ARTICLE

DOI: 10.1002/zaac.200801378
[AlCp
2
]

: Structure, Properties and Isobutene Polymerization

Michael Huber,
[a]
Alexander Kurek,
[b]
Ingo Krossing,
[c]
Rolf Mlhaupt,
[b]
and
Hansgeorg Schnckel
[a]
*
Dedicated to Professor Martin Jansen on the Occasion of His 65th Birthday
Keywords: Sandwich complexes; Aluminium; Cyclopentadienyl ligands; Polymerizations
Abstract. Reaction of the protonic ether compound [H(OEt
2
)
2
]-
[Al(OR
F
)
4
] (R
F
C(CF
3
)
3
) with AlCp
3
leads to the formation of
the [AlCp
2
]

-cation, which is stabilized by the weakly coordinating

[Al(OR
F
)
4
]

ion. Besides [AlCp

2
]

, the ion [AlCp

2
2Et
2
O]

, which
is stabilized by two ether molecules, is formed in an equilibrium
reaction. The so far unknown molecular structure of [AlCp
2
]

and
Introduction
About 15 years ago, we described the structure, bonding
and spectroscopic properties of [AlCp
2
*][Cp*AlCl
3
] (1) [1].
Later, this MgCp*
2
analogue, a sandwich compound, was
obtained by Shapiro et al. [2] and Jutzi et al. [3] on different
routes. The high stability of 1 and its poor ability to initiate
the cationic polymerization of isobutene is in contrast to
the performance of [AlCp
2
][MeB(C
6
F
5
)
3
] (2), observed by
Bochmann [4]. Compound 2 decomposes in CH
2
Cl
2
above
20 C. Below this temperature, 2 is a highly active poly-
merization initiator. Compound 2 has been obtained by
reaction of Cp
2
AlMe and B(C
6
F
5
)
3
and, because of its low
stability, has so far only been characterized in solution at
low temperatures. In order to explore the possibility of a
fine tuning of the stability and activity of the AlR
2

cation,
Shapiro et al. [2] varied the cyclopentadienyl rings to
Cp C
5
Me
4
H and determined the structure of
[Cp
2
Al][B(C
6
F
5
)
4
] (3). Furthermore, Shapiro et al. con-
vincingly demonstrated that 3 is a better initiator for the
* Prof. Dr. H. Schnoeckel
Fax: 49-721-6084854
E-Mail: hansgeorg.schnoeckel@chemie.uni-karlsruhe.de
[a] Institute for Inorganic Chemistry
University of Karlsruhe
Engesserstrasse 15
76131 Karlsruhe, Germany
[b] Freiburg Materials Research Center
Albert-Ludwigs-Universitt Freiburg
Stefan-Meier-Strae 21
79104 Freiburg i. Br., Germany
[c] Institute for Inorganic and Analytical Chemistry
Albert-Ludwigs-Universitt Freiburg
Albertstr. 21
79104 Freiburg i. Br., Germany
Supporting information for this article is available on the
WWW under www.zaac.wiley-vch.de or from the author.
Z. Anorg. Allg. Chem. 2009, 635, 17871793 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1787
the molecular structure of [AlCp
2
2Et
2
O]

are presented in this

work. To get insight in the formation and the equilibrium between
these two cations, quantum mechanical calculations were per-
formed. Moreover, the influence of counterions like [Al(OR
F
)
4
]

and [MeB(C
6
F
5
)
3
]

on the activity of [AlCp

2
]

to act as a polymer-
ization initiating agent for isobutene was investigated.
isobutene polymerization than [AlCp*
2
]

but worse than

[AlCp
2
]

in 2. Within this context, we want to answer two

remaining questions in this contribution:
1) The so far unknown structure of the [AlCp
2
]

ion sta-
bilized with the large WCA (weakly coordinating anion)
[Al(OR
F
)
4
]

(R
F
C(CF
3
)
3
) (2a) [5, 6] will be presented in
the crystalline state.
2) Furthermore, it will be shown that the [Al(OR
F
)
4
]

ion has weaker contacts to [AlCp

2
]

in 2a than
[MeB(C
6
F
5
)
3
]

in 2, inducing a higher activity of [AlCp

2
]

with respect to the polymerization of 2a in solution relative

to 2, since the [MeB(C
6
F
5
)
3
]

anion is better suited to form

a Cp
2
AlMeB(C
6
F
5
)
3
ion pair than [Al(OR
F
)
4
]

(similar
complexes were observed earlier, e.g. Cp
2
Y-Me-B(C
6
F
5
)
3
(Cp C
5
H
4
SiMe
3
) [7]. The high activity of 2a is finally
supported by quantum chemical calculations (Fluoride Ion
Affinity, FIA) [8, 9].
In order to understand the formation of
[AlCp
2
2Et
2
O]

, which was also prominent in the solution

and was isolated and structurally characterized as
[AlCp
2
2Et
2
O][Al(OR
F
)
4
] (2b), additional quantum chemi-
cal calculations were performed.
Results and Discussion
X-ray Structure Determination
In 2004, P. Jutzi et al. succeeded in synthesizing the
SiCp*

-ion an isoelectronic species to monomeric AlCp*

[10, 11] by reaction of SiCp*
2
and [C
5
Me
5
H
2
]

, both in
solution as in the solid state with [B(C
6
F
5
)
4
]

as counterion
[12] and later also by using [H(OEt
2
)
2
]

[Al(OR
F
)
4
]

(R
F

C(CF
3
)
3
) as a proton source [13]. For the synthesis of the
AlCp
2

-cation we similarly used the proton transfer reagent

[H(OEt
2
)
2
]

[Al(OR
F
)
4
]

. The compounds 2a and 2b were

M. Huber, A. Kurek, I. Krossing, R. Mlhaupt, H. Schnckel
ARTICLE
(1)
obtained by reaction of one equivalent of AlCp
3
and
[H(OEt
2
)
2
]

[Al(OR
F
)
4
]

at 30 C in dichloromethane
[Equation (1)]. At 28 C colorless crystals of 2a and 2b,
suitable for crystal structure analysis, were obtained from
the same reaction mixture. As found by analysis of several
batches, either 2a or 2b seem to be slightly preferred de-
pending on the reaction conditions (temperature, concen-
tration of the ether molecules, concentration of the ions).
Compound 2a crystallizes in the monoclinic space group
C2/c with one ion pair in the asymmetric unit (Figure 1,
Table 1). It forms a distorted CsCl packing with an average
cationcation distance of 10.9 A

; the average distance be-

tween the anions is 9.78 A

. The structure of the cationic

AlCp
2

-ion is given in Figure 2. In 2a the Cp rings are

5
-
bonded (stagger angle

30.55) [14] with an average

XAl distance of 178.9 pm (X is the distance between the
center of the Cp-rings and the aluminum atom) and an
XAlX angle of 179.5. The average AlX distances in
[AlCp*
2
]

(1) and [AlCp

2
]

(3) are 178 pm and 176.5 pm

respectively [1, 2]. Interestingly, the less demanding Cp-li-
gand induces a longer AlX distance (AlC distances)
than the bulkier Cp and Cp* ligands: the AlX distance
Figure 1. Section of the crystal structures of the compounds
[AlCp
2
][Al(OR
F
)
4
] (2a) and [AlCp
2
.2Et
2
O][Al(OR
F
)
4
] (2b).
Table 2. Selected bond lengths /pm for the compounds 1, 2a, 2b and 3.
1 av. [min./max] 3 av. [min./max] 2a av. [min./max] 2b av. [min./max]
d(AlX) 177.7(6) 176.5(4) 179.5
d(AlC
Cp
) 215.5(4) [213.7(5)/217(6)] 214.3(4) [210.5(5)/216.1(4)] 215.8(4) [212.8(4)/216.3(4)] 199.1(3) [199.6(3)/198.6(3)]
d(Cp
c
Cp
c
) 142.9(4) [141(4)/144(4)] 142.8(4) [142.3(3)/142.6(5)] 141.8(4) [140.6(3)/143.1(5)] 140.5(3) [134.9(2)/146(2)]
X denotes the center of the Cp-rings.
www.zaac.wiley-vch.de 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2009, 17871793 1788
Table 1. Selected crystallographic data of 2a und 2b.
2a 2b
Molecular formula C
26
H
10
Al
2
F
36
O
4
C
34
H
40
Al
2
F
36
O
6
T /K 150(2) 150(2)
M
r
/g mol
1
1124.26 1272.54
Crystal color colorless colorless
Crystal system monoclinic monoclinic
Space group C2/c P21/n
a /A

19.172(4) 29.964(4)
b /A

19.540(4) 9.5526(19)
c /A

19.405(4) 24.831(5)
/ 90 90
/ 98.02(3) 91.05(3)
/ 90 90
V /A
3
7401(3) 4734.7(16)
Z 8 4

calcd.
/g cm
3
2.023 1.785
/mm
1
0.299 0.246
F(000) 4396 2528
hkl-area 24 h 23, 22 h 22,
23 k 23, 10 k 10,
0 l 23 27 l 27
2 limits / 1.7325.89 4.0823.25
Measured refl. 13079 24105
Independent refl. 7120 6755
R
int
0.0581 0.0529
Observed refl. [F > 4(F)] 4688 4796
No. Parameter / Restraints 663/36 1034/211
Scan method
GooF 1.045 1.030
R
1
/ wR
2
[F > 4(F)] 0.0475/0.151 0.0992/0.2377
R
1
/ wR
2
(all data) 0.0839/0.1276 0.1291/0.2587
Max/min peaks /e A
3
0.279/0.386 0.646/0.469
in 2a is 0.9 pm (2.4 pm) longer than those in 1 (3). This
may be explained by a slight movement of the CH
3
-groups
of the Cp (Cp*)-rings in 1 (3) of about 1.8 (2.0) out of
the Cp-plane [1, 2]. It is in agreement with the more electron
rich nature of the latter two ligands that are better electron
donors, which leads to a closer contact between aluminum
and the substituted Cp rings. Accordingly, the average
AlC
cp
distance in AlCp
2

is with 215.8 pm in the same

range as those observed in [AlCp*
2
]

(215.5 pm) and

[AlCp
2
]

(214.3 pm). The CC distance in the Cp-rings is

141.8 pm ([AlCp*
2
]

: 142.9 pm, [AlCp

2
]

: 142.8 pm).
Selected bond lengths of 1, 2a, 2b and 3 are given in
Table 2.
In 2b the Cp rings are no longer
5
- bonded. Because of
the presence of two diethyl ether molecules in solution
[from the proton source H(OEt
2
)
2

], two of them are coor-

[AlCp
2
]

: Structure, Properties and Isobutene Polymerization

dinated to the aluminocenium cation, the Cp ligands are
now -bonded (
1
). Compound 2b crystallizes in the mono-
clinic space group P2
1
/n. A representation of the cation is
given in Figure 2. The central aluminum atom is tetra-
hedrally surrounded by two Cp and two diethyl ether mol-
ecules. The average AlC
Cp
distance is 199.1 pm and the
distances to the oxygen atoms of the ether molecules are
186.2 pm on average.
Figure 2. Representation of the AlCp
2

-cation: a) Sandwich com-

plex with
5
bonded Cp-rings (2a). b) staggered conformation of
the Cp-ligands (view along the XAlX axis) in 2a. c) Projection
of the AlCp
2

ion with two coordinating molecules of diethyl

ether (2b).
Equilibrium between [AlCp
2
]

(2a) and [AlCp

2
2Et
2
O]

(2b) in Solution
Although the compounds 2a and 2b could be charac-
terized by crystal structure analysis, it was difficult to ob-
tain NMR spectra of the different moieties in solution (
1
H,
13
C,
27
Al). Thus, only a signal at 35 ppm for the central
aluminum atom of the anion [Al(OR
F
)
4
]

could be detected
in the
27
Al-NMR spectrum of the reaction mixture at differ-
ent temperatures. Although other authors described signals
for [AlCp
2
]

[4], we could not observe any signals for the

cationic aluminum atoms in 2a and 2b. In the
1
H-NMR
spectrum of 2b, signals for the protons of the two coordin-
ating ether molecules [ 1.45(t), 4.13 (q)] and the C
5
H
5
-
rings [ 6,17(s)] could be detected. However, we did not
find any signal for the protons of the
5
-C
5
H
5
-rings in 2a,
which was expected at 7.05 [4]. Along these signals, we
observed some weak signals in the area of coordinated ether
molecules [ 4.28(q), 4.33(q) and 1.50(t) 1.51(t)] and
at 6.36, 6.38, 6.40 and 6.41, which were assigned to the
protons of the Cp-rings. To complement the NMR spectro-
scopic results, we investigated the equilibrium between 2a
and 2b in the gas phase [Equation (2)] with the help of
quantum chemical calculations.
(2)
Z. Anorg. Allg. Chem. 2009, 17871793 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de 1789
Quantum Chemical Calculations on the Relative Stability of
[AlCp
2
]

(2a) and [AlCp

2
2Et
2
O]

(2b)
The crystalline compounds 2a and 2b were obtained un-
der similar conditions; moreover, the NMR spectra indi-
cated the presence of intermediate ether solvates. Therefore,
we assumed that equilibrium exists in solution with com-
parable concentrations of 2a and 2b. To assure this con-
clusion, quantum chemical calculations were performed
[1519]. These calculations result in a
r
H
0
gain of
97.2 kJ mol
1
(0 K) by the coordination of two diethyl
ether molecules. The change of the Gibbs energy
r
G
0
(gas)
at 248 and 298 K was additionally calculated to estimate
the position of the equilibrium (Table 2). Accordingly the
position of equilibrium [Equation (2)] is slightly on the side
of 2b (
r
G
0
(gas)
10.7 kJ mol
1
) at 248 K and on the
side of 2a at 298 K (
r
G
0
(gas)
3.8 kJ mol
1
). The calcu-
lated values of the Gibbs energy and the estimated equilib-
rium position suggested that signals of the protons of 2a
should be visible in the
1
H-NMR spectra. However, the
measured NMR spectra showed that the cations in 2a and
2b are only the extremes of an equilibrium that contains
further, unknown entries. Thus, the short lifetime of all
species in this dynamic equilibrium and probably the fluctu-
ation of their structure should play an important role
[2022]. Such processes are serious in
27
Al-NMR spec-
troscopy, because the usually broad signals in most cases
could be further broadened until disappearing [23]. The
chemical environment of the central aluminum atoms in the
considered equilibrium changes very fast at the time scale
of NMR spectroscopic measurements. Because of the nu-
merous dynamic processes, which are present in the ex-
tended equilibrium, an extreme broadening of the signals
in the
27
Al-NMR spectra results, so that they cannot be
detected anymore. In one borderline case there is a
5
coor-
dination of the Cp ligands (2a), in the other case their hap-
ticity is one and the central aluminum atom is additionally
coordinated by two diethyl ether molecules (2b). The
change from one state to the other should proceed through
intermediates, in which only one or two ether molecules are
coordinated, one of which is more coordinated than the
other. The hapticity in these fluctuating intermediates prob-
ably varies between 5 and 1. These considerations are in
line with the observed signals in the
1
H-NMR spectra, in
which no signal is detected for the protons of the undis-
turbed [AlCp
2
]

cation ( 7.05). Instead, in addition to

the signals of [AlCp
2
2Et
2
O]

[ 1.45(t), 4.13 (q), 6,17(s)],

we could observe some intermediate signals in the range of
Cp ligands [ 6.36(s), 6.38(s),6.40(s), 6.41(s)] and in the
range that is typical for coordinating ether molecules [
4.28(q), 4.33(q) and 1.50(t) 1.51(t)]. The last mentioned
signals are broadening while rising the temperature. In sum-
mary, these observations suggest dynamic processes in a dy-
namic, temperature dependent equilibrium [Equation (2)].
M. Huber, A. Kurek, I. Krossing, R. Mlhaupt, H. Schnckel
ARTICLE
Calculations of the Equilibrium between 2a and 2b
Including the Crystalline Compounds
These considerations were made to obtain some infor-
mation about the concentration of the [AlCp
2
]

ion, which
is necessary for the estimation of its initiating activity for
the polymerization of isobutene. Only with this background
we were able to compare our results of the polymerization
experiments (see below) with those obtained by Bochmann
et al [4]. Therefore, some difficulties were expected because
of the presence of diethyl ether in the reaction mixture,
since, in regard to the above mentioned considerations,
compound 2b should be favored. However, its activity as an
initiator should be negligible compared to that of the ether
free aluminocenium cation in 2a, because of the lower
Lewis acidity of 2b (see below). Nevertheless, in order to
force the equilibrium [Equation (2)] on the side of 2a, the
solvents of the reaction mixture (dichloromethane and es-
pecially diethyl ether with its high volatility) were com-
pletely removed within half an hour after the reagents were
combined. Therefore, the residue used for the polymeriz-
ation should mainly contain 2a as a result of the equilib-
rium [Equation (2)]. The complete removal of ether was
controlled by
1
H-NMR measurements. The solid obtained
finally, i.e. the catalyst, was stored at 78 C prior to use
in order to avoid the expected decomposition of [AlCp
2
]

in CH
2
Cl
2
[4].
In order to understand the influence of the crystalline
compounds 2a and 2b on the position of the equilibrium
[Equation (2)], we also worked out a BornFajansHaber
cycle for the heterogeneous equilibrium between 2a and 2b
in the gas phase [24] and in solid state (Figure 3). With the
(3)
Figure 3. Born Fajans Haber cycle for the formation of 2a and 2b as well as in the gas phase as a model for the solution, and in the
solid state. All energies are Gibbs energies at 298 K in kJ mol
1
. The Gibbs energies for the gas phase (
r
G
0
(gas)
) were calculated using
the program package Turbomole (BP86/SV(P)). To calculate G
0
(solv)
experimental data were used [31].
Table 3. Calculated Gibbs energies for the Born Fajans Haber cycle in Figure 3.
Gas Phase
r
H
(g)
/kJ mol
1
T
r
S
(g)
/kJ mol
1

r
G
(g)
/kJ mol
1
T 248.15 K 88.4 77.7 10.7
T 298.15 K 88.6 91.4 3.8
Solid State G
latt,1
/kJ mol
1
G
latt,2
/kJ mol
1
G
solv
/kJ mol
1
G
(s)
/kJ mol
1
T 248.15 K 200.8 181.8 4.5 3.8
T 298.15 K 200.8 181.8 9 13.8
www.zaac.wiley-vch.de 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2009, 17871793 1790
experimental X-ray crystal diffraction data, it is possible to
estimate the lattice enthalpy and entropy of the solids at
298 K (see Experimental Section) [2530]. The calculated
Gibbs energies, which were gained by crystallization of 2a
and 2b, are given in Table 3. Thus, the crystallization of 2a
is about 13.8 kJ mol
1
exergonic (
r
G
0
(s)
) at 298 K com-
pared to 2b (Figure 3) (The equilibrium in the gas phase is
only slightly on the side of 2a at that temperature). There-
fore, its crystallization should be preferred. On the other
hand because of the entropy, the crystalline state of 2b is
favored at low temperatures, e.g. 248 K.
Overall, the calculations are in line with the experiments:
crystalline 2a, which is necessary for best polymerization
activity, is favored at higher temperatures and by lower
ether concentration. However, these conditions, especially
the higher temperatures, limit the crystallization of 2a
through its decomposition above 0 C.
Orientating Investigations for the Isobutene Polymerization
In 1996, Bochmann et al. [4] performed the polymeriz-
ation of isobutene (IB) [Equation (3)] with [AlCp
2
]

(coun-
terion: [MeB(C
6
F
5
)
3
]

) and detected its high initiating

activity. Compared to [MeB(C
6
F
5
)
3
]

, the homoleptic
borate [B(C
6
F
5
)
4
]

is known to be a better anion and to be

similar in coordination quality to [Al(OR
F
)
4
]

[7]. Thus, the

interactions between dissolved AlCp
2

and the counterion

used here, should be weaker than those employing
[MeB(C
6
F
5
)
3
]

. Consequently, it is expected that the alumi-

nocenium cation with [Al(OR
F
)
4
]

as anion has a higher

activity relative to [AlCp
2
]

[MeB(C
6
F
5
)
3
]

[4]. Therefore,
[AlCp
2
]

: Structure, Properties and Isobutene Polymerization

Table 4. Results of the isobutene polymerization compared with
the experimental results (in parentheses) obtained by other authors
[4]. The experiments at 70 C cannot be compared, because of
the poor solubility of 2a at this temperature [33].
t 10 min 50 C 30 C
Yield /g 0.58 (0.18) 1.56 (0.08)
M
w
/10
4
g mol
1
6.1 (62) 1.9 (32)
PDI 2.0 (2.0) 1.7 (1.8)
t 120 min 50 C* 30 C
Yield /g 6.51 5.74
M
w
/10
4
g mol
1
6.1 2.1
PDI 6.0 3.7
* At 50 C the polymerization had to be interrupted because of
the high viscosity of the reaction mixture.
we performed isobutene polymerizations under similar con-
ditions as those run by Bochmann et al [4].
Comparing the polymerization results (Table 4), our
experiments show a lower weight-average molecular weight
M
w
and a polydispersity of the polymers, which is in the
same range at the same temperatures. The higher yield of
polyisobutene in our experiments is remarkable. When the
experiments were conducted over a period of two hours at
50 and 30 C, they had to be interrupted because of the
high viscosity of the reaction mixture [32]. The here pre-
sented polymerization experiments suggest a higher activity
of [AlCp
2
]

, which is a result of the weaker interaction be-

tween [AlCp
2
]

and [Al(OR
F
)
4
]

relative to the experiments

performed by Bochmann et al [4].
Comparison of the Isobutene-Polymerization of [AlCp*
2
]

(1), [AlCp
2
]

(4) [AlCp
2
]

(2a) and [AlCp

2
2Et
2
O]

(2b)
Furthermore, we attempted to scale the different activi-
ties of the cations [AlCp*
2
]

(1), [AlCp
2
]

(4) [AlCp
2
]

(2a) and [AlCp

2
2Et
2
O]

(2b) [34]. Shapiro et al. already

concluded that the relative activity of the cations rises from
1 to 2a, and related this increase to the lower steric demand
of the Cp rings and the hence resulting better access of IB
to the positively charged aluminum atoms [2].
Generally, the activity should not only, but strongly de-
pend on the Lewis acidity of the cationic species. Therefore,
one should expect that the higher the Lewis acidity, the
higher is the activity according to IB polymerization. A
quantitative measure for the Lewis acidity is the fluoride
ion affinity (FIA) [7, 8, 35]. The calculated values for 1, 2a,
2b and 3 are given in Table 5. Comparing these values
it is possible to list the Lewis acidities and the activity for
the polymerization of IB in the following sequence:
[AlCp
2
]

>> [AlCp
2
]

[AlCp*
2
]

>>> [AlCp
2
2Et
2
O]

.
Compound 2a, which was used for the polymerization
experiments, contains only traces of 2b. The large difference
in the FIA between 2a and 2b and also the fact, that the
FIA of 2b is lower than that of 1 (the polymerization of
isobutene does not start with 1 as initiator even at 20 C)
are strong hints, that any 2b still present in samples of 2a is
Z. Anorg. Allg. Chem. 2009, 17871793 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de 1791
Table 5. Calculated FIA of the compounds 1, 2a, 2b and 3. The
reported pF

values are only to order the cations in a quantitative

scale for Lewis acidities given by Christe and Dixon [8].
Lewis Acid FIA /kJ mol
1
pF

[AlCp
2
]

773 18.34
[Al(Cp)
2
]

687 16.40
[AlCp*
2
]

686 16.38
[AlCp
2
2Et
2
O]

311 7.42
expected to be virtually inactive. On the other hand it would
be possible that traces of protonated ether [H(OEt
2
)
2
]

,
used for the synthesis of 2a, induce a too high activity of
the initiator 2a. This scenario is very unlikely, because al-
ready very low concentrations of H(OEt
2
)
2

[Al(OR
F
)
4
]

are very potent IB polymerization initiators. Thus, 5 mg of

H(OEt
2
)
2

[Al(OR
F
)
4
]

are sufficient to polymerize 12 g

(20 mL) of IB at 60 C in one second in quantitative yield
[36, 37]. In our case, 2a did not initiate polymerization at
70 and 60 C. If traces of H(OEt
2
)
2

[Al(OR
F
)
4
]

in 2a
would be the reason for the initiation of IB polymerization,
the polymerization should have also started at these lower
temperatures. Thus, our IB polymerization is due to the ac-
tions of the aluminocenium cation and not induced by
traces of proton sources like H(OEt
2
)
2

[Al(OR
F
)
4
]

.
Summary
The reaction of AlCp
3
with [H(OEt
2
)
2
]

[Al(OR
F
)
4
]

re-
sults in Cp protonation and formation of the aluminocen-
ium cation [AlCp
2
]

, which is stabilized both in solution

and in the solid state by the weakly coordinating anion
[Al(OR
F
)
4
]

(R
F
C(CF
3
)
3
). We crystallized two com-
pounds [AlCp
2
]

[Al(OR
F
)
4
]

(2a) and as the main product

the ether stabilized species [AlCp
2
2Et
2
O)]

[Al(OR
F
)
4
]

(2b). With the help of quantum chemical calculations we

were able to explain the dynamic and temperature depen-
dent equilibrium in solution between 2a and 2b, in which
intermediates exhibiting fluctuating structures should play
an essential role. Therefore, we could detect only signals of
2b and other intermediates but not those of 2a by NMR
spectroscopy in solution. In order to explain the preferred
crystallization of 2b, BornFajansHaber cycle consider-
ations showed that 2b is slightly favored at low tempera-
tures. Furthermore, these calculations confirmed the exper-
imentally observed difficulties during the crystallization of
2a: in the heterogeneous equilibrium the donor free
[AlCp
2
]

2a is preferred near room temperature. However,

2a decomposes far below this temperature; under the con-
ditions described here as well as under those in the experi-
ments of Bochmann et al [4]. Therefore, it is not surprising
that the crystallization of 2a requires green fingers be-
cause its formation is restricted to very sharp experimental
conditions.
Furthermore, we investigated the IB polymerization ac-
tivity of [AlCp
2
]

. The results were compared qualitatively

with those made by Bochmann et al. The higher activity of
our aluminocenium cation is most likely caused by the
M. Huber, A. Kurek, I. Krossing, R. Mlhaupt, H. Schnckel
ARTICLE
less coordinating anion [Al(OR
F
)
4
]

relative to the earlier

used [Me(B(C
6
F
5
)
3
]

. Hence, in our experiments the ac-

tivity of the [AlCp
2
]

cation in solution is enhanced due

to the weaker interactions with the counterion. The Lewis
acidities and therefore the activity of 1, 2a, 2b and 4,
with respect to IB polymerization were quantitatively com-
pared for the first time by calculating their FIA values
([AlCp
2
]

>> [AlCp
2
]

[AlCp*
2
]

>>> [AlCp
2
2Et
2
O]

).
Experimental Section
All manipulations were carried out under nitrogen with solvents
that were pre-dried by using standard procedures. The reagents
AlCp
3
and H(OEt
2
)
2

[Al(OR
F
)
4
]

were synthesized as described in

literature [21, 38].
The NMR spectra were recorded with a Bruker AVANCE 400 in
CD
2
Cl
2
at 30 C and at room temperature. The chemical shifts
are given in ppm. They refer to C
6
D
5
H ( 7.16,
1
H), C
6
D
6
and
the external standards 0.5 [Al(H
2
O)
6
]
3
( 0,
27
Al) and Cl
3
CF
( 0,
19
F).
Preparation of [AlCp
2
][Al(OR
F
)
4
] 2a and
[AlCp
2
2Et
2
O][Al(OR
F
)
4
] (2b)
[H(OEt
2
)
2
][Al(OR
F
)
4
] (2.14 g, 2.0 mmol) was dissolved in CH
2
Cl
2
(10 mL) and afterwards combined at 78 C with AlCp
3
(445 mg,
2.0 mmol) dissolved in CH
2
Cl
2
(5 mL). Thereby the color of the
reaction mixture changed from colorless to slight yellow. After
magnetic stirring for one hour at 78 C, the reaction mixture was
warmed to 30 C and it was kept for two hours at this tempera-
ture. Afterwards, the reaction mixture was concentrated and stored
at 28 C. After several days, colorless crystals of 2a and 2b were
obtained, which were suitable for crystal structure analysis. Crystals
of 2a are preferred in more concentrated solution after removal of
the solvents in vacuo. In the
1
H-NMR spectra, only compound 2b
is observed (see Supporting information). Yield (sum of 2a and 2b):
1.249 g, 0.99 mmol, 41 %.
1
H NMR (400 MHz, 30 C), CD
2
Cl
2
:
1.467 (t,
3
J(H,H) 7,1 Hz, 12 H), 4.134 (q,
3
J
H,H
7,1 Hz,
8 H), 6,17 (s, 10 H).
13
C NMR (100 MHz, 30 C), CD
2
Cl
2
:
13.92 (s), 70.54 (s), 114.3 (s), 121,54 (q,
1
J
C,F
291.5 Hz).
19
F
NMR (376 MHz, 30 C), CD
2
Cl
2
: 75.47 (s).
27
Al NMR
(104 MHz, 30 C), CD
2
Cl
2
: 35 (s) ppm.
Preparation of the Catalyst (2a)
[H(OEt
2
)
2
][Al(OR
F
)
4
] (3.21 g, 2.5 mmol) was dissolved in CH
2
Cl
2
(15 mL) and afterwards combined at 78 C with AlCp
3
(668 mg,
2.5 mmol) dissolved in CH
2
Cl
2
(10 mL). Thereby the color of the
reaction mixture changed from colorless to slight yellow. After
magnetic stirring for five minutes at 78 C, the reaction mixture
was warmed to 30 C. Afterwards, the solvent was completely
removed within 30 minutes and a colorless powder of 2a was ob-
tained. The catalyst was stored at 78 C prior to the polymeriz-
ation procedure.
13
C NMR (100 MHz, 30 C), CD
2
Cl
2
: 13.9
(s), 70.5 (s), 114.3 (s), 121,5 (q,
1
J
C,F
291.5 Hz).
27
Al NMR
(104 MHz, 30 C), CD
2
Cl
2
: 35 (s).
Polymerization Procedure
Isobutene was dried with triisobutylaluminum and recondensed
prior to use. All polymerizations were carried out in standard
www.zaac.wiley-vch.de 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2009, 17871793 1792
Schlenk tubes. For the 10 minutes polymerization procedure, isobu-
tene (10 mL) was condensed into the reaction tubes and allowed to
equilibrate at the appropriate temperature. Compound 2a
(50 mol) was dissolved in CH
2
Cl
2
(5 mL) at 20 C. After cooling
to the appropriate temperature, this solution was added to the rig-
orously stirred isobutene. The reaction was quenched after 10 mi-
nutes with methanol (0.5 mL). Finally, the solvents were evaporated
in an oil-pump vacuum and the remaining polymer was dried in
vacuo until constant weight. By using a polymerization time of 120
minutes, 2a (58 mol) was dissolved in CH
2
Cl
2
(5 mL) at 20 C
in a reaction tube. Isobutene (10 mL) was condensed into this solu-
tion and cooled to 78 C. The reaction mixture was warmed to
the appropriate temperature, stirred for 2 hours at this temperature,
and then quenched with methanol (0.5 mL). The obtained polymer
was dried as described above.
Polymer Characterization
Number- (M
n
) and weight-average (M
w
) molecular weights and po-
lydispersities (M
w
/M
n
) were determined by gel permeation chroma-
tography (GPC) vs. polystyrene standards. The GPC measurements
were carried out at 30 C in chloroform with PSS-SDV columns
(8.0 mm 30 mm, 5 m particles, 10
3
, 10
4
, 10
5
, 10
6
A

pore size).
For detection a refractive index detector was used.
Crystallographic Analysis for 2a and 2b
Crystals of 2a and 2b were mounted on a glass fiber in silicone oil
at 123 C. The data were collected with a STOE IPDS two-circle
diffractometer using graphite-monochromated Mo-K

radiation
and a STOE IPDS area detector. The data were corrected for ab-
sorption by the STOE IPDS software. Lorentz polarization and
absorption corrections were applied. The structural solution (calcu-
lated by direct methods) and refinement (on F
2
, hydrogen atoms
calculated) were carried out using the SHELX97 program suite.
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Center as supplementary publication
no. CCDC-637292 (2a) and CCDC-688755 (2b). Copies of the data
can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [Fax: -44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk].
Quantum Chemical Calculations
All DFT calculations were carried out with the TURBOMOLE
program package [1519]. For all compounds the BP86 functional
with SV(P) basis sets were used. Vibrational frequencies were calcu-
lated with AOFORCE at the BP86/SV(P) level and used to verify
the nature of the obtained minima. On the basis of the calculated
frequencies, thermal corrections to the enthalpy and Gibbs free en-
ergy have been calculated with the FREEH module implemented in
TURBOMOLE. Calculation of solvation energies (solvent CH
2
Cl
2
with 11.16 at T 30 C) were performed as single-point
DFT calculations (BP86/SV(P)) with the COSMO [39] module.
The Gibbs lattice energies for the BornHaberFajans cycle have
been calculated using a molecular volume based modified Kapus-
tinskii equation as introduced by Jenkins and Glasser [25, 2731].
Similarly, the solid state entropy was calculated according to
Jenkins and Glasser [26].
[AlCp
2
]

: Structure, Properties and Isobutene Polymerization

Supporting Information (see footnote on the first page of this arti-
cle): The presence of 2b in solution is confirmed by the
1
H NMR
spectrum.
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27
Al nucleus has a spin of I
5
/
2
and therefore an electri-
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27
Al-NMR spectroscopy. In compounds with a
highly symmetric environment of the
27
Al nucleus, e.g.
[AlCp*
2
]

, and longer life times this effect will be minimized.

Z. Anorg. Allg. Chem. 2009, 17871793 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de 1793
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[32] At 30 the reaction could only be carried out when the reac-
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temperature.
[33] Results of the polymerizations experiments at 70 C: t
10 min: yield /g: 0.05 (0.30), M
w
/10
4
g mol
1
: 17 (18), PDI:
1.8 (2.8), t 120 min: yield /g: 0.47, M
w
/10
4
g mol
1
: 16,
PDI: 1.9.
[34] With these calculations we wanted to show that only [AlCp
2
]

and not [AlCp

2
2Et
2
O]

reacts as an initiator for the isobutene

polymerization, as described in this paper.
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(4)]. For 2b [Equation (5)] was used. Reference is the
experimental value for the FIA of OCF
2
, which is
209 /kJ mol
1
.
(4)
(5)
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Received: December 11, 2008
Published Online: February 13, 2009