Novel indenylzirconium complexes as supported catalysts in the polymerization of ethylene

Article abstract of DOI:10.1002/ejic.200500165

A series of substituted indene {C₉H₇R-3 [R = CH ₂CH₂CH₂OSiMe₃ (1), CH ₂CH₂CH₂OCH₂C₆H ₅ (2), CH₂CH₂CH₂OSiMe₂tBu (3)]}, and ansa-indene compounds {Me₂Si(C₉H ₆R-3)₂-1 [R = CH₂CH₂CH ₂OSiMe₃ (4)], Me₂Si(C₉H ₆R-3)-1(C₅HMe₄) [R = CH₂CH ₂CH₂OSiMe₃ (5), CH₂CH ₂CH₂OCH₂C₆H₅ (6), CH ₂CH=CH₂ (7), CH₂CH₂CH ₂OSiMe₂tBu (8)]} have been prepared. The lithium derivatives of 1-8 were employed in the synthesis of the indenylzirconium complexes [Zr(η⁵-C₉H₆R-1) ₂Cl₂] [R = CH₂CH₂CH ₂OSiMe₃ (17), CH₂CH₂CH ₂OCH₂C₆H₅ (18), CH ₂CH₂CH₂OSiMe₂tBu (19)], rac-[Zr{Me₂Si(η⁵-C₉H₅R-3) ₂-1}Cl₂] [R = CH₂CH₂CH ₂OSiMe₃ (20)], [Zr{Me₂Si(η⁵- C₉H₅R-3)-1(η⁵-C₅Me ₄)}Cl₂] [R = CH₂CH₂CH ₂OSiMe₃ (21), CH₂CH₂CH ₂OCH₂C₆H₅ (22), CH ₂CH=CH₂ (23), CH₂CH₂CH ₂OSiMe₂tBu (24)] and [Zr(Me₂Si{η ⁵-C₉H₅(CH₂CH₂CH ₂O)-3}-1{η⁵-C₅Me₄})Cl] (21a). The alkyl complexes [Zr(Me₂Si{η⁵-C₉H ₅(CH₂CH₂CH₂O)-3}- 1{η⁵-C₅Me₄})Me] (25) and [Zr{Me ₂Si(η⁵-C₉H₅R-3)- 1(η⁵-C₅Me₄)}Me₂] [R = CH ₂CH₂CH₂OSiMe₂tBu (26)] have been synthesized by the reaction of the corresponding ansa-zir-conocene derivative with the alkyl Grignard reagent. The molecular structure of [(Zr{C ₉H₆(CH₂CH₂CH₂O)-1}Cl ₂)2(Zr-O)] (17a), a subproduct in the formation of 17 has been determined by single-crystal X-ray diffraction studies. The indenylzirconium complexes 17-24 have been immobilized on partially dehydroxylated SiO ₂, and these supported systems used to polymerize ethylene in the presence of methylaluminoxane. The catalytic activity of these compounds in both homogeneous and heterogeneous polymerization is reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200500165

FULL PAPER
Novel Indenylzirconium Complexes as Supported Catalysts in the
Polymerization of Ethylene
Carlos Alonso-Moreno,[a] Antonio Antiñolo,[a] Fernando Carrillo-Hermosilla,[a]
Pedro Carrión,[a] Isabel López-Solera,[a] Antonio Otero,*[a] Sanjiv Prashar,[b] and
José Sancho[c]
Keywords: Metallocene / Zirconium / Homogeneous catalysis / Supported catalysts / Polymerization / Ethylene
A series of substituted indene {C9H7R-3 [R = CH2CH2CH2O-
SiMe3 (1), CH2CH2CH2OCH2C6H5 (2), CH2CH2CH2OSiMe2-
tBu (3)]}, and ansa-indene compounds {Me2Si(C9H6R-3)2-1
[R = CH2CH2CH2OSiMe3 (4)], Me2Si(C9H6R-3)-1(C5HMe4)
[R = CH2CH2CH2OSiMe3 (5), CH2CH2CH2OCH2C6H5 (6),
CH2CH=CH2 (7), CH2CH2CH2OSiMe2tBu (8)]} have been
prepared. The lithium derivatives of 1–8 were employed in
the synthesis of the indenylzirconium complexes [Zr(η5-
The alkyl complexes [Zr(Me2Si{η5-C9H5(CH2CH2CH2O)-3}-
1{η5-C5Me4})Me] (25) and [Zr{Me2Si(η5-C9H5R-3)-1(η5-
C5Me4)}Me2] [R = CH2CH2CH2OSiMe2tBu (26)] have been
synthesized by the reaction of the corresponding ansa-zir-
conocene derivative with the alkyl Grignard reagent. The
molecular structure of [(Zr{C9H6(CH2CH2CH2O)-1}Cl2)2(Zr–
O)] (17a), a subproduct in the formation of 17 has been deter-
mined by single-crystal X-ray diffraction studies. The inden-
ylzirconium complexes 17–24 have been immobilized on par-
tially dehydroxylated SiO2, and these supported systems
used to polymerize ethylene in the presence of methylalu-
minoxane. The catalytic activity of these compounds in both
homogeneous and heterogeneous polymerization is reported.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
C9H6R-1)2Cl2]
[R
=
CH2CH2CH2OSiMe3
(17),
CH2CH2CH2OCH2C6H5 (18), CH2CH2CH2OSiMe2tBu (19)],
rac-[Zr{Me2Si(η5-C9H5R-3)2-1}Cl2] [R = CH2CH2CH2OSiMe3
(20)],
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4)}Cl2]
[R
=
CH2CH2CH2OSiMe3 (21), CH2CH2CH2OCH2C6H5 (22),
CH2CH=CH2 (23), CH2CH2CH2OSiMe2tBu (24)] and
[Zr(Me2Si{η5-C9H5(CH2CH2CH2O)-3}-1{η5-C5Me4})Cl] (21a).
these systems have generally been applied in solution. How-
ever, for most industrial applications, it is desirable to em-
ploy these catalysts in gas-phase reactions in order to take
advantage of existing heterogeneous polymerization plant
infrastructure and thus avoiding the costly modification
needed for incorporating homogeneous systems. The single-
site catalysts therefore need to be immobilized on a solid
support in order to be active in gas-phase processes. Sup-
ported single-site catalysts are presently being used world-
wide in the annual production of 1 billionkg of polyethyl-
ene.
Introduction
On the basis of production data for 2000, 85–95 mil-
liontons of polyolefins (essentially homopolymers and co-
polymers of ethylene and propylene) were produced glob-
ally. The worldwide polypropylene capacity is approxi-
mately 34 milliontons, all of which is made with supported
catalysts. Sixty percent of polyethylene is made with sup-
ported catalysts, bringing the current market for polyolefins
produced on supported catalysts to a total of 65–70 mil-
liontonsperyear. This already impressive market is still in
full growth.[1,2]
The most common method of applying metallocene com-
pounds to heterogeneous polymerization is to support the
complexes on inorganic solids (in most cases silica gel).[5–7]
There are four different routes to supported catalysts: (i) Di-
rect adsorption of the metallocene on the carrier surface
leading to physisorption or chemisorption of the metallocene
(direct heterogenization). (ii) Direct adsorption of the metal-
locene/MAO adduct on the support. (iii) Initial adsorption
of MAO to the support followed by adsorption of the metal-
locene (indirect heterogenization). (iv) Covalent bonding be-
tween the ligands of the metallocene complex and the carrier
surface followed by activation with external MAO.
Metallocene/MAO catalytic systems are highly efficient
in producing polyolefins with defined microstructures and
narrow molecular weight distributions,[3,4] although to date,
[a] Departamento de Química Inorgánica, Orgánica y Bioquímica,
Facultad de Ciencias Químicas, Universidad de Castilla–La
Mancha, Campus Universitario,
13071 Ciudad Real, Spain
Fax: +34-926-295-318
E-mail: Antonio.Otero@uclm.es
[b] Departamento de Tecnología Química, Ambiental y de los Ma-
teriales, E.S.C.E.T., Universidad Rey Juan Carlos,
28933 Móstoles, Madrid, Spain
Fax: +34-91-488-8143
E-mail: S.Prashar@escet.urjc.es
[c] Centro Tecnológico de Repsol-YPF, Carretera de Extremadura,
Km. 18, 28931 Móstoles, Madrid, Spain
Several metallocene compounds containing functional
groups linked to cyclopentadienyl or indenyl ligands have
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Indenylzirconium Complexes as Catalysts in the Polymerization of Ethylene
FULL PAPER
been described.[8] One of the most promising methods to
obtain supported catalysts comes from the reaction between
the functional group of these metallocene complexes and
another functional group on the solid surface (route iv).
This option was applied to obtain some supported mono-
or bis(cyclopentadienyl) derivatives.[8b,9–11] When silica is
employed as a support, the surface hydroxy groups have
frequently been used for immobilizing the catalyst although
they can also cause some decomposition of the metallocene
complex. A strained siloxane group generated by dehydrox-
ylation has been shown to react with alkoxysilane
groups,[12] and this reactivity opens up the possibility of
supporting metallocene complexes with pendant alkoxy or
silyloxy groups on dehydroxylated silica.
In this paper we describe the synthesis and characteriza-
tion of a series of alkoxy- and silyloxy-substituted indene
compounds and their zirconium(iv) derivatives, and the
successful immobilization of the metallocene catalysts on
(2)
dehydroxylated silica.
1H and 13C NMR spectra of 17–19 exhibit two sets of
signals in a 1:1 ratio, corresponding to the presence of both
distereomers (see Exp. Sect.). The characterization was sim-
plified by the fact that the rac isomer has C2 symmetry
which makes the two indenyl rings equivalent. This is also
true for the meso isomer because of a mirror plane. In the
1H NMR spectra of 17–19, the protons in position 2 and 3
of the indenyl ligand showed only vicinal coupling and were
Results and Discussion
The preparation of the substituted indene precursors
C9H7R-3 [R
= CH2CH2CH2OSiMe3 (1), CH2CH2-
CH2OCH2C6H5 (2), CH2CH2CH2OSiMe2tBu (3)] was
achieved by the reaction of BrCH2CH2CH2OR (R = SiMe3,
CH2C6H5, SiMe2tBu) and indenyllithium [Equation (1)]. 1H
NMR spectroscopy showed the isolated product of 1–3 to
be virtually exclusively the 3-isomer (Ͼ98%). The 1-H sig-
nal for 1–3 was observed as a doublet, at δ Ϸ 3.2 ppm,
corresponding to two protons and 2-H as a triplet, at δ Ϸ
6.1 ppm, corresponding to one proton. In addition, 1–3
were characterized by electron impact mass spectrometry
(see Exp. Sect.).
1
thus observed as doublets in the H NMR spectra. It was
possible to assign the 2-H and 3-H signals to their respec-
tive diastereomers using NOE experiments. An interesting
observation is that for a sample containing a mixture of the
diastereomers, the “inner-pair” of 2-H and 3-H doublets
were assigned to the rac isomer, whereas for the meso iso-
mer the two doublets were the “outer-pair”. Because of the
complex nature caused by overlapping signals we were not
able to assign the multiplet systems observed for the pro-
tons of both the pendant chain and the indenyl C6 fragment
to their respective diasteromers.
During the preparation of 17, a minor product was, at
times, detected. We were able to isolate this subproduct,
[(Zr{C9H6(CH2CH2CH2O)-1}Cl2)2(Zr–O)] (17a), by frac-
tional recrystallization and characterize it by single-crystal
X-ray diffraction studies. The molecular structure and
atomic numbering scheme are shown in Figure 1. Selected
(1)
Compounds 1–3 were lithiated in the normal manner bond lengths and angles for 17a are given in Table 1.
with n-butyllithium giving the lithium derivatives The structure consists of a dinuclear complex of zirco-
Li(C9H6R-1)
[R
=
CH2CH2CH2OSiMe3
(9), nium. The metal atoms are bound to the indenyl ligand in
CH2CH2CH2OCH2C6H5 (10), CH2CH2CH2OSiMe2tBu an η5 mode, to the oxygen atoms of the pendant chains
(11)]. Compounds 9–11 were treated with ZrCl4 to yield the which bridge the two zirconium atoms, and to two chlorine
zirconocene complexes [Zr(η5-C9H6R-1)2Cl2] [R
=
atoms in a four-legged piano-stool conformation. The in-
CH2CH2CH2OSiMe3 (17), CH2CH2CH2OCH2Ph (18), denyl ligands are in a trans disposition.
CH2CH2CH2OSiMe2tBu (19)] [Equation (2)].
During the preparation of 9 it is possible that a second
The substituted indenyl ligands are prochiral and can lithiation occurs at the oxygen atom of the pendant chain
yield two diastereomers for the zirconocene complexes. A with the elimination of nBuSiMe3 to give Li[C9H6(CH2-
re,re or si,si attachment gives rise to the two enantiomers of CH2CH2OLi)-1]. If this subproduct is present when the re-
the rac diastereomer, whereas a re,si attachment leads to the action of 9 is carried out with ZrCl4, the presence of 17a
meso diastereomer.[13–15] The synthetic approach employed may be detected in the isolated product [Equation (3)].
in this study gave, as shown by NMR spectroscopy, a 1:1
The bridged bis(indene) compound, {Me2Si[(C9H6-
rac/meso isomer ratio.
R-3)-1]2} (4) (R = CH2CH2CH2OSiMe3), was prepared by
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A. Otero et al.
FULL PAPER
the reaction of 2 equiv. of BrCH2CH2CH2OSiMe3, with
Li2[Me2Si(C9H6)2-1] and isolated as a mixture of its meso
and rac isomers [Equation (4) ].
(4)
1H NMR spectroscopy showed the isolated product of 4
to be virtually exclusively (Ͼ98%) the symmetrically substi-
tuted indene isomer. In addition, 4 was characterized by
electron impact mass spectrometry (see Exp. Sect.). Double
deprotonation of 4 with2 equiv. of n-butyllithium gave the
corresponding dilithium derivative, Li2[Me2Si(C9H5R-3)2-1]
(12) (R = CH2CH2CH2OSiMe3), whose reaction with
Figure 1. Molecular structure and atom labelling scheme for
[(Zr{C9H6(CH2CH2CH2O)-1}Cl2)2(Zr–O)] (17a) with thermal el-
lipsoids at 30% probability.
Table 1. Selected bond lengths [Å] and angles [°] for 17a; Cent(1) [ZrCl4(THF)2] in toluene gave the ansa-indenyl complex,
[Zr{Me2Si(η5-C9H5R-3)2-1}Cl2] [R = CH2CH2CH2OSiMe3
is the centroid of C(11)–C(15); * refers to the average bond length
between Zr(1) and the carbon atoms of the C5 ring of the indenyl
(20)], exclusively as the rac isomer [Equation (5)]. Use of
moiety.
[ZrCl4(THF)2] as the zirconium source has been suggested
to modify the ratio of the diastereomers formed.[14] This
proposal is reinforced by the observation that the reaction
of 12 with ZrCl4 gave 20 as a 3:2 rac/meso mixture.
Zr(1)–Cent(1)
2.188
av Zr(1)–C[Cent(1)]*
Zr(1)–Cl(1)
Zr(1)–Cl(2)
2.486(9)
2.415(2)
2.447(2)
2.131(5)
Zr(1)–O(1)
Cent(1)–Zr(1)–O(1)
Cent(1)–Zr(1)–Cl(1)
Cent(1)–Zr(1)–Cl(2)
O(1)–Zr(1)–Cl(1)
O(1)–Zr(1)–Cl(2)
O(1)–Zr(1)–O(1)Ј
Cl(1)–Zr(1)–Cl(2)
Zr(1)–O(1)–C(3)
105.2
109.0
109.7
88.13(15)
143.8(2)
70.1(2)
88.90(3)
122.08(5)
(5)
Compound 20 was characterized by NMR spectroscopy.
The proton signal assignments were made according to a
1
procedure using H and 13C NMR correlated spectroscopy
(HETCOR) (see Exp. Sect.).
The preparation of the asymmetrically substituted ansa
ligand precursors [Me2Si(C9H6R-3)-1(C5HMe4)] [R
=
(3) CH2CH2CH2OSiMe3 (5), CH2CH2CH2OCH2C6H5 (6),
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Indenylzirconium Complexes as Catalysts in the Polymerization of Ethylene
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CH2CH2CH2OSiMe2tBu (8)] was achieved by the reaction
of Me2Si(C5Me4H)Cl and the corresponding lithium deriv-
atives 9–12 [Equation (6)].
(8)
When the lithiation reaction of 5 was carried out in the
presence of excess of n-butyllithium, the trilithium deriva-
tive, Li2{Me2Si[C9H5(CH2CH2CH2OLi)-3]-1(C5Me4)} (13a)
(6)
The reaction of 2 with an excess of nBuLi gave the lith- was formed through the elimination of the SiMe3 moiety
ium derivative Li[C9H6(CH2CH=CH2)-1] (10a) by a bimol- [Equation (9)]. Compound 13a was characterized by 1H
ecular elimination [Equation (7)]. The subsequent reaction NMR spectroscopy which confirmed the loss of the SiMe3
of 10a with Me2Si(C5Me4H)Cl yielded the asymmetrically group. The reaction of 13a with [ZrCl4(THF)2] gave the
substituted ansa ligand precursor, {Me2Si[C9H6- ansa-zirconocene
complex
[Zr(Me2Si{η5-C9H5-
(CH2CH=CH2)-3]-1(C5HMe4)} (7). 1H NMR spectroscopy (CH2CH2CH2O)-3}-1{η5-C5Me4})Cl(Zr–O)] (21a), where
showed the isolated products 5–8 to be virtually exclusively the oxygen atom of the pendant chain is directly bonded to
(Ͼ98%) the regioisomer where the SiMe2 ansa bridge is sit- the metal center [Equation (9)].
uated in position 1 in both the indenyl and cyclopentadienyl
moieties. In addition, 5–8 were characterized by electron
impact mass spectrometry (see Exp. Sect.).
(9)
(7)
Compounds 21–24 were characterized spectroscopically
1
Compounds 5–8 were then lithiated in the normal (see Exp. Sect.). The H NMR spectra show the lack of
way with n-butyllithium to give the corresponding dilithium symmetry in these chiral complexes, with four singlets being
derivatives,
Li2[Me2Si(C9H5R-3)-1(C5Me4)]
[R
=
observed for the cyclopentadienyl methyl groups, two sing-
CH2CH2CH2OSiMe3 (13), CH2CH2CH2OCH2C6H5 (14), lets for the ansa-bridge methyl groups, a singlet for the pro-
CH2CH=CH2 (15), CH2CH2CH2OSiMe2tBu (16)] whose ton of the indenyl C5 ring and four multiplets correspond-
reaction with [ZrCl4(THF)2] gave the ansa-zirconocene ing to the protons of the C6 ring of the indenyl moiety. In
complexes [Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4)}Cl2] [R = addition signals were observed for the pendant alkyl chain.
CH2CH2CH2OSiMe3 (21), CH2CH2CH2OCH2C6H5 (22),
The alkyl derivatives, [Zr(Me2Si{η5-C9H5(CH2CH2-
CH2CHCH2 (23), CH2CH2CH2OSiMe2tBu (24)] [Equation CH2O)-3}-1{η5-C5Me4})Me(Zr–O)] (25) and [Zr{Me2Si-
(8)].
(η5-C9H5R-3)-1(η5-C5Me4)}Me2] [R = CH2CH2CH2OSi-
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FULL PAPER
Me2tBu (26)] were prepared by the reaction of the Grignard terized by spectroscopic methods (see Exp. Sect.). The H
reagent MeMgBr with the corresponding mono- or dihalo NMR spectrum for 25 is similar to that recorded for its
ansa-zirconocene complexes 21a and 24, respectively [Equa- parent compound 21a but in addition a singlet for the me-
tions (10) and (11)]. Compounds 25 and 26 were charac- tal-bonded methyl group is observed. For 26, two signals,
assigned to the inequivalent metal-bonded methyl groups,
were recorded.
Figure 2 shows IR spectra corresponding to the reaction
between a toluene solution of [Zr{Me2Si(η5-C9H5R-3)-
1(η5-C5Me4)}Cl2] [R = CH2CH2CH2OSiMe2tBu (17)] and
the surface of a partially dehydroxilated silica, after removal
of solvent (see Exp. Sect.). The spectrum of silica preheated
at 773 K has a sharp band at 3747 cm–1 (assigned to iso-
lated OH groups) with a small broad shoulder at 3670 cm–1,
which can be attributed to silanols that are perturbed due
to interparticle contact[16] or to OH groups retained deep
(10)
within the pores[17] (Figure 2a). The magnitude of the sil-
anol number, which is independent of the origin and struc-
tural characteristics of amorphous silica, is considered to
be ca. 1.8 OH nm–2 for a silica dehydroxylated at 733 K.[18]
Bands at 1866 cm–1 and 1640 cm–1 are combination and
overtone bands of Si–O network bonds. After contact with
the metallocene solution and removal of the solvent (Fig-
ure 2b), new bands can be seen in the 2900 and 1400 cm–1
regions and these correspond to stretching and bending
modes of the cyclopentadienyl ligands. The OH groups that
were initially isolated are now partially perturbed, generat-
ing broad ν(OH) bands at lower frequencies due to an inter-
(11)
action with the cyclopentadienyl π-electron system through
Figure 2. (a) SiO2 dehydroxylated; (b) after grafting of 17; (c) after addition of MAO; (d) after contact with C2H4.
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Indenylzirconium Complexes as Catalysts in the Polymerization of Ethylene
FULL PAPER
hydrogen bonding.[19] The total intensity of the band due
The amount of supported metallocene was verified by
to the hydroxy groups was slightly modified after the ad- surface elemental analyses (Zr). The average results of se-
dition of an excess of metallocene solution, a situation also veral samples are summarized in Table 3.
observed by dos Santos and co-workers in the reaction be-
tween partially dehydroxylated silica and [Zr(η5-C5H4- similar or higher activities than their reference unsubsti-
nBu)2Cl2].[20]
tuted complexes. We could propose that, at least in these
Supported substituted complexes 17, 21, and 24 show
It is well established that the surface hydroxy group den- cases, more active surface species were obtained than those
sity on silica decreases with thermal activation as a result obtained from “conventional” unsubstituted complexes.
of an increase in the number of siloxane reactive bridges. Later complexes could be fixed on the surface by reaction
These strained groups can activate covalent bonds such as between Zr–Cl moieties and Si–OH acidic groups, to give
the Si–O bond in silicon ethers or N–H in ammonia.[21] strong Zr–O–Si bonding, hard to activate by MAO. In con-
We could propose a similar behavior with our silicon ether trast, the new complexes could be fixed by the reaction be-
metallocene derivatives. Similar results were found in the
reaction of [Zr(η5-C5H5)2Cl2] and dehydroxylated silica.[22]
Table 2. Homogeneous ethylene polymerization results for
The behavior of the catalyst system after the addition of
the MAO cocatalyst was also studied by FT-IR spec-
troscopy. The IR spectrum of a sample of 17-SiO2 treated
with MAO (Al/Zr = 100) is shown in Figure 2c. After ad-
dition of MAO at room temperature, the infrared band at-
tributed to the isolated silanol groups (at 3747 cm–1) disap-
peared completely, indicating a reaction between some basic
methyl groups of MAO and the acidic silanol moieties of
the silica. New infrared bands were observed in the ν(CH)
region (one intense band at 2940 cm–1 and three weak
bands at 2898, 2856 and 2838 cm–1). These signals were as-
17–24, [Zr(η5-C9H7)2Cl2], [Zr{Me2Si(η5-C9H6)2-1,1Ј}Cl2] and
[Zr{Me2Si(η5-C9H6)(η5-C5Me4)}Cl2] as references. Polymerization
conditions: 70 °C, 1.5 bar monomer pressure, 33 μmol Zr, 250 mL
toluene, tPol = 30 min.
Complex
Activity[a,c]
598
Activity[a,b]
[Zr(η5-C9H7)2Cl2]
352
21
[Zr(η5-C9H6R-1)2Cl2]
287
R = CH2CH2CH2OSiMe3 (17)
[Zr(η5-C9H6R-1)2Cl2]
388
145
R = CH2CH2CH2OCH2Ph (18)
[Zr(η5-C9H6R-1)2Cl2]
R = CH2CH2CH2OSiMe2tBu (19)
725
485
88
76
280
26
signed to stretching vibrations of the C–H bonds of the [Zr{Me2Si(η5-C9H6)2-1,1Ј}Cl2]
rac-[Zr{Me2Si(η5-C9H5R-3)2-1,1Ј}Cl2]
methyl groups in MAO. The grafted MAO should be able
R = CH2CH2CH2OSiMe3 (20)
to activate neighboring surface zirconocene molecules.[23]
[Zr{Me2Si(η5-C9H6)(η5-C5Me4)}Cl2]
558
212
180
114
The catalytic activity of 17-SiO2, after treatment with
MAO, towards ethylene polymerization was confirmed,
using FT-IR spectroscopy, by monitoring the appearance
of vibrations due to polyethylene in the regions 3000–2800
and 1500–1300 cm–1 (Figure 2d). Intense bands were ob-
served at 2970, 2850 and 1380 cm–1, which correspond to
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
R = CH2CH2CH2OSiMe3 (21)
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
R = CH2CH2CH2OCH2Ph (22)
831
787
525
115
387
259
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
R = CH2CHCH2 (23)
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
the ν(CH) and δ(CH) vibrations of polyethylene, respec- R = CH2CH2CH2OSiMe2tBu (24)
[a] In kg PE (molZr)h–1. [b] Al/Zr 100:1. [c] Al/Zr 500:1.
tively.
The polymerization of ethylene, under homogeneous
conditions and using 9–13 and 15–17 as the catalyst, with
metal/MAO catalyst ratios of 1:100 (in order to compare
with supported catalysts) or 1:500, has been carried out.
The polymerization experiments were carried out at 70 °C
and at an olefin pressure of 1.5 bar. The results of the ex-
periments are given in Table 2.
In all the cases, as expected, higher activities were found
for the 500:1 Al/Zr ratio. The highest catalytic activities
were recorded for 19, 22 and 23. In comparison, 20 gave a
notably low catalytic activity. The activities recorded for the
ansa-zirconocene complexes 22 and 23 are higher than their
unsubstituted analogue, [Zr{Me2Si(η5-C9H6)(η5-C5Me4)}-
Cl2], although 24 gave a similar value. Only compound 19
shows a higher value than its corresponding unsubstituted
reference complex.
Table 3. Heterogeneous ethylene polymerization results. Polymeri-
zation conditions: 70 °C, 1.5 bar monomer pressure, 250 mL tolu-
ene, 33 μmol Zr (approx. 300 mg of supported catalyst), Al/Zr
100:1, tPol = 30 min.
Complex
% Zr
0.60
0.81
Activity[a]
[Zr(η5-C9H7)2Cl2]
96
85
[Zr(η5-C9H6R-1)2Cl2]
R = CH2CH2CH2OSiMe3 (17)
[Zr(η5-C9H6R-1)2Cl2]
0.67
15
R = CH2CH2CH2OCH2Ph (18)
[Zr(η5-C9H6R-1)2Cl2]
0.72
0.84
0.85
0.94
0.76
32
104
19
R = CH2CH2CH2OSiMe2tBu (19)
[Zr{Me2Si(η5-C9H6)2-1,1Ј}Cl2]
rac-[Zr{Me2Si(η5-C9H5R-3)2-1,1Ј}Cl2]
R = CH2CH2CH2OSiMe3 (20)
[Zr{Me2Si(η5-C9H6)(η5-C5Me4)}Cl2]
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
R = CH2CH2CH2OSiMe3 (21)
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
R = CH2CH2CH2OCH2Ph (22)
[Zr{Me2Si(η5-C9H5R-3)-1(η5-C5Me4}Cl2]
R = CH2CH2CH2OSiMe2tBu (24)
97
The complexes 17–24 were supported on dehydroxylated
silica and, in the presence of MAO (Zr/Al 1:100), were em-
ployed as heterogeneous catalysts in the polymerization of
ethylene. The experiments were carried out at 70 °C and at
an olefin pressure of 1.5 bar and the results are given in
Table 3.
122
0.89
0.82
35
199
[a] In kg PE (molZr)h–1.
Eur. J. Inorg. Chem. 2005, 2924–2934
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2929

A. Otero et al.
FULL PAPER
Scheme 1. Proposed mechanism in the immobilization of the catalyst at the siloxane bridge and its subsequent activation with MAO.
Ethylene (Alphagaz), iBu3Al (TIBA, Aldrich) and MAO (EURE-
CENE, 10, Crompton) were used without further purification. H
tween the (CH2)2OR group and the siloxane bridges, to give
surface species, which remember the structure of the analo-
gous molecular complexes, to give more active catalysts
(Scheme 1).
In addition, it is noteworthy that supported complexes
17, 21 and 24 show similar or higher activities than their
corresponding homogeneous catalysts, with a 100:1 Al/Zr
ratio, showing both the advantages of supporting the com-
plexes (reduced MAO addition to activate), and the use of
pendant reactive chains (more active species).
1
and 13C spectra were recorded with Varian UNITY FT-300, Varian
GEMINY FT-400 and Varian INNOVA FT-500 spectrometers and
referenced to the residual deuterated solvent. Microanalyses were
carried out with a Perkin–Elmer 2400 microanalyzer. Mass spectro-
metric analyses were performed with a Vg Autospec instrument
or a Hewlett–Packard 5988A (m/z = 50–1000) (electron impact).
Infrared spectra were recorded with a Nicolet Magna 550-FT spec-
trophotometer using an infrared cell equipped with CaF2 or KBr
windows; this setup allowed in situ studies. A total of 32 scans were
typically accumulated for each spectrum (resolution 2 cm–1). The
samples consisted of ca. 20 mg of silica pressed into a self-sup-
ported disc of 1 cm diameter. The samples were dehydroxylated at
Conclusions
773 K for 16 h. Zirconocene grafting was performed using a 10–2
solution of the metallocene in toluene to give approximately 1%
m
We have carried out the synthesis of indenyl-containing
zirconium complexes with pendant chains capable of inter- Zr/SiO2. The samples were warmed at 333 K for 1 h, washed with
toluene and dried in vacuo at 343 K until no further change was
observed (sublimation of the excess complex was observed).
acting with dehydroxylated silica. We have successfully im-
mobilized the complexes on silica and tested the activity of
these supported catalysts in the polymerization of ethylene Preparation
of
C9H7(CH2CH2CH2OSiMe3)-3
(1):
BrCH2CH2CH2OSiMe3 (9.04 g, 43.04 mmol) was added to a solu-
tion of Li(C9H7) (5.25 g, 43.04 mmol) in Et2O at –78 °C. The reac-
tion mixture was allowed to warm to room temperature and stirred
for 15 h. The solvent was removed in vacuo and hexane (100 mL)
was added. The mixture was filtered and the solvent removed from
the filtrate under reduced pressure to yield the title compound as
a yellow oil. Compound 1 was purified by flash distillation (8.47 g,
80%). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 0.20 (s, 9 H,
OSiMe3), 1.65 and 2.08 (2 m, each 2 H, CH2CH2CH2O), 3.40 (m,
2 H, 1-H), 3.82 (t, J = 6.3 Hz, 2 H, CH2OSiMe3), 6.32 (m, 1 H, 2-
H), 7.26 and 7.33 (2 t, J = 7.3 Hz, each 1 H, 5-H and 8-H), 7.50
and 7.58 (2 d, J = 7.3 Hz, each 1 H, 6-H and 7-H) ppm. EI MS:
m/z (%) = 246 (30) [M+, C9H7(CH2CH2CH2OSiMe3)+], 130 (100)
[M+ – C9H7], 115 (24) [M+ – CH2CH2CH2OSiMe3].
and compared the results with the reference unsubstituted
complexes.
Experimental Section
General Remarks: All reactions were prepared using standard
Schlenk tube techniques under dry nitrogen. Solvents were distilled
from appropriate drying agents and degassed before use.
[ZrCl4(THF)2], ZrCl4, C9H8, Me2Si(C5HMe4)Cl, SiMe2Cl2,
BrCH2CH2CH2OH and (Me3Si)2NH were purchased from Aldrich
and used directly. Grace Davison XPO 2407 silica (200 m2/g, ac-
cording to data from supplier) was dehydroxylated under vacuum
(10–2 Torr) at 773 K for 16 h, cooled and stored under dry nitrogen.
2930
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 2924–2934

Indenylzirconium Complexes as Catalysts in the Polymerization of Ethylene
FULL PAPER
Preparation of C9H7(CH2CH2CH2OCH2Ph)-3 (2): The synthesis of and 2.56 (2 m, each 2 H, CH2CH2CH2O), 2.94 and 3.22 (2 m, each
2 was carried out in an identical manner to 1: Li(C9H7) (5.25 g, 1 H, C5HMe4 and 1-H), 3.49 (t, J = 6.3 Hz, 2 H, CH2OCH2Ph),
43.04 mmol) and BrCH2CH2CH2OCH2Ph (12.87 g, 43.04 mmol). 4.44 (m, 2 H, OCH2Ph), 6.13 (d, J = 1.6 Hz, 1 H, 2-H), 7.02–7.33
1
Yield (7.39 g, 65%). H NMR (400 MHz, CDCl3, 25 °C): δ = 2.43
(m, 9 H, 5-H–8-H and OCH2Ph) ppm. EI MS: m/z (%) = 442 (26)
and 2.76 (2 m, each 2 H, CH2CH2CH2O), 3.41 (m, 2 H, 1-H), 3.66 [M+, {Me2Si[C9H6(CH2CH2CH2OCH2Ph)](C5HMe4)}+], 321 (15)
(t, J = 6.3 Hz, 2 H, CH2OCH2Ph), 4.62 (s, 2 H, CH2OCH2Ph),
6.29 (m, 1 H, 2-H), 7.29–7.56 (m, 9 H, 5-H–8-H and OCH2Ph)
[M+ – C5HMe4], 179 (100) [M+ – C9H6CH2CH2CH2OCH2Ph].
Preparation of {Me2Si(C9H6(CH2CH=CH2)-3)-1(C5HMe4)} (7):
The synthesis of 7 was carried out in an identical manner
ppm.
EI
MS:
m/z
(%)
=
264
(27)
[M+,
C9H7(CH2CH2CH2OCH2Ph)+], 173 (100) [M+ – CH2Ph], 91 (40)
[M+ – C9H7CH2CH2CH2O].
to
5.
ClMe2Si(C5HMe4)
(3.97 g,
10.15 mmol)
and
Li[C9H6(CH2CH=CH2)-1] (10a) (1.64 g, 10.15 mmol). Yield 2.55 g,
1
Preparation of C9H7(CH2CH2CH2OSiMe2 tBu)-3 (3): The synthe-
sis of 3 was carried out in an identical manner to 1: Li(C9H7)
75%. H NMR (400 MHz, CDCl3, 25 °C): δ = –0.59 and –0.28 (2
s, each 3 H, SiMe2), 1.67, 1.72, 1.84 and 1.88 (4 s, each 3 H,
(5.25 g, 43.04 mmol) and BrCH2CH2CH2OSiMe2tBu (10.90 g, C5Me4), 2.88 and 3.20 (2 m, each 1 H, C5HMe4 and 1-H), 3.22 (m,
43.04 mmol). Yield (7.81 g, 63%). 1H NMR (400 MHz, CDCl3,
25 °C): δ = 0.18 (s, 6 H, OSiMe2tBu), 1.00 (s, 9 H, OSiMe2tBu),
2.01 and 2.68 (2 m, each 2 H, CH2CH2CH2O), 3.38 (m, 2 H, 1-H), 5-H–8-H) ppm. EI MS: m/z (%)
2 H, CH2CH=CH2), 5.06 (m, 2 H, CH2CH=CH2), 5.87 (m, 1 H,
CH2CH=CH2), 6.08 (d, J = 1.6 Hz, 1 H, 2-H), 7.00–7.27 (m, 4 H,
=
334 (12) [M+,
3.79 (t, J = 6.3 Hz, 2 H, CH2OSiMe2tBu), 6.28 (m, 1 H, 2-H), 7.58
and 7.65 (2 t, J = 7.3 Hz, each 1 H, 5-H and 8-H), 7.80 and 7.86
(2 d, J = 7.3 Hz, each 1 H, 6-H and 7-H) ppm. EI MS: m/z (%) =
{Me2Si[C9H6(CH2CH=CH2)](C5HMe4)}+], 213 (41) [M+
C5HMe4], 179 (100) [M+ – C9H6CH2CH=CH2].
–
Preparation
of
{Me2Si[C9H6(CH2CH2CH2OSiMe2tBu)-3]-
287 (7) [M+, C9H7(CH2CH2CH2OSiMe2tBu)+], 231 (100) [M+
tBu], 115 (45) [M+ – CH2CH2CH2OSiMe2tBu].
–
1(C5HMe4)} (8): The synthesis of 8 was carried out in an identical
manner to 5. ClMe2Si(C5HMe4) (4.11 g, 16.98 mmol) and
Li[C9H6(CH2CH2CH2OSiMe2tBu)-1] (5.10 g, 16.98 mmol). Yield
Preparation of {Me2Si([C9H6(CH2CH2CH2OSiMe3)-3]2-1,1Ј} (4):
BrCH2CH2CH2OSiMe3 (8.37 g, 38.14 mmol) was added to a solu-
tion of Li2[Me2Si(C9H6)2] (5.73 g, 19.07 mmol) in Et2O (50 mL)
at –78 °C. The mixture was allowed to warm to 25 °C and stirred
for 15 h. The solvent was removed in vacuo and hexane (100 mL)
was added. The mixture was filtered and the solvent removed from
the filtrate under reduced pressure to yield the title compound as
a yellow oil. Compound 4 was purified by flash distillation (6.28 g,
1
5.35 g, 60%. H NMR (400 MHz, CDCl3, 25 °C): δ = –0.58 and –
0.28 (2 s, each 3 H, SiMe2), –0.05 (s, 6 H, OSiMe2tBu), 0.80 (s, 9
H, OSiMe2tBu), 1.74, 1.78, 1.87 and 1.89 (4 s, each 3 H, C5Me4),
1.82 and 2.54 (2 m, each 2 H, CH2CH2CH2O), 2.93 and 3.39 (2 m,
each 1 H, C5HMe4 and 1-H), 3.60 (t, J = 6.3 Hz, 2 H, CH2OSi-
Me2tBu), 6.10 (d, J = 1.6 Hz, 1 H, 2-H), 7.05–7.31 (m, 4 H, 5-H–
8-H) ppm. EI MS: m/z (%)
=
467 (25) [M+,
1
{Me2Si[C9H6(CH2CH2CH2OSiMe2tBu)](C5HMe4)}+], 345 (35)
[M+ – C5HMe4], 179 (100) [M+ – C9H6CH2CH2CH2OSiMe2tBu].
60%). H NMR (400 MHz, CDCl3, 25 °C, two isomers): δ = 0.06
and 0.07 (2 s, each 18 H, 4×OSiMe3), –0.64 and –0.22 [2 s, each 3
H, SiMe2 (meso)], –0.49 [s, 6 H, SiMe2 (rac)], 1.75 and 2.50 (2 m,
each 8 H, 4×CH2CH2CH2O), 3.24 and 3.35 (2 d, J = 1.6 Hz, each
2 H, 4×1-H), 3.54 (m, 8 H, 4×CH2OSiMe3), 5.97 and 6.17 (2 d,
J = 1.6 Hz, each 2 H, 4×2-H), 7.14–7.46 (m, 16 H, 4×5-H, 6-H,
7-H and 8-H) ppm. EI MS: m/z (%) = 548 (17) [M+, Me2-
Preparation of Li[C9H6(CH2CH2CH2OSiMe3)-1] (9): nBuLi
(1.60 m in hexane) (15.22 mL, 24.35 mmol) was added to a solution
of 1 (5.00 g, 20.29 mmol) in Et2O (100 mL) at –78 °C. The mixture
was allowed to warm to 25 °C and stirred for 15 h. The solvent was
removed in vacuo to give a yellow solid which was washed with
hexane (2×50 mL) and dried under vacuum to yield a yellow solid
of the title complex (4.35 g, 85%). C15H21LiOSi (252.4): calcd. C
71.39, H 8.39; found C 71.03, H 8.30.
Si(C9H6CH2CH2CH2OSiMe3)2+],
230
(70)
[M+
–
C9H6CH2CH2CH2OSiMe3 – SiMe3], 130 (100) [M+ – Me2Si-
(C9H6CH2CH2CH2OSiMe3)(C9H6)].
Preparation of {Me2Si[C9H6(CH2CH2CH2OSiMe3)-3]-1(C5HMe4)}
(5): ClMe2Si(C5HMe4) (4.43 g, 20.8 mmol) in Et2O (50 mL) was
Preparation of Li[C9H6(CH2CH2CH2OCH2Ph)-1] (10): The syn-
thesis of 10 was carried out in an identical manner to 9: 2 (5.25 g,
19.86 mmol) and nBuLi (1.60 m in hexane) (14.90 mL,
23.83 mmol). Yield (3.49 g, 65%). 1H NMR (400 MHz, C6D6/[D8]-
THF, 25 °C): δ = 2.01 and 3.05 (2 m, each 2 H, CH2CH2CH2O),
3.45 (t, J = 6.3 Hz, 2 H, CH2OCH2Ph), 4.19 (s, 2 H, CH2OCH2Ph),
6.08 and 6.58 (2 m, each 1 H, 3-H and 2-H), 6.77–7.62 (m, 9 H, 5-
H–8-H and OCH2Ph) ppm. C19H19LiO (270.29): calcd. C 84.43, H
7.09; found C 84.63, H 7.07.
added to
a solution of Li[C9H6(CH2CH2CH2OSiMe3)-1] (9)
(5.25 g, 20.80 mmol) in Et2O (50 mL) at –78 °C. The reaction mix-
ture was allowed to warm to room temperature and stirred for 15 h.
The solvent was removed in vacuo and hexane (100 mL) was added
to the resulting yellow oil. The mixture was filtered and the solvent
removed from the filtrate under reduced pressure to yield the title
compound as a yellow oil (6.19 g, 70%). 1H NMR (400 MHz,
CDCl3, 25 °C): δ = –0.31 and –0.59 (2 s, each 3 H, SiMe2), 0.01 (s,
9 H, OSiMe3), 1.68, 1.73, 1.86 and 1.88 (4 s, each 3 H, C5Me4),
1.80 and 2.50 (2 m, each 2 H, CH2CH2CH2O), 2.91 and 3.39 (2 m,
each 1 H, C5HMe4 and 1-H), 3.56 (t, J = 6.3 Hz, 2 H, CH2OSi-
Me3), 6.10 (d, J = 1.6 Hz, 1 H, 2-H), 7.04–7.34 (m, 4 H, 5-H–8-H)
Preparation of Li[C9H6(CH2CH=CH2)-1] (10a): The synthesis of
10a was carried out in an identical manner to 9: 2 (5.25 g,
33.60 mmol) and nBuLi (1.60 m in hexane) (63.00 mL,
100.80 mmol). Yield (4.08 g, 75%).1H NMR (400 MHz, C6D6/[D8]-
THF, 25 °C): δ = 3.75 (m, 2 H, CH2CH=CH2), 4.92 (m, 2 H,
CH2CH=CH2), 6.20 (m, 1 H, CH2CHCH2), 6.13 and 6.60 (2 m,
each 1 H, 3-H and 2-H), 6.81–7.64 (m, 4 H, 5-H–8-H) ppm.
C12H11Li (162.2): calcd. C 88.88, H 6.84; found C 88.52, H 6.75.
ppm.
EI
MS:
m/z
(%)
=
424
(14)
[M+,
{Me2Si[C9H6(CH2CH2CH2OSiMe3)](C5HMe4)}+], 303 (24) [M+
C5HMe4], 179 (100) [M+ – C9H6CH2CH2CH2OSiMe3].
–
Preparation of {Me2Si[C9H6(CH2CH2CH2OCH2Ph)-3]-1(C5HMe4)}
(6): The synthesis of 6 was carried out in an identical manner to 5.
ClMe2Si(C5HMe4) (4.33 g, 20.30 mmol) and Li[C9H6(CH2CH2-
CH2OCH2Ph)-1] (5.12 g, 20.30 mmol). Yield 5.39 g, 60%. 1H
NMR (400 MHz, CDCl3, 25 °C): δ = –0.55 and –0.27 (2 s, each 3
H, SiMe2), 1.77, 1.89, 1.91 and 1.92 (4 s, each 3 H, C5Me4), 1.82
Preparation of Li[C9H6(CH2CH2CH2OSiMe2tBu)-1] (11): The syn-
thesis of 11 was carried out in an identical manner to 9: 3 (5.00 g,
17.33 mmol) and nBuLi (1.60 m in hexane) (13.00 mL,
20.80 mmol). Yield (3.67 g, 72%). C18H27LiOSi (294.4): calcd. C
73.43, H 9.24; found C 73.11, H 9.27.
Eur. J. Inorg. Chem. 2005, 2924–2934
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2931

A. Otero et al.
FULL PAPER
Preparation of Li2[Me2Si(C9H5R-3)2-1] (R = CH2CH2CH2OSiMe3)
CDCl3, 25 °C, two isomers): δ = 1.84–2.07 and 2.40–3.13 (2 m,
(12): The synthesis of 12 was carried out in an identical manner to
each
8
H, 4×CH2CH2CH2O), 3.36–3.62 (m,
8
H,
9: 4 (5.00 g, 9.11 mmol) and nBuLi (1.60 m in hexane) (13.67 mL, 4×CH2OCH2Ph), 4.03–4.58 (2 m, each 4 H, 4×OCH2Ph), 5.68 (d,
21.86 mmol). Yield (4.00 g, 78%). C32H46Li2O2Si3 (560.8): calcd. C
68.53, H 8.27; found C 68.21, H 8.24.
J = 3 Hz, 2 H, meso-3-H), 5.88 (d, J = 3 Hz, 2 H, rac-3-H), 6.10
(d, J = 3 Hz, 2 H, rac-2-H), 6.33 (d, J = 3 Hz, 2 H, meso-2-H),
7.14–7.68 (m, 36 H, 4×5-H–8-H and 4×OCH2Ph) ppm. 13C{1H}
Preparation
of
Li2[Me2Si(C9H5R-3)-1(C5Me4)]
(R
=
(75 MHz, CDCl3, 25 °C, two isomers):
δ = 24.4 and 24.7
CH2CH2CH2OSiMe3) (13): The synthesis of 13 was carried out in
an identical manner to 9: 5 (5.00 g, 11.77 mmol) and nBuLi (1.60 m
in hexane) (17.65 mL, 28.25 mmol). Yield (4.16 g, 81%).
C26H38Li2OSi2 (436.6): calcd. C 71.52, H 8.77; found C 71.33, H
8.71.
(CH2CH2CH2O), 29.9 (CH2CH2CH2O), 69.4 (CH2OCH2Ph), 72.9
(OCH2Ph), 99.1 (meso-C-3), 99.3 (rac-C-3), 120.4 (meso-C-2), 122.0
(rac-C-2), 117.9–144.4 (C-5–C-8 and OCH2Ph) (C-4, C-9 not ob-
served) ppm. EI MS: m/z (%)
=
388
688 (15) [M+,
Zr(C9H6CH2CH2CH2OCH2Ph)2Cl2+],
(73)
[M+
–
–
C9H6CH2CH2CH2OCH2Ph
–
Cl], 261 (100) [M+
Preparation of Li2{Me2Si[C9H5(CH2CH2CH2OLi)-3]-1(C5Me4)}
(13a): The synthesis of 13a was carried out in an identical manner
to 9: 5 (5.00 g, 11.77 mmol) and nBuLi (1.60 m in hexane)
(22.10 mL, 35.31 mmol). Yield (3.13 g, 72%).1H NMR (400 MHz,
C6D6/[D8]THF, 25 °C): δ = –0.30 and –0.58 (2 s, each 3 H, SiMe2),
1.68, 1.70, 1.82 and 1.86 (4 s, each 3 H, C5Me4), 1.76 and 2.59 (2
m, each 2 H, CH2CH2CH2O), 3.53 (t, J = 6.3 Hz, 2 H, CH2OSi-
Me3), 6.14 (s, 1 H, 2-H), 6.98 (m, 2 H, 5-H, 8-H), 7.29 (m, 2 H, 6-
H, 7-H) ppm. C23H29Li3OSi (370.40): calcd. C 74.58, H 7.89; found
C 74.12, H 7.92.
C9H6CH2CH2CH2OCH2Ph – 2 Cl – CH2Ph]. C38H38Cl2O2Zr
(688.84): calcd. C 66.26, H 5.56; found C 66.46, H 5.52.
Preparation of [Zr{η5-C9H6(CH2CH2CH2OSiMe2tBu)-1}2Cl2] (19):
The synthesis of 19 was carried out in identical manner to 17. ZrCl4
(0.99 g, 4.25 mmol) and Li[C9H6(CH2CH2CH2OSiMe2tBu)-1] (11)
(2.50 g, 8.49 mmol). Yield: 1.66 g, 53%. 1H NMR (300 MHz,
CDCl3, 25 °C, two isomers): δ = 0.03, 0.05 (2 s, each 12 H,
OSiMe2), 0.89, 0.91 (2 s, each 18 H, OSiMe2tBu), 1.57–1.87 and
2.62–3.04 (2 m, each 8 H, 4×CH2CH2CH2O), 3.57–3.71 (m, 8 H,
4×CH2OSiMe2tBu), 5.68 (d, J = 3 Hz, 2 H, meso-3-H), 5.84 (d, J
= 3 Hz, 2 H, rac-3-H), 6.07 (d, J = 3 Hz, 2 H, rac-2-H), 6.30 (d, J
= 3 Hz, H, meso-2-H), 7.16–7.63 (m, 16 H, 4×5-H–8-H) ppm.
13C{1H} (75 MHz, CDCl3, 25 °C, two isomers): δ = –5.2 (OSi-
Me2tBu), 24.1 and 24.4 (CH2CH2CH2O), 26.0 (OSiMe2tBu), 32.3
(CH2CH2CH2O), 62.3 (CH2OSiMe2tBu), 99.0 (meso-C-3), 99.2
Preparation
of
Li2[Me2Si(C9H5R-3)-1(C5Me4)]
(R
=
CH2CH2CH2OCH2Ph) (14): The synthesis of 14 was carried out
in an identical manner to 9: 6 (5.00 g, 10.57 mmol) and nBuLi
(1.60 m in hexane) (15.85 mL, 25.36 mmol). Yield (3.27 g, 68%).
C30H36Li2OSi (454.6): calcd. C 79.27, H 7.98; found C 79.34, H
7.96.
Preparation of Li2[Me2Si(C9H5R-3)-1(C5Me4)] (R = CH2CH=CH2) (rac-C-3), 120.39 (meso-C-2), 212.89 (rac-C-2), 120.5–139.3 (C-5–
(15): The synthesis of 14 was carried out in an identical manner to
9: 7 (5.00 g, 14.95 mmol) and nBuLi (1.60 m in hexane) (22.43 mL,
C-8) (C-4, C-9 not observed) ppm. EI MS: m/z (%) = 737 (15) [M+
Zr(C9H6CH2CH2CH2OSiMe2tBu)2Cl2+], 699 (14) [M+ – Cl], 261
35.88 mmol). Yield (4.14 g, 80%). C23H28Li2Si (346.4): calcd. C (100) [M+ – C9H6CH2CH2CH2OSiMe2tBu – Cl – SiMe2tBu].
79.74, H 8.15; found C 79.29, H 8.11.
C36H54Cl2O2Si2Zr (773.11): calcd. C 58.66, H 7.38; found C 58.39,
H 7.33.
Preparation of Li2[Me2Si(C9H5R-3)-1(C5Me4)]
(R
=
Preparation of rac-[Zr(Me2Si{η5-C9H5(CH2CH2CH2OSiMe3)-3}2-
1,1Ј)Cl2] (20): Toluene (100 mL) was added to a solid mixture of
[ZrCl4(THF)2] (2.06 g, 5.47 mmol) and Li2{Me2Si[C9H5-
(CH2CH2CH2OSiMe3)-3]2-1,1Ј} (12) (3.09 g, 5.47 mmol). The re-
sulting pale yellow solution was stirred for 15 h. The mixture was
filtered and the filtrate concentrated (10 mL) and cooled to –30 °C
to yield an orange solid of the title complex (1.16 g, 30%). 1H
NMR (500 MHz, CDCl3, 25 °C): δ = 0.09 (s, 18 H, 2×OSiMe3),
CH2CH2CH2OSiMe2tBu) (16): The synthesis of 13 was carried out
in an identical manner to 9: 8 (5.00 g, 10.71 mmol) and nBuLi
(1.60 m in hexane) (16.10 mL, 25.70 mmol). Yield (4.00 g, 78%).
C29H44Li2OSi2 (478.7): calcd. C 72.76, H 9.26; found C 72.54, H
9.17.
Preparation of [Zr{η5-C9H6(CH2CH2CH2OSiMe3)-1}2Cl2] (17):
Toluene (100 mL) was added to a solid mixture of ZrCl4 (1.15 g,
4.95 mmol) and Li[C9H6(CH2CH2CH2OSiMe3)-1] (9) (2.50 g,
9.90 mmol). The resulting pale yellow solution was stirred for 15 h.
The mixture was filtered and the solvent removed in vacuo to yield
a yellow oil of the title complex (1.87 g, 58%). 1H NMR (300 MHz,
CDCl3, 25 °C, two isomers): δ = 0.15, 0.18 (2 s, each 18 H,
1.12 (s,
6 H, SiMe2), 1.77 and 2.86 (2 m, each 4 H,
4×CH2CH2CH2O), 3.55 (m, 4 H, 2×CH2OSiMe3), 5.81 (s, 2 H,
2×2-H), 7.05 and 7.30 (2 t, J = 8.6 Hz, each 2 H, 2×6-H and 7-
H), 7.40 and 7.53 (2 d, J = 8.6 Hz, each 2 H, 2×5-H and 8-H)
ppm. 13C{1H} (75 MHz, CDCl3, 25 °C): δ = –1.2 (SiMe2), –0.2
(OSiMe3), 24.7, (CH2CH2CH2O), 32.9 (CH2CH2CH2O), 62.3
(CH2OSiMe3), 77.4 and 85.4 (C-1 and C-3) (C-4, C-9 not ob-
served), 117.2 (C-2), 124.5, 124.9, 126.7 and 126.8 (C-5–C-8) ppm.
C32H46Cl2O2SiZr (709.1): calcd. C 54.20, H 6.54; found C 54.35,
H 6.57.
4×OSiMe3), 1.60–2.00 and 2.60–3.15 (2 m, each
8 H,
4×CH2CH2CH2O), 3.45–3.80 (2 m, each 4 H, 4×CH2OSiMe3),
5.75 (d, J = 3 Hz, 2 H, meso-3-H), 5.88 (d, J = 3 Hz, 2 H, rac-3-
H), 6.13 (d, J = 3 Hz, 2 H, rac-2-H), 6.37 (d, J = 3 Hz, 2 H, meso-
2-H), 7.20–7.70 (m, 16 H, 4×5-H–8-H) ppm. 13C{1H} (75 MHz,
CDCl3, 25 °C, two isomers): δ = –0.3 (OSiMe3), 24.3 and 24.6
(CH2CH2CH2O), 30.5 (CH2CH2CH2O), 61.9 (CH2OSiMe3), 99.1
(meso-C-3), 99.29 (rac-C-3), 120.2 (meso-C-2), 121.8 (rac-C-2),
118.8–139.0 (C-5–C-8) (C-4, C-9 not observed) ppm. EI MS: m/z
(%) = 652 (13) [M+, Zr(C9H6CH2CH2CH2OSiMe3)2Cl2+], 297
(100) [M+ – C9H6CH2CH2CH2OSiMe3 – Cl]. C30H42Cl2O2Si2Zr
(652.95): calcd. C 55.18, H 6.48; found C 55.36, H 6.45.
Preparation of [Zr(Me2Si{η5-C9H5(CH2CH2CH2OSiMe3)-3}-1{η5-
C5Me4})Cl2] (21): Toluene (100 mL) was added to a solid mixture
of [ZrCl4(THF)2] (2.46 g, 6.53 mmol) and Li2{Me2Si[C9H5-
(CH2CH2CH2OSiMe3)-3]-1(C5Me4} (13) (2.57 g, 6.53 mmol). The
resulting pale yellow solution was stirred for 15 h. The mixture was
filtered and the filtrate concentrated to 10 mL and cooled to –30 °C
1
Preparation of [Zr{η5-C9H6(CH2CH2CH2OCH2Ph)-1}2Cl2] (18): to yield yellow solid of the title complex (0.76 g, 20%). H NMR
The synthesis of 18 was carried out in identical manner to 17. ZrCl4
(1.16 g, 4.96 mmol) and Li[C9H6(CH2CH2CH2OCH2Ph)-1] 10 (2 s, each 3 H, SiMe2), 1.90, 1.94, 1.95 and 2.00 (4 s, each 3 H,
(2.50 g, 9.91 mmol). Yield: 2.33 g, 68%. 1H NMR (300 MHz,
C5Me4), 1.98 and 3.00 (2 m, each 2 H, CH2CH2CH2O), 3.63 (m, 2
(500 MHz, CDCl3, 25 °C): δ = 0.08 (s, 9 H, OSiMe3), 0.94 and 1.17
2932
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 2924–2934

Indenylzirconium Complexes as Catalysts in the Polymerization of Ethylene
H, CH2OSiMe3), 5.59 (s, 1 H, 2-H), 7.06 and 7.33 (2 t, J = 8.6 Hz, tical manner to 21. Li2{Me2Si[C9H5(CH2CH2CH2OSiMe2tBu)-3]-
FULL PAPER
each 1 H, 6-H and 7-H), 7.45 and 7.57 (2 d, J = 8.6 Hz, each 1 H,
5-H and 8-H) ppm. 13C{1H} (125 MHz, CDCl3, 25 °C): δ = –0.5
(OSiMe3), 1.0 and 1.1 (SiMe2), 12.1, 12.6, 14.6, 15.3 (C5Me4), 24.9
1(C5HMe4)} (16) (2.56 g, 5.36 mmol) and [ZrCl4(THF)2] (2.02 g,
5.36 mmol). Yield 1.00 g, 30%. 1H NMR (500 MHz, CDCl3,
25 °C): δ = 0.08 (s, 6 H, OSiMe2tBu), 0.96 and 1.18 (2 s, each 3 H,
(CH2CH2CH2O), 32.7 (CH2CH2CH2O), 62.1 (CH2OSiMe3), 116.3 SiMe2), 0.90 (s, 9 H, OSiMe2tBu), 1.90, 1.93, 1.94 and 2.00 (4 s,
(C-2), 124.3 and 125.4 (C-5 and C-8), 126.1 and 126.3 (C-6 and C-
7), 84.3, 95.6, (C-1, C-3) (C-4, C-9 not observed), 124.0–135.3
each 3 H, C5Me4), 1.85 and 3.02 (2 m, each 2 H, CH2CH2CH2O),
3.64 (m, 2 H, CH2OSiMe2tBu), 5.61 (s, 1 H, 2-H), 7.05 and 7.33
(C5Me4) ppm. C26H38Cl2OSi2Zr (584.9): calcd. C 53.39, H 6.55; (2 t, J = 8.6 Hz, each 1 H, 6-H and 7-H), 7.48 and 7.60 (2 d, J =
found C 53.22, H 6.52.
Preparation of
[Zr(Me2Si{η5-C9H5(CH2CH2CH2O)-3}-1{η5-
8.6 Hz, each 1 H, 5-H and 8-H) ppm. 13C{1H} (125 MHz, CDCl3,
25 °C): δ = –5.0 (OSiMe2tBu), 1.4 and 1.7 (SiMe2), 12.4, 12.7, 14.9,
15.5 (C5Me4), 25.1 (CH2CH2CH2O), 26.2 and 18.6 (OSiMe2tBu),
33.1 (CH2CH2CH2O), 62.8 (CH2OSiMe2tBu), 116.7 (C-2), 124.6
and 125.7 (C-5 and C-8), 126.3 and 126.5 (C-6 and C-7), 84.6,
95.9 (C-1, C-3) (C-4, C-9 not observed), 119.2–138.1 (C5Me4) ppm.
C29H44Cl2OSi2Zr (627.0): calcd. C 55.56, H 7.07; found C 55.61,
H 7.08.
C5Me4})Cl(Zr–O)] (21a): The synthesis of 21a was carried out in
identical manner to 21. Li2{Me2Si[C9H5(CH2CH2CH2OSiMe3)-3]-
1(C5HMe4)} (13a) (2.42 g, 6.53 mmol) and [ZrCl4(THF)2] (2.46 g,
6.53 mmol). Yield: 0.29 g, 29%. 1H NMR (500 MHz, CDCl3,
25 °C): δ = 0.86 and 1.00 (2 s, each 3 H, SiMe2), 1.64, 1.82, 1.86
and 2.01 (4 s, each 3 H, C5Me4), 1.82 and 2.96 (2 m, each 2 H,
CH2CH2CH2O), 3.95 (m, 2 H, CH2O), 5.91 (s, 1 H, 2-H), 6.94 and
7.18 (2 t, J = 8.6 Hz, each 1 H, 6-H and 7-H), 7.34 and 7.41 (2 d,
J = 8.6 Hz, each 1 H, 5-H and 8-H) ppm. 13C{1H} (125 MHz,
CDCl3, 25 °C): δ = 0.0 and 0.6 (SiMe2), 9.8, 10.9, 13.2 and 13.3
(C5Me4), 24.5 (CH2CH2CH2O), 29.6 (CH2CH2CH2O), 68.9
(CH2O), 114.4 (C-2), 122.4 and 123.6 (C-5 and C-8), 124.2 and
124.3 (C-6 and C-7), 89.2, 98.4 (C-1, C-3) (C-4, C-9 not observed),
120.0–130.9 (C5Me4) ppm. C23H29ClOSiZr (476.2): calcd. C 58.01,
H 6.14; found C 58.31, H 6.12.
Preparation of [Zr(Me2Si{η5-C9H5(CH2CH2CH2OCH2Ph)-3}-
1{η5-C5Me4})Cl2] (22): The synthesis of 22 was carried out in iden-
tical manner to 21. Li2{Me2Si[C9H5(CH2CH2CH2OCH2Ph)-3]-
1(C5HMe4)} (14) (1.96 g, 5.65 mmol) and [ZrCl4(THF)2] (2.13 g,
5.65 mmol). Yield: 0.86 g, 26%. 1H NMR (500 MHz, CDCl3,
25 °C): δ = 0.89 and 1.09 (2 s, each 3 H, SiMe2), 1.80, 1.87, 1.90
and 1.94 (4 s, each 3 H, C5Me4), 1.89 and 2.98 (2 m, each 2 H,
CH2CH2CH2O), 3.44 (m, 2 H, CH2OCH2Ph), δA = 4.50, δB = 4.48
(AB, JAB = 12.3 Hz, 2 H, OCH2Ph), 5.50 (s, 1 H, 2-H), 6.98 and
7.25 (2 t, J = 8.6 Hz, each 1 H, 6-H and 7-H), 7.41 and 7.52 (2 d,
J = 8.6 Hz, each 1 H, 5-H and 8-H), 7.21–7.30 (m, 5 H, OCH2Ph)
ppm. 13C{1H} (125 MHz, CDCl3, 25 °C): δ = 1.1 and 1.4 (SiMe2),
12.3, 12.5, 14.7, 15.3 (C5Me4), 25.2 (CH2CH2CH2O), 29.9
(CH2CH2CH2O), 72.9 (CH2OCH2Ph), 77.4 (OCH2Ph), 116.4 (C-
2), 124.3 and 125.4 (C-5 and C-8), 126.2 and 126.3 (C-6 and C-7),
84.5, 95.6 (C-1, C-3) (C-4, C-9 not observed), 124.0–138.5 (C5Me4)
ppm. C30H36Cl2OSiZr (602.8): calcd. C 59.77, H 6.02; found C
59.51, H 5.95.
Preparation
of
[Zr(Me2Si{η5-C9H5(CH2CH2CH2O)-3}-1{η5-
C5Me4})Me(Zr–O)] (25): The synthesis of 25 was carried out in
identical manner to 26. MgMeBr (3 m in THF) (0.21 mL,
0.63 mmol) and 21a (0.30 g, 0.63 mmol). Yield: 0.24 g, 83%. 1H
NMR (500 MHz, C6D6, 25 °C): δ = –1.13 (s, 3 H, Zr–Me), 0.67
and 0.71 (2 s, each 3 H, SiMe2), 1.70, 1.84, 1.87 and 2.03 (4 s, each
3 H, C5Me4), 1.56 and 2.65 (2 m, each 2 H, CH2CH2CH2O), 3.89
(m, 2 H, CH2O), 5.97 (s, 1 H, 2-H), 6.91 and 7.14 (2 t, J = 8.6 Hz,
each 1 H, 6-H and 7-H), 7.32 and 7.36 (2 d, J = 8.6 Hz, each 1 H,
5-H and 8-H) ppm. 13C{1H} (125 MHz, C6D6, 25 °C): δ = –3.1
and –3.0 (SiMe2), 10.7, 11.8, 14.0 and 14.6 (C5Me4), 24.5 (Zr–Me),
25.9 (CH2CH2CH2O), 32.0 (CH2CH2CH2O), 68.3 (CH2O), 115.7
(C-2), 123.9 and 124.0 (C-5 and C-8), 126.1 and 126.2 (C-6 and C-
7), 82.20, 93.11 (C-1, C-3) (C-4, C-9 not observed), 117.66–128.74
(C5Me4) ppm. C24H32OSiZr (455.8): calcd. C 63.24, H 7.08; found
C 63.34, H 7.09.
Preparation of [Zr(Me2Si{η5-C9H5(CH2CH2CH2OSiMe2tBu)-3}-
1{η5-C5Me4})Me2] (26): MgMeBr (3 m in THF) (0.38 mL,
1.15 mmol) was added to a solution of 24 (0.30 g, 0.48 mmol) in
THF (50 mL) at –78 °C. The reaction mixture was allowed to warm
to room temperature and stirred for 4 h. The solvent was removed
in vacuo and hexane (25 mL) added. The mixture was filtered and
the solvent was removed from the filtrate in vacuo to yield the title
complex (0.24 g, 87%). 1H NMR (500 MHz, C6D6, 25 °C): δ =
–1.42 and –0.36 (2 s, each 3 H, Zr–Me), 0.04 (s, 6 H, OSiMe2tBu),
0.98 and 1.83 (2 s, each 3 H, SiMe2), 0.97 (s, 9 H, OSiMe2tBu),
1.61, 0.50, 0.67 and 1.74 (4 s, each 3 H, C5Me4), 1.80 and 3.00 (2
m, each 2 H, CH2CH2CH2O), 3.55 (m, 2 H, CH2OSiMe2tBu), 5.45
(s, 1 H, 2-H), 6.88 and 7.16 (2 t, J = 8.6 Hz, each 1 H, 6-H and 7-
H), 7.26 and 7.57 (2 d, J = 8.6 Hz, each 1 H, 5-H and 8-H) ppm.
13C{1H} (125 MHz, C6D6, 25 °C): δ = –5.0 (OSiMe2tBu), 11.5 and
25.5 (SiMe2), 1.0, 1.3, 14.9, 18.4 (C5Me4), 24.6 (CH2CH2CH2O),
25.5 and 21.4 (OSiMe2tBu), 33.7 (CH2CH2CH2O), 36.5 and 36.7
(Zr–Me), 62.3 (CH2OSiMe2tBu), 117.5 (C-2), 126.3 and 124.2 (C-
5 and C-8), 124.0 and 127.7 (C-6 and C-7), 80.11, 90.38 (C-1, C-3)
(C-4, C-9 not observed), 120.8–129.5 (C5Me4) ppm. C31H50OSi2Zr
(586.1): calcd. C 63.52, H 8.60; found C 63.68, H 8.64.
Preparation
of
[Zr(Me2Si{η5-C9H5(CH2CH=CH2)-3}-1{η5-
C5Me4})Cl2] (23): The synthesis of 23 was carried out in identical
manner to 21. Li2{Me2Si[C9H5(CH2CH=CH2)-3]-1(C5HMe4)} (15)
(2.59 g, 7.47 mmol) and [ZrCl4(THF)2] (2.82 g, 7.47 mmol). Yield:
0.85 g, 23%. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 0.93 and
1.17 (2 s, each 3 H, SiMe2), 1.84, 1.93, 1.94 and 2.00 (4 s, each 3
H, C5Me4), δA = 3.72, δAЈ = 3.68 (AAЈBBЈC, JAAЈ = 16.4 Hz, 2 H,
CH2CH=CH2), δB = 5.06, δBЈ = 5.09 (AAЈBBЈC, JBBЈ = 1.1, JBC
2.4, JBCЈ = 10 Hz, 2 H, CH2CH=CH2), 5.61 (s, 1 H, 2-H), δC
=
=
5.98 (AAЈBBЈC, JAC = JAЈC = 6.3 Hz, 1 H, CH2CH=CH2), 7.05
and 7.34 (2 t, J = 8.6 Hz, each 1 H, 6-H and 7-H), 7.47 and 7.57
(2 d, J = 8.6 Hz, each 1 H, 5-H and 8-H) ppm. 13C{1H} (125 MHz,
CDCl3, 25 °C): δ = 1.1 and 1.4 (SiMe2), 12.1, 12.5, 14.9, 15.3
(C5Me4), 33.4 (CH2CH=CH2), 116.3 (CH2CH=CH2), 136.0
(CH2CH=CH2), 117.1 (C-2), 124.3 and 125.5 (C-5 and C-8), 126.4
and 126.5 (C-6 and C-7), 84.5, 98.3 (C-1, C-3) (C-4, C-9 not ob-
served), 124.1–137.0 (C5Me4) ppm. C23H28Cl2SiZr (494.7): calcd.
C 55.84, H 5.71; found C 55.92, H 5.73.
X-ray
Crystal-Structure
Determination
of
[(Zr{C9H6-
(CH2CH2CH2O)-1}Cl2)2(Zr–O)] (17a): Intensity data were col-
lected with a NONIUS-MACH3 diffractometer equipped with a
graphite monochromator and a Mo-Kα radiation source (λ =
0.71073 Å) using an ω/2θ-scan technique. The final unit-cell
parameters were determined from 25 well-centered reflections and
refined by least-squares methods. Data were corrected for Lorentz
Preparation of [Zr(Me2Si{η5-C9H5(CH2CH2CH2OSiMe2tBu)-3}- and polarization effects but not for absorption. The structure was
1{η5-C5Me4})Cl2] (24): The synthesis of 24 was carried out in iden- solved by direct methods using the SHELXS computer program[24]
Eur. J. Inorg. Chem. 2005, 2924–2934
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2933

A. Otero et al.
FULL PAPER
and refined on F2 by full-matrix least squares (SHELXL-97).[25] All
non-hydrogen atoms were refined with anisotropic thermal param-
eters. The hydrogen atoms were included in calculated positions
and were refined with an overall isotropic temperature factor using
a riding model. Weights were optimized in the final cycles. Crystal-
lographic data are given in Table 4. CCDC-259059 contains the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
The reaction mixture was then quenched by the addition of acidi-
fied methanol. The polymer was collected by filtration, washed
with methanol and dried under vacuum at room temperature for
24 h.
Acknowledgments
We gratefully acknowledge financial support from the Ministerio
de Educación y Ciencia, Spain (grant nos. BQU2002-04638-C02-
01 and MAT2003-05345), the Junta de Comunidades de Castilla–
La Mancha (grant nos. PAC-02-003 PAI-02-010), and the Uni-
versidad Rey Juan Carlos (GVC-2004-165). P. C. and C. A.
acknowledge fellowships from REPSOL-YPF-UCLM (contracts
CTR-01-165 and CTR-00-084).
Table 4. Crystal data and structure refinement for 17a.
Emprical formula
Formula mass
T [K]
Crystal system
Space group
a [Å]
C12H12Cl2OZr
334.34
293(2)
orthorombic
Pbca
12.2690(10)
[1] A. Razavi, Metallocene catalyst technology and environment,
Clean Processes and Environment: the Catalytic Evolution,
Feluy, Belgium, 1999.
[2] D. J. B. Potter, L. Tattum, “Polypropylene Annual Review”,
Chem. Week 1999, 30, 4–11, supplement.
b [Å]
13.4540(10)
14.4320(10)
2382.2(3)
c [Å]
V [Å3]
Z
8
Dc [g cm–3]
1.864
1.345
[3] W. Kaminsky, Macromol. Chem. Phys. 1996, 197, 3907–3945.
[4] W. Kaminsky, M. Arndt, Adv. Polym. Sci. 1997, 127, 143–187.
[5] W. Kaminsky, D. Arrowsmith, C. Strübel, J. Polym. Sci., Part
A: Polym. Chem. 1999, 37, 2959–2968.
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Uzick, J. Polym. Sci., Part A: Polym. Chem. 1999, 37, 677–682.
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[8] See, for example: a) U. Siemeling, Chem. Rev. 2000, 100, 1495–
1526; b) P. Jutzi, T. Redeker, Eur. J. Inorg. Chem. 1998, 663–
674; c) R. Leino, P. Lehmus, A. Lehtonen, Eur. J. Inorg. Chem.
2004, 3201–3222; d) B. Y. Lee, J. S. Oh, J. Organomet. Chem.
1998, 552, 313–317.
[9] a) M. Galan-Fereres, T. Koch, E. Hey-Hawkins, M. S. Eisen,
J. Organomet. Chem. 1999, 580, 145; b) M. Antberg, H. Lüker,
L. Böhm, Eur. Pat. 293815, 1988.
[10] J. Sancho-Royo, G. Hidalgo-Llinas, A. Muñoz-Escalona-Laf-
uente, F. Martínez-Nuñez, C. Martín-Marcos, P. Lafuente-
Cañas, B. Peña-Garcia, Eur. Pat. Appl. 839836, 1998.
[11] B. Y. Lee, J. S. Oh, Macromolecules 2000, 33, 3194–3195.
[12] J. Blümel, J. Am. Chem. Soc. 1995, 117, 2112–2113.
[13] C. Krüger, F. Lutz, M. Nolte, G. Erker, M. Aulbac, J. Or-
ganomet. Chem. 1993, 452, 79.
[14] G. Erker, M. Aulbach, M. Knickmeier, D. Winbermühle, C.
Krüger, S. Werner, J. Am. Chem. Soc. 1993, 115, 4590–4601.
[15] W. Kaminsky, A. Laban, Appl. Catal., A 2001, 222, 47–61.
[16] B. A. Morrow, Stud. Surf. Sci. Catal. 1990, 57, 161.
[17] M. C. Haag, C. Krug, J. Dupont, G. Barrera, J. H. Z. dos San-
tos, T. Uozumi, T. Sano, K. Soga, J. Mol. Cat. A: Chem. 2001,
169, 275–281.
[18] P. Hoffman, E. Knoezinger, Surf. Sci. 1987, 188, 181.
[19] L. T. Zhuraviev, Colloids Surf., A 1993, 74, 71.
[20] J. H. Z. dos Santos, C. Drug, M. Barbosa, F. C. Stedile, J. Du-
pont, M. de Camargo, J. Mol. Catal. A: Chem. 1999, 139, 199–
207.
μ [mm–1]
F(000)
1328
0.3×0.2×0.1
2.65 to 24.27
0 Յ h Յ 14, 0 Յ k Յ 15, 0 Յ l
Crystal dimensions [mm]
θ range [°]
hkl ranges
Յ 17
2096
1084
0.965
No. of reflections measured
Reflections observed
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)][a]
R1 = 0.0522, wR2 = 0.1015
Largest difference peak [e/Å3] 0.509/–0.502
2
2 2
[a] R1 = Σ||Fo| – |Fc||/Σ|Fo|; wR2 = [Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]0.5
.
Homogeneous Polymerization Experiments: Polymerizations were
carried out in a 1-L glass reactor using toluene as a solvent
(250 mL). Catalysts (33 μmol) were treated with the appropriate
quantity of a solution of MAO in toluene (10% Al) for 15 min.
Toluene (230 mL), TIBA scavenger (2 mL) and activated catalyst
were introduced, in this order, into the reactor and the temperature
was fixed at 343 K. The nitrogen was removed and a continuous
flow of ethylene (1.5 bar) was introduced over 30 min. The reaction
mixture was then quenched by the addition of acidified methanol.
The polymer was collected by filtration, washed with methanol and
dried under vacuum at room temperature for 24 h.
Heterogeneous Polymerization Experiments: The supported cata-
lysts were prepared under an inert gas using Schlenk techniques
and a glove-box. A solution of the zirconocene complex (quantity
needed to obtain a theoretical level of 1% Zr/SiO2) in toluene
(30 mL) was added to partially dehydroxylated silica (1.00 g) and
the mixture was stirred at 333 K for 16 h. The slurries were filtered
through fritted discs and washed with toluene (10×20 mL). The
resultant solids were carefully washed with toluene and dried under
vacuum. Polymerizations were carried out in a 1-L glass reactor
using toluene as a solvent (250 mL). The supported catalysts (ap-
prox. 300 mg) were treated with the appropriate quantity of a solu-
tion of MAO in toluene (10% Al) for 15 min. The solvent and the
volatiles were removed in vacuo. Toluene (230 mL), TIBA scaven-
ger (2 mL) and activated catalyst in freshly distilled toluene
(20 mL) were introduced, in this order, into the reactor and the
temperature was fixed at 343 K. The nitrogen was removed and a
continuous flow of ethylene (1.5 bar) was introduced over 30 min.
[21] B. A. Morrow, I. A. Cody, J. Phys. Chem. 1976, 80, 1998.
[22] C. Alonso, A. Antiñolo, F. Carrillo-Hermosilla, P. Carrión, A.
Otero, E. Villaseñor, J. Sancho, J. Mol. Cat. A: Chem. 2004,
220, 286.
[23] J. C. W. Chien, Top. Catal. 1999, 7, 23–26.
[24] G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467.
[25] G. M. Sheldrick, Program for the Refinement of Crystal Struc-
tures from Diffraction Data, University of Göttingen,
Göttingen, Germany, 1997.
Received: February 24, 2005
Published Online: June 21, 2005
2934
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 2924–2934