Zirconium and hafnium complexes of the thio(bisphenolato) ligand: Synthesis, structural characterization and testing as 1-hexene polymerization catalysts

Article abstract of DOI:10.1039/b907560g

Thio(bisphenolato) complexes of the type [M₂(-tbop- κ³O,S,O)₂Cl₄] [M = Zr 1, Hf 2 and tbop = 2,2′-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenolate}] were prepared by HCl elimination from tbopH₂ and MCl<

Full text of DOI:10.1039/b907560g

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PAPER
www.rsc.org/dalton | Dalton Transactions
Zirconium and hafnium complexes of the thio(bisphenolato) ligand: synthesis,
structural characterization and testing as 1-hexene polymerization catalysts†
Zofia Janas,*a Dorota Godbole,a Tomasz Nerkowskia and Krzysztof Szczegotb
Received 16th April 2009, Accepted 20th July 2009
First published as an Advance Article on the web 18th August 2009
DOI: 10.1039/b907560g
3
Thio(bisphenolato) complexes of the type [M2(m-tbop-k O,S,O)2Cl4] [M = Zr 1, Hf 2 and tbop =
2,2¢-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenolate}] were prepared by HCl elimination from tbopH2
and MCl4. Substitution of the chlorides in 1 and 2 by 2,6-diisopropylphenolato groups (dipp) generates
3
new compounds [M2(m-tbop-k O,S,O)2(dipp)4] (M = Zr 3, Hf 4). The structures of 1–4 were confirmed
by NMR spectroscopy; complexes 3 and 4 were further investigated by X-ray crystallography. These
studies showed 1–4 to be dimers either in the solid state or in solution and to have metal centers
adopting distorted octahedral geometry. However treatment of MCl4 with [Al2(m-OEt)2(tbop-
3
3
3
k O,S,O)2] or [Al2(m-tbop-k O,S,O)2Me2] gave heterotrinuclear complexes [M(tbop-k O,S,O)2-
Cl2(m-AlX2)2] (M = Zr, X = Cl 5, X = Me 7 and M = Hf, X = Cl 6, X = Me 8) for which the
single-crystal X-ray diffraction analysis showed zirconium and hafnium centers to have
eight-coordinate dodecahedral geometry. Complexes 1–6 after activation with aluminium alkyls and
supporting on MgCl2 showed a lack of activity in the ethene polymerization process and moderate
activity towards 1-hexene producing high molecular weight atactic poly(1-hexenes).
and generation of active centers occurs via the abstraction of
Introduction
coligands from the titanium atom. On the contrary, homoleptic
3
In recent years there is a growing recognition that non-metallocene
complexes hold great promise as homogenous olefin polymeriza-
tion catalysts.1 Systematic ligand design has explored new families
of group IV metal monoanionic phenoxides,1 bis(phenoxyimines)2
and phosphanylphenoxides3 in highly active systems. The most
successful developments in terms of catalysis has appeared using
chelating bis-phenoxide ligands,4 in particular tridentate and
tetradentate having additional neutral donors.1d,1e,5–21 However,
there is growing evidence that softer second-row donors like sulfur
may offer beneficial stabilization of the highly reactive metal center
in homogenous catalysis.3e,7e,19g,20–22
[M(tbop-k O,S,O)2]/aluminium alkyl systems demonstrate a lack
of catalytic activity towards ethene. It has been found and well
3
documented that treatment of [M(tbop-k O,S,O)2] with AlMe3
leads to the formation of the coordinatively saturated [M(tbop-
3
k O,S,O)2Me2(m-AlMe2)2] species.23d In this context inactivity
3
demonstrated for octahedral [Zr(tbmp-k O,S,O)Cl2] [tbmp = 2,2¢-
thiobis(6-tert-butyl-4-methylphenolato)] in ethene as well as in the
1-hexene polymerization process is surprising, and to this date no
explanation has been found. In comparison, the corresponding
4
double sulfur donor system [Zr(dtbmp-k OSSO)(bn)2]/B(C6F5)3
[dtbmp = 2,2¢-ethanedithiobis(6-tert-butyl-4-methylphenolato);
With this in mind we have explored group IV metal
complexes containing the 2,2¢-thiobis{4-(1,1,3,3-tetramethyl-
butyl)phenolato} (tbop) ligand as potential precursors in the a-
olefin heterogeneous polymerization process. As a result heterolep-
bn = benzyl] having the same substituents at the phenolate
3
group like the tbmp ligand in [Zr(tbmp-k O,S,O)Cl2], effectively
polymerizes 1-hexene.22e Because of this we have been tried to
extend our investigation on the tbop-based group IV metal
systems to the 1-hexene polymerization process. Here we report
on homodinuclear octahedral and heterotrinuclear dodecahedral
zirconium and hafnium complexes with the tbop ligand, as well as
their behavior towards 1-hexene after activation with aluminium
alkyls.
3
tic, aryloxo-bridged [Ti2(m-tbop-k O,S,O)2L2] (L = Cl, diisopropy-
lphenolato, =NR) and alkoxo-bridged [Ti2(m-OR)2(OR)2(tbop-
3
k O,S,O)2] (R = Me, Et) as well as homoleptic [M(tbop-
3
k O,S,O)2] (M = Ti, Zr, Hf) complexes have been obtained
and characterized.23 Among them only heteroleptic titanium
compounds when activated with aluminium alkyls and sup-
ported on MgCl2 showed to be effective, well-defined, single-site
heterogeneous ethene polymerization catalysts.23a–c It has been
proved that during the ethene polymerization process, the tbop
ligand does not migrate to the aluminium atom of the activator
Results and discussion
Synthesis and crystallographic studies of homometallic zirconium
and hafnium complexes
aFaculty of Chemistry University of Wrocław, 14, F. Joliot-Curie, 50-383
Wrocław, Poland. E-mail: zj@wchuwr.pl; Fax: +48-71-328-23-48; Tel: +48-
71-375-74-80
The preparation of new thio(bisphenolato) zirconium and
hafnium dichloride compounds was carried out by employing
a method based on the s-bond metathesis reaction between an
appropriate thio(bisphenol) and a homoleptic metal precursor
such as MCl4 enabling HCl elimination. The reaction of MCl4
where M = Zr, Hf and a stoichiometric amount of tbopH2 in
bInstitute of Chemistry, University of Opole, 48 Oleska Street, 45-052 Opole,
Poland
† CCDC reference numbers 721082–721085. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b907560g
8846 | Dalton Trans., 2009, 8846–8853
This journal is
The Royal Society of Chemistry 2009
©

Scheme 1 Synthesis of zirconium and hafnium complexes 1–4.
toluene leads to the formation of microcrystalline products [M2(m-
3
tbop-k O,S,O)2Cl4] (1) for M = Zr and (2) for M = Hf (Scheme 1).
The IR spectra of 1 and 2 show characteristic modes for
terminally coordinated chlorides at 356, 380 and 320, 338 cm-1,
1
respectively. The H NMR spectra of 1 and 2 contain one set of
resonances due to the tbop ligand and are similar to the previ-
3
ously described, well characterized [Ti2(m-tbop-k O,S,O)2Cl4].23b
Attempts to grow crystals of 1 and 2 suitable for X-ray diffraction
proved unsuccessful. However we have found that the 1 : 2 s-
bond metathesis reaction of 1 and 2 with Li(dipp) (dipp = 2,6-
diisopropylphenolato) in diethyl ether proceeded readily and se-
3
lectively to yield colorless crystals of [M2(m-tbop-k O,S,O)2(dipp)4]
where M = Zr (3) and Hf (4). The 1H NMR spectra of 3
and 4 contain septet and doublet resonances for the isopropyl
substituents at the dipp groups and one resonance set of the
tbop ligand similar to those detected for 1 and 2. The molecular
structures of the two isostructural complexes 3 and 4 were
determined by X-ray crystallography. Fig. 1 shows complex 3, and
selected structural parameters for the two complexes are given in
the figure caption.
Crystals of 3 and 4 are composed of dimeric [M2(m-tbop-
k O,S,O)2(dipp)4] molecules in which two distorted octahedral
3
metal centers are linked by a double bridge formed through the
oxygen atoms of the tbop ligands in a manner shown in Scheme 1.
These oxygen atoms together with both oxygen atoms of the dipp
groups are situated in equatorial positions whereas the sulfur and
the second oxygen atom of the tbop ligand occupy the axial sites.
The dipp ligands are terminally coordinated to the metal centers
in cis positions. The M–O distances are very similar and within
the expected ranges for Zr and Hf aryloxides.7d,17d,21a,23d However,
there is a significant decrease in the metal–sulfur bond distance on
going from Zr to Hf. This structural feature presumably reflects
a decrease in oxophilicity on descending group IV, although the
influence of the crystal packing is not excluded. The molecular
structures of 3 and 4 suggest that complexes 1 and 2 may have
also in the solid state dimeric nature with terminally coordinated
chloride atoms.
3
Fig. 1 Molecular structure of [M2(m-tbop-k O,S,O)2(dipp)4] [where
M
=
Zr (3) or Hf (4)] (3 shown, hydrogen atoms omitted for
clarity). Selected bond lengths (A) and angles (◦): 3, Zr(1)–S(1)
2.848(1), Zr(1)–O(1) 1.948(2), Zr(1)–O(8) 1.954(2), Zr(1)–O(7) 2.206(2),
O(2)–Zr(1)–S(1) 75.70(6), O(1)–Zr(1)–O(5) 157.14(7), S(1)–Zr(1)–O(8)
160.53(6). 4, Hf(1)–S(1) 2.820(2), Hf(1)–O(1) 1.940(3), Hf(1)–O(5)
2.186(2), Hf(1)–O(8) 1.960(2), S(1)–Hf(1)–O(1) 74.99(7), O(2)–Hf(1)–O(5)
155.97(9), S(1)–Hf(1)–O(8) 160.92(7).
˚
geometry and two tetrahedral aluminium atoms linked via oxygen
atoms of the tbop ligands. The Zr–O and Zr–S distances are very
similar to those in [Zr(m-tbop-k O,S,O)2Me2(m-AlMe2)2]23d and as
expected slightly shorter than those detected for the octahedral
complex 3. The Al–O and Al–Cl bond lengths are close to those
found in other structures of aluminium aryloxides and chlorides
respectively.23b,c,24,25
3
1
The H NMR spectra of 5 and 6 were similar and afforded a
Synthesis and crystallographic studies of heterometallic zirconium,
hafnium and aluminium complexes
single set of resonances for the tbop ligand in accordance with the
ground-state structure established by crystallography. Compounds
5 and 6 are the chloride analogues of the previously described
3
Treatment of MCl4 with [Al2(m-OEt)2(tbop-k O,S,O)2]23c at 2 : 1
3
molar ratio in toluene leads after workup to colorless crystals of
methyl derivatives [M(tbop-k O,S,O)2Me2(m-AlMe2)2] (M = Ti,
3
3
[M(tbop-k O,S,O)2Cl2(m-AlCl2)2] (5)·0.5C6H14 for M = Zr and (6)
Zr, Hf) obtained in the reaction of [M(tbop-k O,S,O)2] with two
for M = Hf in 82% and 84% yield, respectively (Scheme 2).
The molecular structure of 5·0.5C6H14 was determined by
X-ray crystallography and is shown in Fig. 2. The structure
of 5 reveals an eight-coordinate Zr center with a dodecahedral
equivalents of AlMe3.23d
The reaction of MCl4 with organoaluminium precursor [Al2(m-
tbop-k O,S,O)2Me2]23c at 2 : 1 molar ratio in toluene resulted in
3
the formation of colorless solids (A) for M = Zr and (B) for
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8846–8853 | 8847
©

Scheme 2 Synthesis of zirconium and hafnium complexes 5–8.
3
Fig.
2
Molecular structure of [Zr(tbop-k O,S,O)2Cl2(m-AlCl2)2]
(5)·0.5C6H14 (hydrogen atoms and C6H14 omitted for clarity). Selected
◦
˚
bond lengths (A) and angles ( ): Zr–S(1) 2.765(2), Zr–S(2) 2.780(2),
Zr–O(1) 2.198(2), Zr–O(2) 2.338(2), Zr–Cl(1) 2.400(2), Al(1)–O(1)
1.799(2), Al(1)–O(3) 1.777(2), Al(1)–Cl(3) 2.096(2), Al(1)–Cl(4) 2.087(2),
S(1)–Zr–S(2) 150.00(3), O(1)–Zr–O(2) 77.11(8), O(1)–Zr–O(4) 89.17(8),
O(3)–Zr–Cl(2) 146.06(6), Cl(2)–Zr–Cl(1) 92.77(3), O(3)–Al(1)–O(1)
85.45(11), O(3)–Al(1)–Cl(4) 112.84(11), O(1)–Al(1)–Cl(3) 110.14(9).
M = Hf. The 1H NMR spectra of A and B show signals at -0.01
and -0.03 ppm for A, and -0.02 and -0.06 ppm for B indicating
inequivalent methyl groups attached to aluminium atoms and two
sets of resonances due to the tbop ligand. These may suggest that A
and B are a mixture of chemically different compounds in solution.
The solid state structure of crystals obtained by recrys-
tallization of B from CH2Cl2 showed it to be the cocrys-
3
Fig. 3 Molecular structure of the cocrystallite [Hf(tbop-k O,S,O)2Cl2(m-
3
AlCl2)2]3[Hf(tbop-k O,S,O)2Cl2(m-AlMe2)2]2 (6·8)·CH2Cl2 (6 at the top,
3
tallite of [Hf(tbop-k O,S,O)2Cl2(m-AlCl2)2] (6) and [Hf(tbop-
8 at the bottom) (hydrogen atoms and CH2Cl2 omitted for clarity).
3
k O,S,O)2Cl2(m-AlMe2)2] (8) species in a 3 : 2 ratio (Scheme 2)
Selected bond lengths (A) and angeles (◦): Hf–S(1) 2.782(2),
˚
(Fig. 3).
Hf–S(2) 2.776(2), Hf–O(1) 2.309(2), Hf–O(2) 2.189(2), Hf–O(3)
2.164(2), Hf–Cl(1) 2.405(2), Al(1)–O(1) 1.796(2), Al(1)–O(3) 1.834(2),
S(1)–Hf–S(2) 148.61(3), O(1)–Hf–O(2) 76.47(7), O(1)–Hf–O(4) 125.56(7),
O(3)–Hf–Cl(2) 149.23(5), Cl(2)–Hf–Cl(1) 92.05(4), O(3)–Al(1)–O(1)
83.63(10).
Thus, the structure of 6·8·CH2Cl2 is composed of two chemically
independent molecules, which are statistically distributed in the
crystal and one molecule CH2Cl2 of crystallization. The Hf–O
and Hf–S bond lengths and angles are in a similar range and
8848 | Dalton Trans., 2009, 8846–8853
This journal is
The Royal Society of Chemistry 2009
©

Table 1 1-Hexene polymerization results with complexes 1–6a
3
close to those of previously reported [Hf(tbop-k O,S,O)2Me2(m-
AlMe2)2].23d However, because of disorder at the tetrahedral
aluminium atoms arising from unequal distribution of carbon
atoms of methyl groups and chlorides at aluminium centers (see
Experimental section) discussion of Al–C and Al–Cl distances is
impossible. The 1H NMR spectra of A is similar to B and suggest
Activity
Run Compound Activator [g PH/mmol-1 h-1] Mw 10-3 Mw/Mn
1
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
Al(iBu)3
MAO
33
25
17
37
14
0
40
0
0
31
24
0
32
16
14
43
25
23
93.7
—
—
59.5
—
—
63.5
—
—
84.7
—
—
51.8
—
—
55.4
—
—
3.3
—
—
3.4
—
—
2.6
—
—
3.1
—
—
2.7
—
—
2.4
—
—
2
3b
4
MAO
3
it to be also a mixture of 5 and [Zr(tbop-k O,S,O)2Cl2(m-AlMe2)2]
Al(iBu)3
MAO
(7).
5
6b
7
MAO
The formation of compounds 5–8 occurs via the substitution of
two chlorides at the central transition metal by two tridentate tbop
groups and as a result zirconium and hafnium reach a coordination
number of eight in formed anionic [M(tbop-k O,S,O)2Cl2]2- species
Al(iBu)3
MAO
8
9b
MAO
3
10
Al(iBu)3
MAO
whereas two cationic [AlCl2]+ or [AlMe2]+ moieties undergo
addition to the oxygen atoms of the tbop ligands to achieve a
tetrahedral geometry. Although compounds 5 and 6 are chloride
analogs of methyl derivatives, to our knowledge they represent
the first examples of eight-coordinate dichloride zirconium or
hafnium complexes bearing AlCl2 moieties. Unfortunately, at-
tempts to obtain 7 and 8 in a pure form failed.
11
12b
13
MAO
Al(iBu)3
MAO
14
15b
16
MAO
Al(iBu)3
MAO
17
18b
MAO
a Polymerization conditions: [M]0 = 0.1 mmol dm-3, [Al] = 2 mmol dm-3,
Mg/M = 10, T = 293 K. b Without MgCl2.
Polymerization of 1-hexene
To assess the potential of complexes 1–6 in a-olefin polymerization
catalysis, we performed the preliminarily tests in ethene and 1-
hexene polymerization, using both heterogeneous and homoge-
neous processes with different cocatalysts and under variable
conditions. Upon activation of compounds 1–6 with aluminium
alkyls (AliBu3, MAO) and supporting on MgCl2 in n-hexane no
active catalysts for ethene polymerization had formed whereas the
same systems acted as a catalyst in the 1-hexene polymerization
process. Catalysts for 1-hexene polymerization were prepared in
n-hexane by milling a slurry of [MgCl2(thf)2] with the zirconium
or hafnium compound (10 : 1). Then the sample of precatalyst
suspension was added to the mixture of 1-hexene and aluminium
activator (40 : 1). The activity of catalysts was found to be
practically independent on temperature (293 K or 323 K) and
the geometry of zirconium and hafnium sites in precursors and
was calculated to be higher (about 40 g mmol-1) for AliBu3 than
for MAO as cocatalysts (Table 1). Lower activity or its lack was
achieved for systems activated with MAO in homogeneous systems
(runs 3, 6, 9, 12, 15, 18, Table 1).
to produce atactic poly(1-hexene) (30 g mmol-1 h-1). Thus, so
far accessible data have not been indicative of factors deter-
mining the activity, molecular weight and stereoregularity of 1-
hexene polymerization by the sulfur donor based systems and
further studies in this area are essential for explanation of this
problem.
Conclusions
We have demonstrated the synthesis of a family of neutral zirco-
nium and hafnium complexes of the tridentate thio(bisphenolato)
ligand (tbop). An effective route for the preparation of [M2(m-tbop-
3
k O,S,O)2Cl4] M = Zr 1, Hf 2 species was based on the direct reac-
tion between MCl4 and one equivalent of tbopH2 in toluene. Sub-
stitution of the chlorides in 1 and 2 by 2,6-diisopropylphenolato
groups (dipp) generates new dimeric compounds [M2(m-tbop-
3
k O,S,O)2(dipp)4] (M = Zr 3, Hf 4). The structures of 1–4
were confirmed by NMR spectroscopy; complexes 3 and 4 were
The 13C NMR spectra of poly(1-hexenes) revealed a regioregular
and stereoirregular (atactic) structure. The polymers had very
high molecular weights in the range 518 000–937 000 g mmol-1
and a narrow molecular weight distribution. These results are
further investigated by X-ray crystallography. The use of the tbop-
3
aluminium precursors [Al2(m-OEt)2(tbop-k O,S,O)2] or [Al2(m-
3
tbop-k O,S,O)2Me2] in reactions with MCl4 creates heterotrinu-
3
clear complexes [M(tbop-k O,S,O)2Cl2(m-AlX2)2] (M = Zr, X = Cl
3
in contrast to the [Zr(tbmp-k O,S,O)Cl2]/MAO system which
5, X = Me 7 and Hf X = Cl 6, X = Me 8). The single-crystal X-ray
diffraction analysis of those complexes showed for zirconium and
hafnium centers to have eight-coordinate dodecahedral geometry
and aluminium atoms to have tetrahedral surroundings. Com-
plexes 1–6 after activation with aluminium alkyls and supporting
on MgCl2 showed a lack of activity in the ethene polymerization
process and moderate activity towards 1-hexene producing high
molecular weight atactic poly(1-hexenes). Their narrow molecular
weight distribution indicates that the operation of heterogeneous
single-site catalysts occurs. Similar activities of those systems
towards 1-hexene suggests that independently on the geometry
of zirconium and hafnium sites in precursors 1–6 the same type of
active centers are produced during their activation with aluminium
alkyls.
do not polymerize 1-hexene.3a It has been suggested that the
tbmp ligand provides sufficient steric hindrance to suppress
2,1-insertion of 1-hexene. However, the corresponding double
4
sulfur donor system [Zr(dtbmp-k OSSO)(bn)2]/B(C6F5)3 having
the same substituents at the phenolate groups like the tbmp,
effectively polymerizes 1-hexene and reveals an atactic structure
of poly(1-hexene) with a relatively low molecular weight (7400 g
3
mol).22e In this context the activity of the [Ti2(tbmp-k O,S,O)2(m-
Cl2)2Cl2]/MAO system in a specific polymerization of 1-hexene
affording atactic poly(1-hexene) is not comprehensible. It is worthy
to mention that our heterotrinuclear titanium complex [Ti(tbop-
3
k O,S,O)2Me2(m-AlMe2)2]23d supported on MgCl2 upon activation
with AliBu3 showed moderate activity in 1-hexene polymerization
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8846–8853 | 8849
©

and storage at 253 K for a one week provided colorless crystals of
3 (2.39 g, 62%). (Found C 73.01; H 8.51; S 3.81. C104H148O8S2Zr2
requires C 73.10; H 8.73; S 3.75%.) nmax/cm-1 446 (m), 478 (s),
525 (m), 568 (m), 631 (m), 739 (m), 762 (s), 839 (vs), 881 (m), 982
(m), 1067 (s), 1120 (m), 1144 (m), 1261 (vs), 1274 (m), 1334 (s),
1358 (s), 1412 (m), 1433 (s), 1591 (m) (Nujol). dH (300 MHz,
C6D6, 298 K) 7.63–6.70 (24H, m, C6H3), 3.72 [8H, septet,
C6H3{CH(CH3)2}2], 1.76, 1.68 [8H, s, C(CH3)2CH2C(CH3)3],
1.33, 1.29 [24H, s, C(CH3)2CH2C(CH3)3], 1.21 [48H, d,
C6H3{CH(CH3)2}2], 0.84 [36H, s, C(CH3)2CH2C(CH3)3]. dC
(75.5 MHz, C6D6, 298 K) 163.6, 140.9, 136.9, 133.9, 131.7, 129.7,
123.8, 123.5, 118.6 (C6H3), 56.7 [C(CH3)2CH2C(CH3)3], 37.9, 32.2,
31.5, 27.9 [C(CH3)2CH2C(CH3)3], 27.2 [C6H3{CH(CH3)2}2], 22.9
[C6H3{CH(CH3)2}2].
Experimental
General remarks
All operations were carried out under a dry dinitrogen atmosphere,
using standard Schlenk techniques. All the solvents were distilled
under dinitrogen from the appropriate drying agents prior to
use. The compounds ZrCl4, HfCl4, AlMe3, MAO, Al(iBu)3 and
2,2¢-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenol} (tbopH2) were
obtained from the Aldrich Chemical Co. and used without
further purification unless stated otherwise. [Al2(m-OEt)2(tbop-
3
3
k O,S,O)2] and [Al2(m-tbop-k O,S,O)2Me2] were prepared by lit-
erature method.23c Infrared spectra were recorded on a Perkin-
Elmer 180 spectrophotometer in Nujol mulls. NMR spectra were
performed on a Bru¨ker ARX 300 spectrometer. Microanalysis
were conducted with a ASA-1 (GDR, Karl-Zeiss-Jena) instrument
(in-house).
[Hf2(l-tbop-j3O,S,O)2(dipp)4] (4)
[Zr2(l-tbop-j3O,S,O)2Cl4] (1)
This complex was prepared in an analogous manner to that
employed to 3 from 2 (1.88 g; 1.36 mmol) and Li(dipp) (1.00 g;
5.45 mmol) as colorless crystals (1.78 g, 67%). (Found C 65.91;
H 7.56; S 3.47. C104H148O8S2Hf2 requires C 66.32; H 7.92; S
3.40%.) nmax/cm-1 442 (m), 455 (m), 471 (s), 485 (w), 531 (m),
558 (w), 582 (m), 611 (s), 656 (m), 667 (vs), 725 (s), 738 (s),
764 (vs), 836 (vs), 862(m), 866 (s), 912 (m), 924 (m), 964 (w),
1071 (vs), 1106 (m), 1128 (m), 1231 (s), 1262(s), 1270 (vs),
1324 (m), 1362 (vs), 1374 (w), 1581 (m) (Nujol). dH (300 MHz,
C6D6, 298 K) 7.63–6.70 (24H, m, C6H3), 3.74 [8H, septet,
C6H3{CH(CH3)2}2], 1.76, 1.68 [8H, s, C(CH3)2CH2C(CH3)3], 1.34
[24H, s, C(CH3)2CH2C(CH3)3], 1.25 [48H, d, C6H3{CH(CH3)2}2],
0.83 [36H, s, C(CH3)2CH2C(CH3)3]. dC (75.5 MHz, C6D6,
298 K) 163.6, 141.1, 133.9, 131.9, 129.75, 123.7, 123.1,
121.2, 119.4 (C6H3), 56.6 [C(CH3)2CH2C(CH3)3], 37.9, 32.4,
32.2, 31.5 [C(CH3)2CH2C(CH3)3], 27.3 [C6H3{CH(CH3)2}2], 22.9
[C6H3{CH(CH3)2}2].
To a suspension of ZrCl4 (1.35 g; 5.79 mmol) in toluene (40 mL)
was added tbopH2 (2.56 g; 5.79 mmol). The mixture was stirred
at room temperature until the evolution of HCl had ceased (48 h).
Then all volatiles were removed under reduced pressure to obtain a
light yellow solid (2.54 g, 73%). (Found: C 55.39; H 6.58; Cl 11.29;
S 5.43. C56H80Cl4O4S2Zr2 requires C 55.79; H 6.69; Cl 11.56; S
5.32%.) nmax/cm-1 356 (m), 380 (s), 452 (m), 492 (s), 524 (s), 556 (m),
622 (s), 730 (3), 760 (s), 832 (vs), 884 (s), 976 (m), 1062 (s), 1100 (m),
1148 (m), 1252 (vs), 1268 (s), 1324 (s), 1364 (s), 1376 (s), 1402 (m),
1412 (s), 1596 (m) (Nujol). dH (300 MHz, C6D6, 298 K) 8.53–6.57
(12H, m, C6H3), 1.62 [8H, s, C(CH3)2CH2C(CH3)3], 1.26 [24H, s,
C(CH3)2CH2C(CH3)3], 0.72 [36H, s, C(CH3)2CH2C(CH3)3]. dC
(75.5 MHz, C6D6, 298 K) 154.5, 146.9, 130.9, 128.9, 124.2,
117.9 (C6H3), 57.1 [C(CH3)2CH2C(CH3)3], 38.2, 32.8, 31.3, 30.3
[C(CH3)2CH2C(CH3)3].
[Hf2(l-tbop-j3O,S,O)2Cl4] (2)
[Zr(tbop-j3O,S,O)2Cl2(l-AlCl2)2] (5)·0.5C6H14
This complex was prepared in an analogous manner to that
employed to 1 from HfCl4 (1.26 g; 3.93 mmol) and tbopH2 (1.74 g;
3.93 mmol) as a colorless solid (2.22 g, 82%). (Found C 48.55;
H 5.55; Cl 9.85; S 4.68. C56H80Cl4O4S2Hf2 requires C 48.73; H
5.84; Cl 10.28; S 4.65%.) nmax/cm-1 320 (m), 338 (vs), 420 (vw),
440 (w), 466 (m), 462 (s), 474 (w), 528 (m), 558 (w), 586 (m),
600 (s), 676 (m), 732 (vs), 736 (s), 756 (vs), 830 (vs), 852 (m),
868 (s), 924 (m), 976 (w), 1056 (vs), 1100 (m), 1140 (m), 1224
(vs), 1250 (vs), 1278 (vs), 1324 (m), 1364 (vs), 1372(m), 1376
(vs), 1596 (m) (Nujol). dH (300 MHz, C6D6, 298 K): 8.64–6.96
(12H, m, C6H3), 1.68 [8H, s, C(CH3)2CH2C(CH3)3], 1.29 [24H, s,
C(CH3)2CH2C(CH3)3], 0.82 [36H, s, C(CH3)2CH2C(CH3)3]. dC
(75.5 MHz, C6D6, 298 K) 129.2, 128.5, 126.3, 125.6, 125.1,
124.8 (C6H3), 56.8 [C(CH3)2CH2C(CH3)3], 38.3, 32.2, 32.0, 31.9
[C(CH3)2CH2C(CH3)3] ppm.
A mixture of ZrCl4 (1.64 g; 7.02 mmol) and [Al2(m-OEt)2(tbop-
k O,S,O)2] (3.6 g; 3.51 mmol) in toluene (40 mL) was stirred at
3
room temperature for 18 h. The resulting mixture was filtered to
remove [ZrCl2(OEt)2], and the filtrate was evaporated in vacuo,
leaving a colorless solid, which was washed with n-hexane (2 ¥
5 mL) and dried under vacuum to give a colorless powder
(3.57 g, 82%). (Found: C 54.02; H 6.68; Cl 16.96; S 5.33.
C56H80Cl6O4S2Al2Zr requires C 54.28; H 6.41; Cl 17.16; S 5.17%.)
n
max/cm-1 379 (s), 451 (m), 484 (s), 536 (s), 557 (m), 632 (s), 728
(3), 762 (s), 832 (vs), 874 (s), 972 (m), 1054 (s), 1101 (m), 1149 (m),
1253 (vs), 1266 (s), 1323 (s), 1364 (s), 1369 (s), 1410 (m), 1434 (s),
1582 (m) (Nujol). dH (300 MHz, C6D6, 298 K) 7.67–7.09 (12H, m,
C6H3), 1.63, 1.57 [8H, s, C(CH3)2CH2C(CH3)3], 1.28, 1.22 [24H, s,
C(CH3)2CH2C(CH3)3], 0.77 [36H, s, C(CH3)2CH2C(CH3)3]. dC
(75.5 MHz, C6D6, 298 K) 159.3, 145.5, 140.2, 131.9, 130.1,
117.8 (C6H3); 57.5 [C(CH3)2CH2C(CH3)3]; 38.1, 32.0, 31.8, 30.9
[C(CH3)2CH2C(CH3)3].
[Zr2(l-tbop-j3O,S,O)2(dipp)4] (3)
To a solution of 1 (2.62 g; 2.17 mmol) in diethyl ether (30 mL)
was added Li(dipp) (1.60 g; 8.70 mmol) dissolved in diethyl ether
(20 mL). The mixture was stirred over a period of 12 h and then
filtered to remove LiCl. Reduction of the filtrate volume to 10 mL
Crystals suitable for X-ray analysis were obtained by recrystal-
lization from a mixture of n-hexane–CH2Cl2 (1 : 4) at 258 K.
The crystal structure shows the presence of 0.5 molecule of
hexane in the unit cell, however the elemental analysis indicates
8850 | Dalton Trans., 2009, 8846–8853
This journal is
The Royal Society of Chemistry 2009
©

that this is absent from the powder sample analyzed, presumably
removed by the vacuum drying to which they were subjected.
(s), 848 (m), 862 (s), 921 (m), 972 (w), 1062 (vs), 1112 (m), 1139 (m),
1234 (vs), 1244 (vs), 1281 (vs), 1326 (m), 1363 (s), 1370 (m), 1374
(s), 1592 (m) (Nujol). dH (300 MHz, C6D6, 298 K) 7.28–6.8 (24H,
m, C6H3), 1.74, 1.68 1.63, 1.57 [16H, s, C(CH3)2CH2C(CH3)3],
1.21, 1.20, 1.16, 1.17 [48H, s, C(CH3)2CH2C(CH3)3], 0.67, 0.66
[72H, s, C(CH3)2CH2C(CH3)3], -0.02, -0.06 (12H, s, Al–CH3).
dC (75.5 MHz, C6D6, 298 K) 155.6, 155.3, 146.8, 146.6 131.2,
131.1, 130.3, 130.1, 123.8, 123.7, 117.8, 117.6 (C6H3), 57.2, 57.1
[C(CH3)2CH2C(CH3)3], 38.3, 38.2, 32.3, 32.2, 31.9, 31.8, 31.8, 31.7
[C(CH3)2CH2C(CH3)3]; 10.9, 8.5 (Al–CH3).
[Hf(tbop-j3O,S,O)2Cl2(l-AlCl2)2] (6)
This complex was prepared as described above for 5 starting
3
from HfCl4 (0.93 g; 2.92 mmol) and [Al2(m-OEt)2(tbop-k O,S,O)2]
(1.50 g; 1.46 mmol). Workup afforded a white powder of 6
(1.63 g, 84%). (Found: C 50.01; H 6.01; Cl 15.95; S 4.58.
C56H80Cl6O4S2Al2Hf requires C 50.70; H 6.08; Cl 16.04; S 4.82%).
n
max/cm-1 318 (w), 336 (vs), 422 (w), 445 (w), 456 (m), 464
The crystal structure shows the presence of one CH2Cl2
molecule in the unit cell, however the elemental analysis indicates
that this is absent from the powder sample analyzed, presumably
removed by the vacuum drying to which they were subjected.
(s), 478 (w), 532 (m), 562 (w), 582 (m), 612 (s), 666 (m),
736 (s), 732 (s), 749 (vs), 832 (s), 849 (m), 862 (s), 920 (m),
966 (w), 1049 (vs), 1105 (m), 1138 (m), 1228 (vs), 1246 (vs),
1282 (vs), 1314 (m), 1358 (vs), 1370 (m), 1374 (vs), 1586 (m)
(Nujol). dH (300 MHz, C6D6, 298 K) 7.67–7.09 (12H, m, C6H3),
1.63, 1.57 [8H, s, C(CH3)2CH2C(CH3)3], 1.28, 1.22 [24H, s,
C(CH3)2CH2C(CH3)3], 0.68 [36H, s, C(CH3)2CH2C(CH3)3]. dC
(75.5 MHz, C6D6, 298 K) 159.2, 145.5, 140.2, 131.9, 130.1,
117.8 (C6H3); 57.5 [C(CH3)2CH2C(CH3)3]; 38.1, 32.9, 31.8, 30.9
[C(CH3)2CH2C(CH3)3].
Polymerization of 1-hexene
A slurry of [MgCl2(THF)2] (100 mmol) and zirconium or hafnium
precatalyst (10 mmol) in n-hexane was milled under argon in a
glass mill (capacity 250 ml, with 20 balls of diameter 5–15 mm) at
room temperature for 24 h. The sample of precatalyst suspension
(containing 0.1 mmol of Zr or Hf)) was added to the mixture of 1-
hexene (80 mmol) and aluminium activator (2 mmol) in n-hexane
(50 mL). The reaction mixture was stirred at 293 K or 323 K
under argon and after 1 h polymerization was terminated by the
addition of 20 mL of 5% solution of HCl in ethanol and dried
under vacuum at 40 ◦C for 12 h.
[Zr(tbop-j3O,S,O)2Cl2(l-AlCl2)2]3[Zr(tbop-j3O,S,O)2Cl2(l-
AlMe2)2]2 (5·7)
These complexes were prepared as described above for 5 and
6 starting from ZrCl4 (0.66 g; 2.87 mmol) and [Al2(tbop-
3
k O,S,O)2Me2] (2.78 g; 2.87 mmol). Workup afforded a white
Molecular weight and polydispersities of poly-1-hexene were
measured by GPC method (Gel Permeation Chromatography),
Waters-150, at 415 K in 1,2,4-trichlorobenzene.
powder which after recrystallization from CH2Cl2 gave colorless,
microcrystalline product. Yield for white powder: 2.52 g, 73.9%
(calc. for starting ZrCl4). Elemental analysis as well as NMR
spectra were identical for both the powder and the crystalline form.
(Found C 56.11; H 6.94; Cl 14.01; S 5.38. C289H426Cl24O20S10Al10Zr5
requires C 56.74; H 7.02; Cl 13.91; S 5.24%.) nmax/cm-1 382 (s),
449 (m), 486 (s), 532 (s), 552 (m), 629 (s), 722 (3), 758 (s), 827 (vs),
879 (s), 966 (m), 1057 (s), 1107 (m), 1152 (m), 1249 (vs), 1262 (s),
1328 (s), 1359 (s), 1366 (s), 1412 (m), 1424 (s), 1586 (m) (Nujol). dH
(300 MHz, C6D6, 298 K) 7.94–6.83 (24H, m, C6H3), 1.74, 1.68 1.63,
1.57 [16H, s, C(CH3)2CH2C(CH3)3], 1.28, 1.22, 1.20, 1.14 [48H, s,
C(CH3)2CH2C(CH3)3], 0.72, 0.71 [72H, s, C(CH3)2CH2C(CH3)3],
-0.01, -0.03 (12H, s, Al–CH3). dC (75.5 MHz, C6D6, 298 K)
155.3, 155.1, 146.9, 146.8, 131.5, 131.4, 130.2, 130.1, 123.7, 123.5,
118.4, 118.2 (C6H3), 57.1, 57.0 [C(CH3)2CH2C(CH3)3], 32.3, 32.1,
31.9, 31.8, 31.5, 31.4, 31.3, 31.1 [C(CH3)2CH2C(CH3)3], 14.3, 10.5
(Al–CH3).
Crystallographic analysis
Crystal data and refinement details for all compounds are given
in Table 2.
The crystals were mounted on glass fibers and then flash-frozen
to 100(2) K (Oxford Cryosystem-Cryostream Cooler). Preliminary
examination and intensities data collections were carried out
on a Kuma KM4 CCD k-axis diffractometer with graphite-
monochromated Mo Ka radiation. All data were corrected for
Lorentz, polarization and absorption effects. Data reduction and
analysis were carried out with the Kuma Diffraction programs.26
All structures were solved by direct methods and refined by
the full-matrix least-squares method on all F2 data using the
SHELXTL software.27 Carbon bonded hydrogen atoms were
included in calculated positions and refined in the riding mode
using SHELXTL default parameters. Other hydrogen atoms were
located in a difference map. All crystals were poorly shaped
and weakly diffracting, giving low resolution data and relatively
high R-values. One reason for this might be the high amount of
disorder in the crystal structure. The high temperature factors
of the terminal carbon atoms suggest their disorder, which
unfortunately, could not be resolved. It was found that the struc-
ture of 6·8·CH2Cl2 is composed of two chemically independent
[Hf(tbop-j3O,S,O)2Cl2(l-AlCl2)2]3[Hf(tbop-j3O,S,O)2Cl2(l-
AlMe2)2]2 (6·8)·CH2Cl2
These complexes were prepared as described above for 5·7 starting
3
from HfCl4 (0.72 g; 2.25 mmol) and [Al2(tbop-k O,S,O)2Me2]
(2.18 g; 2.25 mmol). Workup afforded a white powder which
after recrystallization from CH2Cl2 gave colorless crystals suitable
for X-ray analysis. Yield for white powder: 2.29 g, 78.96% (calc.
for starting HfCl4). Elemental analysis as well as NMR spectra
were identical for both the white powder and the crystalline
form of 6·8. (Found: C 52.48; H 6.46; Cl 13.12; S 5.01.
C289H426Cl24O20S10Al10Hf5 requires C 52.96; H 6.55; Cl 12.96; S
4.88%.) nmax/cm-1 326 (vw), 336 (s), 422 (w), 452 (m), 458 (s), 478
(w), 542 (m), 556 (w), 581 (m), 611 (s), 672 (m), 744 (s), 758 (vs), 826
3
3
[Hf(tbop-k O,S,O)2Cl2(m-AlCl2)2] and [Hf(tbop-k O,S,O)2Cl2(m-
AlMe2)2]molecules whichare statisticallydistributed inthecrystal.
The terminal Cl and Me ligands in these complexes were refined
with a 0.6 and 0.4 occupancy, respectively. Moreover the CH2Cl2
solvent molecule is split over three sites.
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8846–8853 | 8851
©

Table 2 Crystal data and collection parameters of complexes 3, 4, 5·0.5C6H14 and 6·8·CH2Cl2
Compound
3
4
5·0.5C6H14
6·8·CH2Cl2
Empirical formula
M
C104H148O8S2Zr2
1772.78
Monoclinic
C104H148Hf2O8S2
1947.32
Monoclinic
C59H87Al2Cl6O4S2Zr
1282.29
Triclinic
¯
P1
14.737(5)
15.552(5)
16.690(5)
73.73(2)
86.36(2)
62.22(2)
3239(2)
C58.60H86.80Al2Cl6.40HfO4S2
1378.73
Triclinic
¯
P1
Crystal system
Space group
P21/c
P21/c
˚
a/A
19.830(5)
19.186(5)
28.187(4)
90
112.15(2)
90
9933(4)
4
1.186
0.332 ¥ 0.231 ¥ 0.121
0.304
2.82 to 27.00
112 927
21 660, 0.0529
1073
19.776(5)
19.173(5)
28.240(4)
90
112.24(2)
90
9911(4)
4
1.305
0.322 ¥ 0.210 ¥ 0.083
2.188
2.83 to 28.53
26 452
23 439, 0.032
1081
14.802(4)
15.571(4)
16.625(4)
73.88(3)
86.93(3)
62.71(3)
3259.2(18)
2
1.405
0.324 ¥ 0.215 ¥ 0.112
1.996
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
3
˚
V/A
Z
2
Dc/Mg m-3
1.311
0.32 ¥ 0.17 ¥ 0.11
0.551
2.89 to 27.00
26 815
13 944, 0.0538
688
Crystal size/mm3
m/mm-1
q/◦
2.88 to 27.00
37 547
14 204, 0.056
742
Reflections collected
Unique reflections, R(int)
Parameters
Final R1, wR2 [I > s(I)]
Final R1, wR2 (all data)
Goodness-of-fit (S)
0.0647, 0.1063
0.0924, 0.1140
1.245
0.0384, 0.0855
0.0565, 0.0908
1.080
0.0507, 0.0822
0.0822, 0.0916
0.936
0.0343, 0.0534
0.0572, 0.0568
0.984
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Acknowledgements
The authors wish to thank the State Committee for Scientific
Research (Poland) for financial support of this work (grant No
N204089 31/2127). We also thank Dr Lucjan B. Jerzykiewicz for
his help in crystallographic analysis with Dr Dorota Godbole.
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