ cation.
Another weaker hydrogen bond is established between the oxygen
Table 3
Crystal data and structure refinement for 4 and 12.
4
12
Empirical
C33H40O2S2Zr
[C36H30O6S6Zr][C6H16N]2 Â 2C6H6
formula
These structural data (angles and distances) are consistent with
the different hybridization modes of the oxygen atoms around the
zirconium centre. For example, atom O(3) has the longest Zr–O
bond distance and lowest Zr–O–C(Ph) bond angle as it has sp2
hybridization and therefore has a lower donor capacity to the zir-
conium atom. In this particular case the metal–oxygen interaction
could be considered as double bond due to additional electronic
transfer from the non-hybridized p orbital of the oxygen atom to
the zirconium atom. In contrast, the O(2) oxygen atom has the low-
est Zr–O bond distance and highest Zr–O–C(Ph) bond angle – this
oxygen would have sp hybridization and will act as a better donor
atom. In the latter case the metal–oxygen interaction can be con-
sidered as a triple bond and the oxygen atom interacts with the
metal atom through its two lone pairs. Finally, the O(1) oxygen
atom has intermediate bond angles and bond distances and corre-
spondingly presents intermediate behaviour between the sp and
sp2 hybridization modes.
If we define the equatorial plane (EP) formed by the O1–O1A–
O3–O3A atoms and Ph1 by the mean plane of the (C1–C6) atoms,
Ph2 by the mean plane of (C7–C12) and Ph3 by the mean plane
of (C13–C19), we can see the different orientations for the phenyl
rings of the phenolate ligands. Thus, the dihedral angle formed be-
tween EP and Ph2 is very close to 90° (89.63°), while for Ph1 and
Ph3 the values are only 53.71° and 71.29°, respectively. Closer
inspection of the structure provides a plausible explanation for this
Formula weight
Temperature
Wavelength
Crystal system
Space group
Unit cell
623.99
1202.85
180(2) K
0.71073 Å
Orthorhombic
Pbca
180(2) K
0.71073 Å
Triclinic
ꢀ
P1
a = 8.8369(10) Å
b = 9.1048(10) Å
c = 19.996(2) Å
a = 18.3856(18) Å
b = 17.6546(17) Å
c = 18.7389(18) Å
dimensions
a
= 86.144(2)°
a
= 90°
b = 82.088(2)°
b = 90°
c
= 68.772(2)°
c = 90°
Volume
Z
Density
6082.5(10) Å3
2
6082.5(10) Å3
4
1.395 mg/m3
1.313 mg/m3
(calculated)
Absorption
coefficient
F(0 0 0)
Crystal size
Theta range for
data collection
Index ranges
0.539 mmÀ1
0.436 mmÀ1
652
2528
0.38 Â 0.21 Â 0.08 mm3 0.43 Â 0.36 Â 0.34 mm3
2.06–26.41°
1.93–26.46°
À11 6 h 6 11
À11 6 k 6 11
À25 6 l 6 25
10 150
À22 6 h 6 23
À21 6 k 6 22
À22 6 l 6 23
39 973
Reflections
collected
Independent
reflections
5967 [Rint = 0.0324]
98.0%
6266 [Rint = 0.1578]
99.8%
Completeness to
theta = 26.46°
Max. and min.
transmission
Refinement
method
Data/restraints/
parameters
Goodness-of-fit
on F2
0.9581 and 0.8214
0.8659 and 0.8346
Full-matrix least-squares on F2
6266/0/343
observation: the Ph1 ring takes part in an intermolecular C–H/
p
interaction with the methylenic proton H23B of the [HNEt3]+ cat-
ion (the H23B–(centroid of C1–C6) distance is 3.130 Å and that
for H23B is 2.727 Å out of the plane defined by C1–C6); the Ph3
Full-matrix least-
squares on F2
5967/18/392
ring is involved in an intermolecular S–H/p interaction [20] estab-
1.029
0.837
lished with the S2(HB) atom (Fig. 6) (the HB–(centroid of C13–C18)
distance is 2.833 Å and that for HB is 2.504 Å out of the plane de-
fined by C13–C18). In contrast, Ph2 does not take part in any
interactions.
Final R indices
[I > 2r(I)]
R indices (all
data)
R1 = 0.0425,
wR2 = 0.0929
R1 = 0.0534,
wR2 = 0.0980
R1 = 0.0402, wR2 = 0.0899
R1 = 0.0728, wR2 = 0.0979
In this structure, the [HNEt3]+ cation should be stabilized by the
two hydrogen bonds observed (see Table 3 and Fig. 6). Each
[HNEt3]+ cation shows two intermolecular hydrogen bonds with
Largest diff. peak 0.439 and À0.318 eÅÀ3 0.443 and À0.520 eÅÀ3
and hole

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A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
atoms O(1) and the methylenic proton H21B of one ethyl group of
the triethylammonium cations. Similar interactions have been ob-
served in analogous homoleptic octahedral complexes [12] (Fig. 7).
Compound 12 can also be obtained by the reaction between six
equivalents of 4-mercaptophenol and NEt3 with a ZrCl4 suspension
in toluene. This reaction affords a colourless solution. The appro-
priate work up procedure furnishes white crystals that give spec-
troscopic and X-ray diffraction data that are consistent with
those of compound 12.
2.3. Stability and reactivity of complex 12
According to the 1H NMR spectrum at 25 °C the six mercapto-
phenolate ligands of 12 are equivalent, which reveals a dynamic
exchange between them. In the solid state, however, this equilib-
rium is blocked by the presence of hydrogen bonds as described
above.
The homoleptic six-coordinate complex 12 decomposes slowly
in the solid state under an inert atmosphere and more rapidly in
solution. Similar results have been observed for other related com-
plexes that contain a dialkylammonium cation [21]. This behaviour
was followed by 1H NMR spectroscopy of 7 in C6D6 over one week
at 25 °C (Scheme 2). The initial 1H NMR spectrum shows the sig-
nals for the octahedral complex 12 along with two much lower
intensity signals in the aromatic region, which were identified as
being due to [HNEt3][OC6H4SH] (13). Over time the intensity of
the signals of 12 decreased while the additional aromatic signals
increased in intensity. At the same time a white precipitate began
to form. After seven days the 1H NMR spectrum corresponded only
to the salt [HNEt3][OC6H4-4-SH] (13).
Fig. 7. View of the hydrogen bonds between [HNEt3]+ cation with [Zr(
j,O-OC6H4-4-
SH)6]2À dianionic complex. The hydrogen atoms are omitted.
It was established by NMR experiments that this process is
highly dependent on the temperature and the nature of the sol-
vent. Thus, the evolution of 12 is faster on increasing the temper-
ature and on using non-aromatic solvents.
Attempts to prepare the tetracoordinate complex from zirco-
nium tetrachloride with 4-mercaptophenol in a 1:4 stoichiometry
and NEt3 in excess were unsuccessful and the only product isolated
was 12 – in 23% yield after crystallization from a toluene solution.
We previously mentioned that the uncoordinated SH groups in
complex 12 should be able to act as bridges to give homo- or het-
eronuclear species. In this respect, we attempted the reaction of 12
with 2 equivalents of 8 in toluene at room temperature to generate
a trinuclear zirconium compound. However, the product obtained
was complex 10 and this was characterized by NMR and IR spec-
troscopy (Scheme 3). This behaviour could be due to the faster
reaction of 8 with the ammonium salt 13 (always present in a solu-
tion of 12) rather than the reaction with the zirconium complex 12.
3. Conclusions
In conclusion, we have described the synthesis and character-
ization of several new chiral C-ansa and not ansa zirconocene
complexes with functionalised methoxythiolate and mercapto-
phenolate ligands. These ligands are coordinated to the metal cen-
tre in a monodentate fashion by the sulfur donor atom in the case
of the methoxythiolate ligands and by the oxygen atom in the mer-
captophenolate ligands. The steric hinderance caused by the func-
tionalised phenylenic ligands on position 2 or 3 gives rise to
Scheme 2. 1H NMR in C6D6 at T = 25 °C evolution of complex 12 overtime.
Scheme 3. Synthesis of [Zr(g
5-C5H5)2(OC6H4-4-SH)2] from [HNEt3]2[Zr(OC6H4-4-SH)6].

A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
3495
monosubstituted complexes but the presence of the substituent on
position 4 produces the disubstituted complexes.
12.0, 12.1 13.6, 13.8, 16.5, 17.2 (C5Me4), 29.3, 29.5 (ZrMe), 30.0,
30.1 (C(CH3)3), 33.3, 33.4 (C(CH3)3), 51.3, 52.5 (CH), 54.9, 55.0
(OMe), 100.2–146.6 (C5Me4 and C5H4), 126.2, 126.3, 128.7, 128.8,
129.0, 129.1, 145.6, 145.8, 159.8, 160.0 (C6H4). Anal. Calc. for
The new homoleptic six-coordinate zirconium complex 12 has
been synthesized by the reaction of the C-ansa-dichlorozircono-
cene derivative 11 with the protic compound 4-mercaptophenol
in the presence of NEt3.
C27H36OSZr (499.86): C, 64.88; H, 7.26; S, 6.41. Found: C, 64.51;
H, 6.98; S, 6.26%.
Finally, the reaction of complex 12 with [Zr(
g
5-C5H5)2Me2]
5-C5H4)2(
gives the disubstituted complex [Zr(g j-O-OC6H4-4-
4.4. Synthesis of [Zr{(t-Bu)HC(g g j,S-SC6H4-4-
5-C5Me4)( 5-C5H4)}(
OMe)2] (4)
SH)2] (10).
4. Experimental
The preparation of 4 was carried out in an identical manner to
that for 1: from solution of [Zr{t-BuCH(
5-C5Me4)(g5
a
g
-
4.1. General procedures
C5H4)}2Me2] (0.50 g, 1.33 mmol) in toluene (50 mL) and HSC6H4-
4-OMe (0.36 g, 2.66 mmol). In this case crystals for an X-ray study
were obtained by cooling to À30 °C a concentrated solution of 5 mL
in toluene. Yield: 0.55 g, 83%. 1H NMR (500 MHz, C6D6, 25 °C): d/
ppm = 1.09 (s, 9H, C(CH3)3), 1.79, 1.82, 1.91, 1.92 (4s, each 3H,
C5Me4), 3.24 (s, 6H, 2 Â OMe), 3.59 (s, 1H, CH), 5.01, 5.17, 6.16,
6.20 (4m, each 1H, C5H4), 7.23, 7.40, 7.63, 7.73 (4m, each 2H,
2 Â C6H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d/ppm = 11.3,
11.4, 13.6, 13.8 (C5Me4), 30.3 (C(CH3)3), 30.5 (C(CH3)3), 51.5 (CH),
54.8 (2 Â OMe), 99.7–134.0 (C5Me4 and C5H4), 127.4, 127.9,
128.1, 128.3, 132.6, 133.2, 135.4, 135.5, 157.9, 158.0 (2 Â C6H4).
Anal. Calc. for C33H40O2S2Zr (624.02): C, 63.52; H, 6.46; S, 10.28.
Found: C, 63.19; H, 6.33; S, 10.07%.
All reactions were performed using standard Schlenk tube tech-
niques under dry nitrogen. Solvents were distilled from appropri-
ate drying agents and degassed before use. Racemic mixtures of
complexes [Zr{(t-Bu)HC(
CHCH2)CH(
5-C5Me4)( 5-C5H4)}Me2] (5) and [Zr{t-BuCH(
5-C5H4)}2Cl2] (11) were prepared as described earlier [4]. ZrCl4,
g
5-C5Me4)(
g
5-C5H4)}Me2] (1), [Zr{(CH2@
5-C5Me4)
g
g
g
(g
HSC6H4-4-OH, HSC6H4-2-OMe, HSC6H4-3-OMe and HSC6H4-4-OMe
were purchased from Aldrich and used directly. NEt3 purchased from
Aldrich was distilled and stored over molecular sieves under an inert
atmosphere before use. Literature methods were used to prepare
[Zr(g g
5-C5H4)2Me2] (8) from commercial [Zr( 5-C5H4)2Cl2] [22] 1H
and 13C{1H} NMR spectra were recorded on a Varian Inova FT-500
spectrometer and referenced to the residual deuterated solvent. IR
spectra were recorded on a Perkin-Elmer PE 883 IR spectrophotome-
ter. Microanalyses were carried out with a Perkin-Elmer 2400
microanalyzer.
4.5. Synthesis of [Zr{(t-Bu)HC(g g j,O-OC6H4-4-
5-C5Me4)( 5-C5H4)}(
SH)2] (6)
To a solution of [Zr{t-BuHC(g g
5-C5Me4)( 5-C5H4)}2Me2] (0.50 g,
1.33 mmol) in toluene (50 mL) was added HOC6H4-4-SH (0.33 g,
2.66 mmol) at room temperature and stirred for 6 h. The evolution
of methane was observed. The resulting pale yellow solution was
filtered and evaporated under vacuum. The yellow residue was
washed with hexane (2 Â 20 mL) to give the title complex
4.2. Synthesis of [Zr{(t-Bu)HC(g g j,S-SC6H4-2-
5-C5Me4)( 5-C5H4)}Me(
OMe)] (2)
To a solution of [Zr{t-BuHC(g g
5-C5Me4)( 5-C5H4)}2Me2] (0.50 g,
1.33 mmol) in toluene (50 mL) was added HSC6H4-2-OMe (0.36 g,
2.66 mmol) at room temperature and stirred for 2 h. The evolution
of methane was observed. The solution was evaporated to dryness
under vacuum to yield complex 2 (0.54 g, 81%). 1H NMR (500 MHz,
C6D6, 25 °C) isomer A and isomer B: d/ppm = À0.05 (s, 6H, ZrMe),
1.15, 1.17 (2s, each 9H, C(CH3)3), 1.57, 1.66, 1.68, 1.77, 1.82, 1.89,
2.04, 2.06 (8s, each 3H, C5Me4), 3.18, 3.19 (2s, each 3H, OMe),
3.52, 3.82 (2s, each 1H, CH), 4.92, 4.98, 5.46, 5.70, 5.73, 6.02,
6.16, 6.41 (8m, each 1H, C5H4), 6.52, 6.93, 7.80, 7.96 (4m, each
2H, C6H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C) isomer A and iso-
mer B: d/ppm = 29.9, 30.9 (ZrMe), 10.3, 10.7, 11.6, 11.9, 12.0,
13.2, 15.2, 15.6 (C5Me4), 32.1, 33.0 (C(CH3)3), 32.3, 33.1 (C(CH3)3),
50.1, 50.9 (CH), 55.1 (OMe), 98.3–126.4 (C5Me4 and C5H4), 127.5,
127.9, 128.1, 129.3, 136.1, 136.2, 158.2, 158.3 (C6H4). Anal. Calc.
for C27H36OSZr (499.86): C, 64.88; H, 7.26; S, 6.41. Found: C,
64.72; H, 7.01; S, 6.14%.
(0.45 g, 56%). IR (KBr;
m mSH = 2553, m
(cmÀ1)): ZrO = 459. 1H NMR
(500 MHz, C6D6, 25 °C): d/ppm = 1.21 (s, 9H, C(CH3)3), 1.67, 1.68,
1.70, 1.91 (4s, each 3H, C5Me4), 3.10, 3.11 (2s, each 1H, SH), 4.02
(s, 1H, CH), 5.13, 5.40, 5.80, 6.03 (4m, each 1H, C5H4), 6.53, 6.54,
3
7.17, 7.18 (4d, JH–H = 8.8 Hz, each 2H, 2 Â C6H4). 13C{1H} NMR
(125 MHz, C6D6, 25 °C): d/ppm = 10.8, 29.5, 30.5, 30.6 (C5Me4),
33.6 (C(CH3)3), 39.3 (C(CH3)3), 52.5 (CH), 105.2, 109.8, 112.6,
118.8, 129.3 (C5H4), 112.5, 116.2, 120.7, 125.0, 132.8 (C5Me4),
112.7, 112.9, 119.4, 133.3 164.2, 164.4 (2 Â C6H4). Anal. Calc. for
C31H36O2S2Zr (595.97): C, 62.47; H, 6.09; S, 10.76. Found: C,
63.09; H, 6.63; S, 11.28%.
4.6. Synthesis of [Zr{(CH2@CHCH2)HC(
OC6H4-4-SH)2] (7)
g g j,O-
5-C5Me4)( 5-C5H4)}(
The preparation of 7 was carried out in an identical manner to
that of 6; from 5 (0.50 g, 1.39 mmol) and HSC6H4-4-OMe (0.35 g,
2.78 mmol). Yield: 0.44 g, 54%. 1H NMR (500 MHz, C6D6, 25 °C):
d/ppm = 1.65, 1.67, 1.80 (3s, 6:3:3H, C5Me4), 2.84 (m, 2H,
4.3. Synthesis of [Zr{(t-Bu)HC(g g j,S-SC6H4-3-
5-C5Me4)( 5-C5H4)}Me(
OMe)] (3)
3
The preparation of 3 was carried out in an identical manner to
that of 1: from solution of [Zr{t-BuCH(
5-C5Me4)(g5
CH2CH@CH2), 3.09, 3.11 (2s, 2H, SH), 4.16 (t, JH–H = 8.5 Hz, 1H,
a
g
-
CH), 5.05, 5.17 (m, 2H, CH2CH@CH2), 5.18, 5.34, 5.88, 5.97 (4m,
3
C5H4)}2Me2] (0.50 g, 1.33 mmol) in toluene (50 mL) and HSC6H4-
3-OMe (0.36 g, 2.66 mmol). Yield: 0.53 g, 80%. 1H NMR (500 MHz,
C6D6, 25 °C) isomer A and isomer B: d/ppm = À0.04, À0.05 (2s, each
3H, ZrMe), 1.04, 1.05 (2s, each 9H, C(CH3)3), 1.60, 1.64, 1.74, 1.77,
1.88, 1.89, 2.04, 2.07 (8s, each 3H, C5Me4), 3.37, 3.39 (2s, each
3H, OMe), 3.44, 3.57 (2s, each 1H, CH), 4.77, 5.01, 5.13, 5.18, 5.70,
6.16, 6.18, 6.20 (8m, each 1H, C5H4), 7.32, 7.36, 7.48, 7.56 (4m, each
2H, C6H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d/ppm = 11.3, 11.4,
4H, C5H4), 5.88 (m, 1H, CH2CH@CH2), 6.54 (d, JH–H = 8.7 Hz, 4H,
3
2 Â C6H4), 7.16, 7.17 (2d, JH–H = 8.4 Hz, 4H, 2 Â C6H4) 13C{1H}
NMR (125 MHz, C6D6, 25 °C): d/ppm 10.5, 10.7, 11.8, 13.7
(C5Me4), 39.7 (CH), 35.4 (CH2CH@CH2), 103.4, 106.1, 114.6, 116.7,
125.8 (C5H4), 109.2, 113.8, 116.2, 119.9, 126.7 (C5Me4), 116.6
(CH2CH@CH2), 118.0, 118.1, 119.4, 133.3, 136.0, 164.2, 164.3
(2 Â C6H4). Anal. Calc. for C30H32O2S2Zr (579.64): C, 62.13; H,
5.56; S, 11.06. Found: C, 60.79; H, 6.03; S, 9.75%.

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A. Antiñolo et al. / Inorganica Chimica Acta 363 (2010) 3489–3497
5-C5H5)2(OC6H4-3-SH)2] (9)
5-C5H5)2Me2] (8) (0.50 g,
Table 4
4.7. Synthesis of [Zr(
g
Hydrogen bonds for compound 12 (Å, °).
Method a. To a solution of [Zr(
g
D–HÁ Á ÁA
d(H–A)
\DHA
d(DÁ Á ÁA)
1.98 mmol) in toluene (50 mL) was added HOC6H4-3-SH (0.50 g,
3.97 mmol) at room temperature. The evolution of methane was
observed and the solution was stirred for 6 h. The resulting suspen-
sion was filtered and the solvent was dried in vacuo to yield a yel-
N1–H1Á Á ÁO3
1.771(2)
2.477(2)
175.8(1)
138.9(2)
2.757(3)
3.287(3)
C21–H21BÁ Á ÁO(1A)a
a
The symmetry operation that generates the atoms is: Àx, Ày, Àz + 1.
low solid (0.71 g, 75%). Method b. To a solution of [Zr(g
5-C5H5)2Cl2]
(0.50 g, 1.71 mmol) in toluene (50 mL) were added HOC6H4-4-SH
(0.43 g, 3.42 mmol) and NEt3 (0.47 mL, 3.42 mmol) at room tem-
perature. The resulting solution was stirred for 15 h. After filtration
the solvent was evaporated to dryness and the residue washed with
hexane (2 Â 20 mL) to give complex 7 (0.47 g, 58%). IR (KBr;
of 4 and 12 were mounted on a glass fibre and transferred to a
Bruker X8 APEX II CCD-based diffractometer equipped with a
graphite monochromated Mo K
Several sets of narrow data ‘‘frames” were collected using 0.3° wide
scan frames covering the complete spheres of the reciprocal
a radiation source (k = 0.71073 Å).
x
m
(cmÀ1)): ZrO = 621. 1H NMR (500 MHz, C6D6, 25 °C):
mSH = 2581, m
space with a crystal-to-detector distance of 6.0 cm. Data were inte-
grated using SAINT [23] and an absorption correction was based on
multiple scans with the program SADABS [24]. The software package
SHELXTL version 6.12 [25] was used for space group determination,
structure solution and refinement by full-matrix least-squares
methods based on F2. All non-hydrogen atoms were refined with
anisotropic thermal parameters. Hydrogen atoms were placed
using a ‘‘riding model” and were included in the refinement at cal-
culated positions. For 3, the tert-butyl group is disordered over two
positions and this was modelled as a 50:50 mixture.
d/ppm = 3.22 (s, 2H, 2 Â SH), 5.83 (s, 10H, 2 Â C5H5), 6.43 (d, 3JH–H
=
3
7.9 Hz, 2H, C6H4), 6.66 (d, JH–H = 7.8 Hz, 2H, C6H4), 6.69 (s, 2H,
3
C6H4), 6.93 (t, JH–H = 7.9 Hz, 2H, C6H4). 13C{1H} NMR (125 MHz,
C6D6, 25 °C): d/ppm = 113.4 (C5H5), 115.9, 119.3, 120.7, 130.2,
132.2, 166.2 (2 Â C6H4). Anal. Calc. for C22H20O2S2Zr (471.75): C,
56.01; H, 4.27; S, 13.59. Found: C, 55.61; H, 4.38; S, 13.77%.
4.8. Synthesis of [Zr(g
5-C5H5)2(OC6H4-4-SH)2] (10)
The preparation of 10 was carried out in an identical manner to
that of 9: Method a. From [Zr(
5-C5H5)2Me2] (8) (0.50 g,
1.98 mmol) and HOC6H4-4-SH (0.50 g, 3.97 mmol). Yield 0.73 g,
78%. Method b. From [Zr(
5-C5H5)2Cl2] (0.50 g, 1.71 mmol),
HOC6H4-4-SH (0.43 g, 3.42 mmol) and NEt3 (0.47 mL, 3.42 mmol).
Yield 0.56 g, 70%. IR (KBr; SH = 2538,
(cmÀ1)): ZrO = 512. 1H
g
5. Supplementary material
g
CCDC 768525 and 768526 contain the supplementary crystallo-
graphic data for 3 and 5. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif.
m
m
m
NMR (500 MHz, C6D6, 25 °C): d/ppm = 3.21 (s, 2H, 2 Â SH), 5.84
3
(s, 10H, 2 Â C5H5), 6.48, 7.17 (2d, JH–H = 8.6 Hz, each 4H,
2 Â C6H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d/ppm = 113.2
(C5H5), 117.6, 118.3, 119.1, 132.7, 133.1, 164.8 (2 Â C6H4). Anal.
Calc. for C22H20O2S2Zr (471.75): C, 56.01; H, 4.27; S, 13.59. Found:
C, 56.21; H, 4.51; S, 13.26%.
Acknowledgments
We gratefully acknowledge financial support from the Ministe-
rio de Educación y Ciencia, Spain (Grant No. CTQ2009-09214), the
Junta de Comunidades de Castilla-La Mancha (Grant No. PCI08-
0032-0957) and the program Consolider-Ingenio 2010 ORFEO
CSD2007-00006.
4.9. Synthesis of [HNEt3]2[Zr(j,O-OC6H4-4-SH)6] (12)
Method a. To a solution of [Zr{t-BuHC(
g
5-C5Me4)( 5-C5H4)}Cl2]
g
(11) (0.50 g, 1.20 mmol) in THF (50 mL) were added NEt3 (0.33 mL,
2.40 mmol) and HOC6H4-4-SH (0.30 g, 2.40 mmol) at room temper-
ature and stirred for 12 h to give a pale yellow oil and a colourless
solution. The solution was filtered, concentrated and cooled to
À30 °C to yield colourless crystals of the title complex (0.42 g,
33%). Method b. To a solution of ZrCl4 (0.50 g, 2.14 mmol) in toluene
(50 mL) were added HOC6H4-4-SH (1.62 g, 12.87 mmol) and NEt3
(1.79 mL, 12.87 mmol) at room temperature and stirred for 15 h
to give pale yellow oil and a colourless solution. The solution
was filtered, concentrated and cooled to À30 °C to yield colourless
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