Synthesis of unsymmetrical ansa-fluorenyl metallocenes

Article abstract of DOI:10.1016/j.molcata.2003.07.020

General syntheses of unsymmetrical ansa-fluorenyl (flu)-containing ligands of the type flu-bridge-flu' (bridge: C₂H₄, CH ₂-SiMe₂, SiMe₂, SiPh₂) and of the corresponding [flu-bridge-flu']ZrC

Full text of DOI:10.1016/j.molcata.2003.07.020

Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
Synthesis of unsymmetrical ansa-fluorenyl metallocenes
A.R. Siedle∗, Richard A. Newmark, Brook F. Duerr, Peter C. Leung1
3M Corporate Research Laboratories, St. Paul, MN 55144-1000, USA
Received 3 March 2003; received in revised form 22 April 2003; accepted 14 July 2003
Abstract
General syntheses of unsymmetrical ansa-fluorenyl (flu)-containing ligands of the type flu-bridge-flu’ (bridge: C2H4, CH2-SiMe2, SiMe2,
SiPh2) and of the corresponding [flu-bridge-flu’]ZrCl2 metallocenes are described. Substituent effects in [2,7-R2-flu-C2H4-flu]ZrCl2 (R: H,
t-Bu, F, Cl) on rates of 1-octene polymerization are described.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Bridged fluorenyl metallocenes; Catalysts; Olefin polymerization
1. Introduction
describes bridged metallocene catalysts containing two flu-
orenyl ligands and focuses in particular on unsymmetrical
compounds that contain two different fluorenyl moieties.
We have recently reported that introduction of substituents
at C(4,5) in one of the fluorenyl rings in ansa-fluorenyl
metallocenes provides a rational means to sculpt catalyst
shapes and thereby influence their stereoregulating abilities
[14]. Cs metallocenes substituted in this way are useful for
synthesis of a novel class of nanocrystalline polypropy-
lenes [15]. Efficient syntheses of the starting ligands (and
hence the derived metallocenes) have not previously been
available. They are the subjects of this paper.
Cyclopentadienyl-containing compounds have played
an important role in the development of organometal-
lic chemistry as a discrete intellectual endeavor and of
the first “single site”, homogeneous olefin polymeriza-
tion catalysts exemplified by combinations of Cp2ZrCl2,
(ind)2MX2 or (flu)2MX2 (Cp: cyclopentadienyl; ind: in-
denyl; flu: 9-fluorenyl; X = halogen) with organoaluminum
co-catalysts such as methylaluminoxane (MeAlO)x [1,2].
Organic chemists early developed routes to symmetrical
bridging ligands such as Me2Si(ind)2 [3], 1,2-(ind)2C2H4
[4], Ph2Si(flu)2, [5] and 1,2-(flu)2C2H4 [6]. ansa-Derivatives
of the type [(ind)2-bridge]MX2 (bridge = C2H4 and R2Si;
M = Ti, Zr, Hf; X = Cl, Br), in which the carbocyclic lig-
ands are connected by a bridging group, were then found to
be very active catalysts and useful for the synthesis of at-
actic or isotactic polypropylene, depending on whether the
meso or rac isomers were employed [7,8]. The compound
[Cp-CMe2-flu]ZrCl2 was one of the first highly syndiospe-
cific polymerization catalysts [9,10], a development which
stimulated investigation of other fluorenyl-containing met-
allocenes [11]. Ewen observed that, for polypropylene,
polymer molecular weights increased about 10-fold for ev-
ery C6 aromatic ring fused to the C5 ring [12] and we have
made similar observations for polyhexene [13]. This paper
2. Results and discussion
2.1. Ligand syntheses
The problems in synthesizing asymmetrical difluorenyl
ligands are illustrated by the difficulties in obtaining the
symmetrical compound 1,2-di(9-fluorenyl)ethane (1), in
good yield. Originally, reaction of Na(flu) with 1,2-Br2C2H4
gave flu-C2H4-Br which, when treated with more Na(flu),
produced flu-C2H4-flu [6,16]. Problems arise when Li(flu),
readily obtained from fluorene and BuLi, is used instead.
Li(flu) can react with 1,2-Br2C2H4 to produce the inter-
mediate flu-C2H4-Br. Subsequent reaction with a second
equivalent of Li(flu) can proceed by nucleophilic attack
at the CH2Br carbon to produce the desired product. Al-
ternatively, deprotonation at the C(9) position in the flu-
orene ring can occur and it is followed by intramolecular
∗
Corresponding author. Tel.: +1-651-736-1994;
fax: +1-651-737-2590.
E-mail address: arsiedle@mmm.com (A.R. Siedle).
1
Deceased.
1381-1169/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2003.07.020

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A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
Scheme 1.
cyclization to produce spiro-cyclopropane-9-fluorene. This
compound is difficult to separate from 1 and it is easily
recognized by the characteristic 1H NMR peak from the
spiro-cyclopropane ring at 1.74 ppm. Which of the two
pathways is followed depends critically on reaction condi-
tions. We find that the best yield of 1 is obtained by adding
Br2C2H4 to Li(flu) in THF at low temperature. Yields are
much lower at 25◦ and repeated recrystallization is required
in order to obtain pure 1. Addition of tetramethylethylene-
diamine (TMEDA) or use instead of ethylene glycol di-
tosylate did little to improve yields. Our approach to the
synthesis of unsymmetrical ethylene-bridged difluorenyl
ligands of the type fluorenyl-C2H4-Rn-fluorenyl required
as an intermediate a compound fluorenyl-CH2-CH2X in
which nucleophilic attack at carbon with displacement
of X− would be much faster than deprotonation fol-
lowed by intramolecular ring closure. Proton loss from
carbon-centered acids, although thermodynamically favor-
able, is kinetically slow [17]. Triflate, CF3SO3−, is known
to be a very good leaving group. Therefore, we set out
to prepare fluorenyl-C2H4-OSO2CF3 (2). Because 2 was
expected to be very sensitive to nucleophilic attack, it was
generated in an apolar solvent so that no potentially nu-
cleophilic by-products were formed. Thus, treatment of
flu-C2H4-OH in toluene with one equivalent of BuLi af-
forded flu-C2H4-OLi (3). The stoichiometry of this reaction
was easily followed by observation of color for 3 is color-
less but removal of an additional proton from C(9) forms an
orange dianion. Treatment of 3 with CF3SO3F then yielded
2 and inert LiF. The compound CF3SO3F is a gas at room
temperature and any excess employed was easily removed
by pumping. After filtration to remove LiF and evaporation
of solvent, 2 was obtained as a colorless oil, stable, either
under nitrogen or when redissolved in toluene, for at least
several days at room temperature [18].
(11), flu-C2H4-2,7-(t-Bu)2-flu (12), flu-C2H4-9-Me-2,3-
benzoflu (13), and flu-C2H4-2,7-t-Bu2-4-␣-Npflu (14), re-
spectively, as indicated in Scheme 1. Dimethoxyethane or
diethyl ether are solvents preferred to THF so as to avoid
complications from triflate-catalyzed oligomerization of
THF.
For synthesis of compounds of the type flu-C2H4-X, tri-
flate (X = CF3SO3) was the best leaving group found. Other
leaving groups failed to give the desired products or led
to unexpected results. For example, treatment of a toluene
solution of flu-C2H4-OLi with Me2NSO2Cl and then with
Li[2,7-F2-flu] in ether produced a coupling product, 9,9ꢀ-
(2,7-F2-flu)2 (15) in 40% yield. A similar reaction using
(CF3CO)2O and Li[2,7-Br2-flu] led to the ketone 9-CF3CO-
2,7-Br2-flu (16), in 60% yield.
Even symmetrical derivatives of 2,7-dichlorofluorene
(17), are difficult to obtain because reaction of its lithium
salt with ethylene oxide forms the diol 2,7-Cl2-flu-9,9-
(C2H4OH)2 [19]. One of the C(9) positions must be
protected. Thus, treatment of the Li+ salt of 2,7-Cl2-flu
with Me3SiCl afforded 2,7-Cl2-9-Me3Si-flu (18). Depro-
tonation with BuLi and reaction with ethylene glycol
ditosylate afforded the protected intermediate 1,2-(2,7-
Cl2-9-Me3Siflu)2C2H4 (19). Removal of the Me3Si group
was achieved with [Bu4N]F in THF under N2 followed
by quenching of the resulting carbanion with CF3CO2H
to afford 1,2-(2,7-Cl2-flu)2C2H4 (20). Choice of reaction
conditions was important. Run in air, the deprotection reac-
tion produced 1,2-(2,7-Cl2-9-HOflu)2C2H4 (21). If the acid
quench were omitted and workup with dichloromethane
started, reaction of the intermediate anion with this solvent
occurred to give spiro-2,2ꢀꢀ,7,7ꢀꢀ-tetrachlorodi(fluorene-9,1ꢀ-
cyclopentane-3ꢀ,9ꢀꢀ-fluorene) (22), as shown in Scheme 2.
A ligand having an unsymmetrical bridge, flu-SiMe2-
CH2-flu (23) was also prepared. Reaction of Li(flu) with
ClSiMe2-CH2Br afforded flu-SiMe2-CH2Br, 24. To en-
hance reactivity at the methylene carbon (24) was converted
to flu-SiMe2-CH2I (25) by metathesis with NaI in acetone.
Compound 25 was quite reactive towards both acids (pro-
tiodesilation, cf. Section 2.5) and bases. The latter caused
elimination of HI and formation of a silacyclopropane. Sila-
cyclopropanes undergo nucleophilic ring opening far more
readily than cyclopropanes. The ring opening by fluorenyl
carbanions is not regiospecific. Thus, treatment of 25 with
two equivalents of K(2,7-t-Bu2-flu) produced an insepara-
ble mixture of the isomers flu-SiMe2-CH2-(2,7-t-Bu2-flu),
In preparative experiments, 2 was not isolated. Sub-
sequent addition to the crude reaction mixture of Li+
salts in ethereal solvents of cyclopentaphenanthrene
(CPA), 4,5-dihydrocyclopentaphenanthrene (H2CPA), 4,5-
dimethylfluorene, 2,7-Cl2-fluorene, 2,7-F2-fluorene, 4-Me-
fluorene, 4-i-Prfluorene, 2,7-(p-tolyl)2-fluorene, 2,7-t-Bu2-
fluorene, 9-Me-benzo[c]fluorene, and 2,7-t-Bu2-4-Npflu
(Np ≡ ␣−naphthyl) afforded the ligands flu-C2H4-CPA (4),
flu-C2H4-H2CPA (5), flu-C2H4-4,5-Me2-flu (6), flu-C2H4-
2,7-Cl2-flu (7), flu-C2H4-2,7-F2-flu (8), flu-C2H4-4-Meflu
(9), flu-C2H4-4-i-Prflu (10), flu-C2H4-2,7-(p-tolyl)2-flu

A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
189
Scheme 2.
26, and flu-CH2-SiMe2-(2,7-t-Bu2-flu), 27. These two com-
pounds correspond to two possible pathways for C–Si bond
cleavage by a second equivalent of 2,7-t-Bu2-flu produced
by the second equivalent of this base. Therefore, this syn-
thetic method is usually an inefficient route to compounds
of the type flu(1)-SiMe2-CH2-flu(2) where the two fluorenyl
ligands, 1 and 2, are different. In general, the Mg–C bond in
organomagnesium compounds is considered to be more co-
valent than those in alkali metal compounds and, therefore,
the former are anticipated to be weaker bases [20]. Accord-
ingly, reaction of 25 with one half equivalent of flu2Mg
produced pure 23 and no fluorene. Similarly, reaction of 24
with Li [2,7-Cl2-flu] in 1,2-dimethoxyethane-hexane pro-
duced flu-SiMe2-CH2-(2,7-Cl2-flu), 28, in modest (19%)
yield.
with two equivalents of BuLi followed by removal of the
ethereal solvent and reaction with metal salts such as ZrCl4
or HfCl4 as described in Section 2.18. Solvents used in the
metal insertion step were CH2Cl2 (at −78 ◦C) or toluene
at room temperature. The latter was preferred and probably
safer. In this way, the ligands 4–14, 20, 23, 29–31 were
converted to the metallocenes [flu-C2H4-CPA]ZrCl2 (32),
[flu-C2H4-H2CPA]ZrCl2 (33), [flu-C2H4-4,5-Me2-flu]ZrCl2
(34), [flu-C2H4-2,7-Cl2-flu]ZrCl2 (35), [flu-C2H4-2,7-F2-
flu]ZrCl2 (36), [flu-C2H4-4-Meflu]ZrCl2 (37), [flu-C2H4-
4-i-Prflu]ZrCl2 (38), [flu-C2H4-2,7-(p-tolyl)2-flu]ZrCl2
(39), [flu-C2H4-2,7-t-Bu2-flu]ZrCl2 (40), [flu-C2H4-9-
Mebenzo[c]flu]ZrCl2 (41), [flu-C2H4-2,7-t-Bu2-4-(␣-Np)
flu]ZrC2 (42), [Cl2-flu-C2H4-Cl2-flu]ZrCl2 (43), [flu-
SiMe2-CH2-flu]ZrCl2 (44), [flu-SiMe2-CPA]ZrCl2 (45),
[flu-SiMe2-H2CPA]ZrCl2 (46), and [flu-SiPh2-H2CPA]ZrCl2
(47). The new fluorenyl-containing metallocenes separated
as finely divided, bright red luminescent solids that were
most conveniently isolated by centrifugation. Those con-
taining a C2H4 bridge were sufficiently hydrolytically stable
that by-product LiCl and other salts could be removed by
rapid washing with absolute ethanol. Metallocenes contain-
Unsymmetrical ligands of the type flu-SiR2-flu’, con-
taining a R2Si bridge, were prepared from flu-SiR2Cl (R=
Me, Ph) and Li[flu’]. In this way, CPA-SiMe2-flu, 29,
H2CPA-SiMe2-flu, 30, and H2CPA-SiPh2-flu, 31 were ob-
tained.
The new ligands described above could be converted to
the corresponding metallocenes by treatment in ether or THF

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A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
ing a Me2Si bridge were quickly decomposed by ethanol
and were purified by recrystallization from CH2Cl2, one of
the few suitable, non-reactive solvents. They are extremely
moisture sensitive in solution and rigorously dried solvent
is required. Solubility of most of the ansa-bridged fluorenyl
metallocenes in CH2Cl2 is low, on the order of several hun-
dred mg l−1, which makes obtention of good NMR spectra
difficult. However, it is possible to use the metallocenes
in other settings without removal of the lithium salts. We
have used these compounds to polymerize propylene and
their stereoregulating properties have been described else-
where [14,15]. Here, we focus on some electronic effects
in metallocene-catalyzed olefin polymerization.
analysis: (1) the initiating metallocenium species are (often)
ion pairs and the degree of ion pairing, and hence reactivity
can depend on the structure (i.e. number and type of car-
bocyclic ligands) of the ions; (2) the overall rate observed
is a convolution of rates of several elementary steps includ-
ing initiation, propagation, chain transfer, chain termination
and catalyst deactivation. All of these rates are, in principle,
influenced by the steric and electronic effects exerted by a
substituent.
Thus, in the indenyl metallocenes (5,6-X2C9H5)2ZrCl2
and the ethylene-bridged analogues [1,2-(5,6-X2C9H4)2C2
H4]ZrCl2, the empirical rate of ethylene polymerization
was decreased (relative to X = H) when X was Cl or OMe.
However, the effect of the methoxy group was obscured
by a competing catalyst deactivation reaction [22]. In the
metallocenes [2,7-X2-flu-CMe2-Cp]ZrCl2, relative rates
for propylene polymerization were in the order X = H >
2.2. Substituent effects in olefin polymerization
The relative rates of 1-octene polymerization by
[2,7-R2-flu-C2H4-flu]ZrCl2 (R = H, R: Cl, 35; F, 36; and
t-Bu, 40) at 30 ◦C in the presence of methylaluminoxane as
co-catalyst were examined. Octene is a convenient substrate
because it is a liquid at room temperature and so reactions
can be carried out in glass jars at atmospheric pressure.
Results are collected in Table 1 along with GPC data
for the product polymers. The electron-withdrawing sub-
stituents Cl and F are associated with 1.7- and 1.9-fold in-
creases, respectively, in conversion efficiencies with a slight
increase in polyoctene molecular weight. The effect of two
t-butyl groups in the 2,7 positions of one fluorenyl ring on
conversion efficiency is striking—a 17-fold reduction. There
is only a slight decrease in the polymer molecular weight.
Incorporation of t-butyl groups into the second fluorenyl
ring, i.e. [2,7-t-Bu2-flu-C2H4-2,7-t-Bu2-flu]ZrCl2 (48) re-
duces the polymerization rate and polymer molecular weight
even further.
t−Bu > F
Cl [23]. A study of the unbridged met-
allocenes (4,7-R2-indenyl)2ZrCl2 indicated that electron-
withdrawing substituents (Cl, F) decreased both catalyst
molecular weights and polypropylene molecular weights;
and that electron-releasing substituents such as Me affected
neither [24].
A study of the constrained-geometry catalysts (XC9H5)-
(SiMe2-t-Bu)TiMe2, activated with (C6F5)3B, revealed an
increase in activity for ethylene-octene copolymerization
and in polymer molecular weight for X = 2-OMe; and
a dramatic increase for the 3-N-pyrrolidine compound
X = c-C4H8N [25]. In contrast, the activity of rac-[2-
Me2NC9H6)2SiMe2]ZrCl2 was lower than that of the un-
substituted compound. Additionally, the Me2N-substituted
ansa-indenyl metallocene exhibited an unusually long in-
duction period. The dominant chain termination process was
exchange of Me and polymer chains between Al centers of
the (MeAlO)x co-catalyst and Zr in the metallocene [26].
It is difficult to distill a consensus from these results.
Indeed, it might seem reasonable to suspect that even the
sign of a substituent effect can depend on the structure
of the metallocene molecule. Here, the accelerating effect
on polymerization rate of Cl and F in (2,7-X2-flu-C2H4-
flu)ZrCl2 is regarded as electronic in nature, a consequence
of the electron-withdrawing properties of these halogen
substituents. In a study of the rates of activation of ansa-
bridged fluorenyl metallocenes by (MeAlO)x, we found
that F and Cl substituents also accelerate this reaction,
which transforms (flu-C2H4-flu)ZrCl2 into the resting state
2.3. Discussion of substituent effects
Our results above appear to be inconsistent with some
earlier studies. Although substituent effects in metallocene
catalysts have been incisively reviewed [21], we believe that
a complete and comprehensive theory of these effects has
yet to be put forward. Two problems lie at the core of the
Table 1
1-Octene polymerization data
Metallocene
Conversion
efficiency
(kg polyoctene h−1
(g Zr)−1
Mw, Mn (×10−5
;
+
g mol−1
)
of the catalyst, (flu-C2H4-flu)Zr(␮-Me2)AlMe2 [27]. So
they appear to have the same effect on rates of octene
polymerization. However, these trends run counter to those
described above for halogen substituents. We surmise that
electron-withdrawing substituents should accelerate olefin
polymerization because they render the metal center in the
catalyst more nucleophilic. On the other hand, a more nu-
cleophilic metal center should have enhanced interactions
with the “non-coordinating” counterion associated with
the metallocenium ion initiator, leading, in turn, to slower
(flu-C2H4-flu)ZrCl2
(Cl2-flu-C2H4-flu)ZrCl2 (35)
(F2-flu-C2H4-flu)ZrCl2 (36)
(t-Bu2-flu-C2H4-flu)ZrCl2
(40)
59
100
113
3.4
2.2, 1.0
2.7, 1.3
2.7, 1.3
2.1, 1.1
(t-Bu2-flu-C2H4-t-
0.6
1.5, 0.6
Bu2-flu)ZrCl2 (48)
Conditions: run in neat octene, [Zr] = 2 ppm, [Al]/[Zr] = 2400.

A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
191
initiation and propagation. Which situation predominates
2.5. Experimental
depends on the structure of the metallocene. If the metal
center is incompletely shielded by the steric bulk of the
ligands, then the effect of tighter ion pairing should prevail.
If, on the other hand, the metal is well protected by bulky
fluorenyl groups, as is the case here with (2,7-X2-flu-C2H4-
flu)ZrCl2 metallocenes, tighter ion pairing is disfavored and,
instead, increased metal nucleophilicity results in enhanced
interactions with an olefin substrate.
It is tempting to think that the effect of t-Bu substituents
in 40 and 48 is of steric origin. We determined the solid
state structure of 48 in an effort to find ground state struc-
tural differences in this metallocene that would account for
the much slower rate of octene polymerization. However,
the molecular structure appears not to differ significantly
from that reported for [flu-C2H4-flu]ZrCl2 [28]. At this
point, we are faced with a conundrum because the problem
is under-determined. It is possible that the steric effects of
the t-Bu groups are manifested in one of the intermediates
in the polymerization reaction rather than in the ground
state structure of the precursor metallocene. Alternatively,
they may be due to the electron-releasing properties of t-Bu
groups. The data are insufficient to make a distinction.
Reactions were conducted under an atmosphere of dry
nitrogen unless otherwise indicated. Fluorenyl ligands
were isolated and purified in air in which they are stable.
Dichlorozirconium and hafnium metallocenes are stable
to oxygen but are moisture sensitive to varying degrees.
They were isolated and stored under dry nitrogen. THF,
diethyl ether and toluene were distilled under N2 from
Na-benzophenone; CH2Cl2 was distilled from CaH2. NMR
spectra were obtained on Varian XL-400 or Unity 500 in-
struments. Chemical shifts are referenced to internal Me4Si
(1H, 13C, 29Si) and CFCl3 (19F) with positive shifts, in
ppm, being downfield of the references. Coupling constants
are given in Hz. Physical properties of new compounds
and some starting materials are collected in Table 3. The
compounds 2,7-di-(p-tolyl)fluorene, 2,7-di-t-Butylfluorene
[29], 9-Mebenzo[c]fluorene [30], 2,7-Cl2-fluorene [31],
7-F2-fluorene [32], 4,5-Me2-fluorene [33], flu-SiMe2Cl
[34], flu-SiPh2Cl [35] and flu-C2H4OH2 were prepared
by literature methods. CF3SO2F was a 3 M product. The
compound flu-C2H4-OH was kept under N2 for long term
storage for it very gradually became gummy in air. Simi-
lar deterioration was observed for flu-C2H4Br which, over
10 months, there accrued 15 mol% of an impurity whose
NMR spectra were consistent with 9-HOO-9-(BrC2H4)flu.
n-BuLi refers to a 2.5 M solution in hexane. Mass spec-
tra were obtained in electron impact mode using 70 eV
electron beam energy. Thermal desorption was used for
neutral ligands; laser desorption was more successful for
metallocenes.
2.4. Structure of [2,7-t-Bu2-flu-C2H4-2,7-t-Bu2-flu]ZrCl2
(48)
Compound 48 crystallized from chloroform as a 1:1 sol-
vate whose structure was determined by X-ray crystallogra-
phy. Selected bond distances are given in Table 2. Because
the structure is similar to that of [flu-C2H4-flu]ZrCl2, only
key differences in the Zr–C distances will be highlighted.
Zirconium is bonded to all five carbon atoms in the ␩5-
fluorenyl rings. It is, however, displaced toward the unique,
bridgehead carbon atoms and these participate in the shortest
Zr–C bonds, d(Zr–C)av = 2.147(5) Å. The bonds to the pairs
of carbon atoms ␣ and ␤ to this carbon atom, 2.571(5) and
2.682(5) Å, respectively, are progressively longer. Bonding
2.6. 1-Octene polymerization
Methylaluminoxane was obtained from Albemarle
Corp. as a solution in toluene that contained 26 wt.%
(MeAlO)x and 5.2 wt.% Me3Al. It was diluted with toluene
(vacuum transferred from i-Bu3Al) to give a solution having
an aluminum concentration (determined by ICP analysis)
of 1.7 M. In a drybox, metallocenes and this (MeAlO)x
solution were combined in toluene to give [Zr] = 2 ppm
and [Al]/[Zr] = 2400 after dilution with monomer. After
stirring for 30 min, the catalyst was added to neat octene
that had been vacuum transferred from NaK alloy. Re-
actions were run for 1 h, quenched with deoxygenated
methanol and removed from the drybox. The precipitated
polymer was separated and dried in a vacuum oven at
75 ◦C. GPC analyses were performed on toluene solu-
5
is therefore distorted from a ␩ arrangement towards ␩3. In
[flu-C2H4-flu]ZrCl2, the corresponding Zr–C distances are
2.426(5), 2.550(5) and 2.670(5) Å.
Table 2
Selected bond distances (Å) and angles (◦) in 48·CHCl3
Zr-C212
Zr-C112
Zr-C113
Zr-C213
Zr-C211
Zr-C111
Zr-C15
Zr-C26
Zr-C25
Zr-C16
Zr-C11
2.414(5)
2.421(5)
2.563(5)
2.565(5)
2.574(5)
2.583(5)
2.670(5)
2.673(6)
2.689(6)
2.694(6)
2.410(2)
2.411(2)
100.07(6)
2
cf. [18]. Successful reaction of the Li+ salt of a fluorenide with ethy-
lene oxide appears to be very sensitive to reaction conditions. The proce-
dure, applied to 2,7-Cl2-fluorene, yields 9,9-(HOC2H4)2-2,7-Cl2-flu [19].
Applied to cyclopentaphenanthrene, a mixture of 9,9-(HOC2H4)2CPA
(51) and 9-HOC2H4CPA (52) was obtained. Despite repeated re-
crystallization, the latter was never obtained in more than 85 mol%
purity.
Zr-C12
Cl1-Zr-C12

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A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
Table 3
Characterization data for ligands and metallocenesa
Flu-C2H4-flu (1): 1H NMR (CDCl3): 7.75 (d, 8), 7.37 (td, 8, 2), 7.30–7.29 (m), 3.83 (H9), 1.73 (CH2). 13C NMR: 146.7, 141.2 (Cipso), 126.8, 126.7,
124.0, 119.6, 46.9 (C9), 26.5 (CH2). Mass spectrum: m/z 358 (M+), 191 (C13H11+), 178 (C14H10+), mp 222–223 ◦C (xylenes), 36%.
Flu-C2H4-OSO2CF3 (2): 1H NMR (CDCl3): 7.81 (d,7, H4,5), 7.54 (dd, 8, 1, H1,8), 7.45 (t, 7, H3,6), 7.39 (td, 8, 1, H2,7), 4.41 (t, 7, CH2OSO2), 4.18
(t, 6, H9), 2.62 (td, 7, 6 CH2CH2OSO2). 13C NMR: 144.6, 140.8, 127.6, 127.2, 123.9, 120.1, 74.4 (CH2OSO2), 43.4 (C9), 32.1 (CH2CH2OSO2). 19F
NMR: −78.8.
Flu-C2H4-CPA (4): 1H NMR (CDCl3): 7.81 (s, H4∗,5∗), 7.80 (d, H3∗,6∗), 7.74 (dt, 7, 1, H4,5), 7.61 (dd, 8, 7, H2∗,7∗), 7.51 (d, 7, H1∗,8∗), 7.37 (dd, 7,
1, H1,8), 7.35 (tm, 7, H3,6), 7.28 (td, 7, 1, H2,7), 4.39 (t, 6, H9∗), 3.91 (t, 5, H9), 2.01 (m, CPA-CH2), 1.91 (m, Flu-CH2). 13C NMR: 146.7, 145.4,
141.2, 137.4, 127.7, 127.2, 126.9, 126.8, 125.2, 125.1, 122.8, 120.6, 119.7, 49.5 (C9), 47.0 (C9∗), 28.4 (CPA-CH2), 27.0 (flu-CH2). Mass spectrum:
m/z 382 (M+), 203 (C16H11+). mp 225–227 ◦C (heptane–toluene), 51%. Anal. C, 94.2 (94.1); H, 5.8 (5.9).
Flu-C2H4-H2CPA (5): 1H NMR (CDCl3): 7.73 (dt, 7, 1, H4,5), 7.39 (dq, 7, 1, H1,8), 7.35 (tdd, 7, 1, 0.6, H3,6), 7.28 (td, 8, 1, H2,7), 7.16 (m, 4H,
H2CPA), 7.08 (m, 2H, H2CPA), 3.92 and 3.91 (overlapping t, 2H, H9,9∗), 3.12 (m, 4H, H2CPA-H4,5), 2.01 (m, 2H, H2CPA-CH2), 1.72 (m, 2H,
flu-CH2). 13C NMR: 146.8, 144.1, 141.2, 138.5, 130.2, 127.2, 126.83, 126.79, 124.83, 124.16, 122.0, 119.7, 49.3 and 47.1 (H9,9∗), 28.6 (CH2), 27.1
(CH2), 26.0 (H2CPA CH2). Mass spectrum: m/z 384.1813 (M+, calcd. 384.1827), 206 (M+ − C14H10). mp 189–190 ◦C (CH2Cl2–acetone), 65%.
Anal. C, 93.8 (93.7); H, 6.2 (6.2).
Flu-C2H4-4,5-Me2-flu (6): 1H NMR (CDCl3): 7.66 (d, 8, H4,5), 7.28 (m, H3,6), 7.21–7.19 (m, H2,7, H1,8), 7.12 (t, 7, H2∗,7∗), 7.08 (d, 7, H1∗,8∗ or
H3∗,6∗), 7.02 (d, 7, H3∗,6∗ or H1∗,8∗), 3.71 and 3.67 (t, 5, H9 and H9∗), 2.67 (s, CH3), 1.61 (m, CH2), 1.50 (m, CH2). 13C NMR: 148.0, 146.8,
141.19, 141.16, 131.8, 130.6, 126.77, 126.74, 126.56, 124.1, 121.3, 119.6, 46.86 and 46.45 (C9,9∗), 26.9 and 25.6 (CH2), 25.3 (CH3). Mass
spectrum: m/z 386.2036 (M+, calcd. 386.2029). mp 173–175 ◦C (heptane), 57%. Anal. C, 92.8 (92.9); H, 7.2 (7.0).
Flu-C2H4-2,7-Cl2-flu (7): 1H NMR (CDCl3): 7.74 (d, 7, H4,5), 7.58 (d, 8, H4∗,5∗), 7.37 (t, 7, H3,6), 7.32 (m, H2,7 and H3∗,6∗), 7.27 (d, 8, H1,8), 7.19
(m, H1∗,8∗), 3.83 and 3.75 (H9 and H9∗), 1.64 and 1.58 (CH2). 13C NMR: 148.2, 146.2, 141.3, 138.8, 132.9, 127.4, 127.0, 126.9, 124.5, 124.0,
120.6, 119.7, 46.8 and 46.6 (C9,9∗), 25.9 and 25.7 (CH2). Mass spectrum: m/z 426.0964 (M+, calcd. 426.0937). mp 206–208 ◦C (toluene), 45%.
Anal. C, 78.7 (78.4); H, 4.7 (4.8).
Flu-C2H4-2,7-F2-flu (8): 1H NMR (CDCl3): 7.76 (d, 8, H4,5), 7.60 (dd, 8, 5 [4JHF], H4∗,5∗), 7.39 (td, 8, 2, H3,6), 7.32 (td, H2,7) overlapping 7.29 (m,
3
3
3
4
H
1,8), 7.06 (t, JHH and JHF = 9, m, H3∗,6∗), 6.94 (dd, JHH = 9, JHH = 2, H1∗,8∗), 3.88 (m, H9∗), 3.78 (m, H9), 1.67 and 1.54 (m, CH2). 13C
1
3
4
NMR: 162.2 (d, JCF = 245, H2∗,7∗), 148.6 (d, JCF = 10, H1∗,8∗), 146.2 (C1a,8a), 141.2 (C4a,5a), 136.4 (d, JCF = 2, C4a∗,5a∗), 126.9, 126.8, 123.9,
3
2
2
120.2 (d, JCF = 10, H4∗,5∗), 119.7, 114.1 (d, JCF = 23, C1∗,8∗ or C3∗,6∗), 111.4 (d, JCF = 23, C3∗,6∗ or C1∗,8∗), 49.93 and 49.60 (C9 and C9∗),
25.95 and 25.90 (CH2). 19F NMR: −116.2 (td, 9, 5). Mass spectrum: m/z 394.1472 (M+, calcd. 394.1526), 201 (C13H7F2+), 180 (C14H12+). mp
207–208 ◦C (toluene–hexane), (50%). Anal. C, 85.3 (85.5); H, 5.1 (5.3).
Flu-C2H4-4-Meflu (9): 1H NMR (CDCl3): 7.90 (d, 8, H5∗), 7.76 (d, 7, H4,5), 7.40–7.36 (m, 3H), 7.34–7.30 (m, 6H), 7.21 (t, 7, H2∗), 7.16 (t, 8, H2,7),
3.83 (2H, br, H9,9∗), 1.75–1.70 (m, 4H, CH2). 13C NMR: 147.07, 147.03, 146.69, 142.2, 141.2, 139.2, 132.8, 129.1, 126.78, 126.73, 126.70, 126.42,
126.05, 124.1, 123.9, 122.9, 121.5, 119.6, 46.89 and 46.65 (C9,9∗), 26.55 and 26.17 (CH2), 21.0 (CH3). Mass spectrum: m/z 372.1892 (M+, calcd.
372.1873), 192 (C15H12+), 178 (C14H10+), 165 (C13H9+). mp 194–195 ◦C (CH2Cl2–EtOH), 69%. Anal. C, 93.(93.4); H, 6.5 (6.8).
Flu-C2H4-4-i-Prflu (10): 1H NMR (CDCl3): 7.92 (d, 8, H5∗), 7.71 (d, 8, H4,5), 7.36–7.25 (m, 11H), 7.12 (d, 7, H3∗), 3.78 (m, H9,9∗ and CHCH3),
1.67 (m, CH2), 1.43, (d, 7, CH3), 1.37 (d, 7, CH3). 13C NMR: 147.34, 147.32, 146.7, 144.1, 141.57, 141.17, 141.16, 138.0, 126.77, 126.75, 126.71,
126.0, 124.06, 124.04, 123.9, 123.36, 123.15, 121.4, 119.6, 46.9 and 46.5 (C9,9∗), 29.4 (CHCH3), 26.61 and 26.16 (CH2), 22.92 and 22.57 (CH3).
Mass spectrum: m/z 400 (M+), 357 (M+ − C3H7). mp 115–117 ◦C (heptane), 65%. Anal. C, 93.0 (92.9); H, 7.0 (7.0).
Flu-C2H4-2,7-(p-tolyl)2-flu (11): 1H NMR (CDCl3): 7.80 (d, 8, H4∗5∗), 7.76 (d, 7, H4,5), 7.62 (dd, 8, 2, H3∗6∗), 7.56 (AAꢀXXꢀ pattern, d, 8, Htolyl
meta to CH3), 7.50 (s, H1∗,8∗), 7.35 (t, 7, H3,6), 7.30 (AAꢀXXꢀ pattern, d, 8, Htolyl ortho to CH3), 7.28 (d, 8, H1,8), 7.20 (td, 8, 1, H2,7), 3.92 and
3.84 (m, H9,9∗), 2.45 (s, CH3), 1.76 (m, CH2). 13C NMR: 147.5, 146.6, 141.2, 139.96, 139.66, 138.4, 136.8, 129.4, 126.87, 126.78, 126.77, 125.9,
124.1, 122.5, 119.89, 119.65, 46.91 and 46.78 (C9,9∗), 26.0 and 25.9 (CH2), 21.1 (CH3). Mass spectrum: m/z 538.2640 (M+, calcd. 538.2655). mp
242–243 ◦C (toluene), 70%. Anal. C, 93.7 (93.6); H, 6.3 (6.4).
Flu-C2H4-2,7-t-Bu2-flu (12): 1H NMR (CDCl3): 7.80 (d, 8, H4,5), 7.66 (d, 8, H4∗5∗), 7.41 (d, 7, H3∗,6∗), 7.40 (tm, 7, H3,6), 7.35 (s, H1∗8∗), 7.33 (t, 7,
H
2,7), 7.30 (d, 7, H1,8), 3.84 and 3.83 (t, H9 and H9∗), 1.67 (m, CH2), 1.41 (s, CH3). 13C NMR: 149.6, 146.86, 146.70, 141.3, 138.7, 126.79,
126.78, 123.76, 123.72, 120.8, 119.7, 118.9, 46.65 and 46.61 (C9,9∗), 34.8 (CCH3), 31.6 (CH3), 25.4 and 24.1 (CH2). Mass spectrum: m/z 470.2896
(M+, calcd. 470.2968), 413 (M+ − C4H9), 357 (m/z 413-C4H8). mp 227–228 ◦C (heptane), 70%. Anal. C, 91.9 (91.9); H, 8.1 (8.0).
Flu-C2H4-9-Mebenzo[c]flu (13): 1H NMR (CDCl3): 8.76 (d, 8, H1∗), 8.26 (d, 8, H11∗), 7.98 (d, 8, H4∗), 7.81 (d, 8, H5∗), 7.78 (d, 7, H4,5), 7.65 (ddd,
8, 7, 1, H2∗), 7.54 (td, 7, 1, H3∗), 7.46 (d, 8, H6∗), 7.40 (t, 7, H3,6), 7.34–7.24 (m, H2,7, H1,8 and H10∗), 7.18 (s, H8∗), 3.88 (t, 5, H7∗), 3.80 (t, 5,
H9), 2.50 (s, CH3), 1.75–1.65 (m, CH2 next to benzoflu), 1.53 (m, CH2 next to flu). 13C NMR: 147.9, 146.6, 145.2, 141.25, 141.21, 139.7, 135.83,
135.62, 133.4, 129.20, 129.01, 127.76, 127.24, 126.80, 126.76, 126.64, 126.25, 124.87, 124.67, 124.07, 123.7, 122.35, 122.13, 119.6, 46.87 and
46.82 (CHCH2), 25.65 and 25.62 (CH2), 21.48 (CH3). Mass spectrum: m/z 422 (M+), 229 (C15H13+), 257 (M+ − C13H9). mp 154.5–156 ◦C
(CH2Cl2–EtOH), 62%. Anal. C, 93.8 (93.6); H, 6.2 (6.3).
Flu-C2H4-2,7-t-Bu2-4-(␣-Np)flu (14): 1H NMR (CDCl3): 7.98 (m, 2H), 7.82 (m, 2H), 7.64–7.20 (m), 6.87 (dm, 8, 1, 1H), 6.13 (t, 9, 1H), 3.90 (m,
H9,9∗), 1.8–1.7 (m, CH2), 1.44 (s, CH3), 1.28 (s, CH3). 13C NMR: Over 43 peaks between 149.1 and 119.7 ppm, 46.77 and 46.69 (C9,9∗), 34.81 and
34.58 (CCH3), 31.60 and 31.43 (CH3), 25.85, 25.49, 25.32 and 25.17 (CH2). Mass spectrum: m/z 596.3513 (M+, calcd. 596.3438), 483, 305, 291.
Mp 115 ◦C (MeOH), 45%. Anal. C, 92.6 (92.4); H, 7.4 (7.4).
3
9,9ꢀ-(2,7-F2-flu)2 (15): 1H NMR (CD2Cl2): 7.53 (dd, 8, 5 [4JHF], H4,5), 7.00 (td, 9 (3JHH and JHF), 2 (4JHH), H3,6), 6.61 (br, H1,8), 4.66 (s, H9). 13C
NMR: 161.8 (d, 246 (1JCF), C2,7), 145.7 (d, 8 (3JCF), C1a,8a), 136.6 (s, C4a,5a), 120.5 (d, 9 (3JCF), C4,5), 114.9 (d, 23 (2JCF), C1,8 or C3,6), 111.3
(d, 23 (2JCF), C3,6 or C1,8), 49.5 (C9). 19F NMR: −115.3 (br). Mass spectrum: m/z 402 (M+), 201 (C13H7F2+). mp 233–234 ◦C (heptane), 40%.
Anal. C, 77.6 (77.9); H, 3.5 (3.6).

A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
193
Table 3 (Continued )
9-CF3CO-2,7-Br2-flu (16): 1H NMR (CDCl3): 7.64–7.60 (m, 6H), 5.21 (s, H9). 13C NMR: 188.1 (q, JCF = 36, CO), 139.99, 139.92, 132.3, 128.3,
2
1
121.78, 121.76, 115.3 (q, 293, JCF = 293, CF3), 55.7 (C9). Mass spectrum: m/z 418 (M+), 321 (M+ − COCF3). IR: 1770 cm−1 (Nujol). mp
125.5–126 ◦C (heptane), 60%. Anal. C, 42.9 (43.3); H, 1.7 (1.9).
2,7-Cl2-9-Me3Siflu (18): 1H NMR (CDCl3): 7.70 (d, 8, H4,5), 7.44 (d, 2, H1,8), 7.32 (dt, 8, 2, H3,6), 3.82 (H9), −0.37 (CH3). 13C NMR: 147.1, 137.7,
131.9 (CCl), 125.7, 123.9, 120.7, 42.9 (C9), −2.8 (CH3). Mass spectrum: m/z 306.0400 (M+, calcd. 306.0393), 291 (M+ − CH3), 233 (M+
SiMe3); self-CIMS m/z 309, 307 (M+ + H). mp 127.5–128 ◦C (hexane), 47%. Anal. C, 62.5 (62.5); H, 5.2 (5.3).
−
1,2-(2,7-Cl2-9-Me3Siflu)2C2H4 (19): 1H NMR (CDCl3): 7.73 (d, 8 H4,5), 7.36 (dd, 8, 2, H3,6), 7.10 (d, 2, H1,8), 1.60 (CH2), −0.47 (CH3). 13C NMR:
149.4, 137.7, 132.4, 126.1, 122.8, 120.8, 49.9 (C9), 24.6 (CH2), 4.32 (CH3). Mass spectrum: m/z 638.0896 (M+, calcd. 638.0948), 550 (M+
SiMe3). mp >260◦ (CH2Cl2–heptane), 86%. Anal. C, 63.8 (64.2); H, 5.3 (5.2); Cl, 22.2 (22.1).
−
1,2-(2,7-Cl2-flu)2C2H4 (20): 1H NMR (CDCl3): 7.62 (d, 8, H4,5), 7.36 (dd, 2, 8, H3,6), 7.27 (m, H1,8), 3.83 (C9), 1.67 (CH2). 13C NMR: 147.8
(C4a,5a), 138.7 (C1a,8a), 133.1 (C2,7), 127.6 (H3,6), 124.4 (C1,8), 120.7 (C4,5), 46.7 (C9), 26.2 (CH2). Mass spectrum: m/z 494.0157 (M+, calcd.
494.0242), 459 (M+ − Cl). mp 240–241 ◦C (toluene), 66%. Anal. C, 67.7 (67.4); H, 3.6 (3.8).
1,2-(2,7-Cl2-9-HOflu)2C2H4 (21): 1H NMR (CDCl3): 7.50 (d, 8, H4,5), 7.36 (dd, 8, 1, H3,6), 7.23 (d, 2, H1,8), 1.64 (s, CH2). 13C NMR: 149.1
(C4a,5a), 137.0 (C1a,8a), 134.2 (CCl), 129.5 (C3,6), 123.9 (C1,8), 121.1 (C4,5), 81.6 (C9), 33.0 (CH2). IR (Nujol): 3524 cm−1. Mass spectrum: m/z 526
(M+), 249 (C13H7OCl2+), 37%. Anal. C, 73.5 (73.7); H, 3.9 (3.8).
spiro-1,3-(2,7-Cl2C13H6)2C3H2 (22): 1H NMR (CDCl3): 7.79 (d, 2, H1,8), 7.61 (d, 8, H4,5), 7.38 (dd, 8, 2, H3,6), 2.76 (CH2), 2.65 (CH2CH2). 13C
NMR: 154.9, 137.0, 133.7, 127.7, 123.4, 120.8, 58.7 (C9,9∗), 50.5 (CH2), 42.0 (CH2CH2). Mass spectrum: m/z 506 (M+), 260 (C15H10Cl2+), 246
(C14H8Cl2+). mp >260 ◦C (CH2Cl2–hexane), 6%. Anal. C, 68.5 (68.4); H, 3.5 (3.5); Cl, 28.0 (28.2).
Flu-SiMe2-CH2-flu (23): 1H NMR (CDCl3): 7.91(8, 2, H4∗,5∗), 7.70 (d, 8, H4,5), 7.40 (d, 7, H1∗,8∗), 7.39 (t, 7, H3∗,6∗), 7.32 (t, 8, H3,6), 7.31 (td, 8, 1,
H2∗,7∗), 7.21 (td, 7, 1, H2,7), 7.11 (dd, 8, 1, H1,8), 3.92 (t, 6, H9), 3.68 (s, H9∗), 0.98 (d, 6, CH2), −0.47 (s, CH3). 13C NMR: 148.2, 145.4, 140.46,
140.32 126.73, 126.64, 125.90, 125.13, 124.30, 124.00, 119.76, 119.53, 43.2 and 42.9 (C9,9∗), 14.1 (CH2), −2.34 (CH3). 29Si NMR: 5.8 (s). Mass
spectrum: m/z 237 (M+ − C13H9), 165 (C13H9+); M+ not observed. mp 145–147 ◦C (heptane), 63%. Anal. C, 86.6 (86.3), H, 6.5 (6.7).
Flu-SiMe2-CH2Br (24): 1H NMR (CDCl3): 7.90 (d, 8, H4,5), 7.56 (d, 8, H1,8), 7.41 (t, 8, H3,6), 7.35 (t, 8, H2,7), 4.16 (s, H9), 2.47 (s, CH2), 0.03 (s,
CH3). 13C NMR: 144.3, 140.4, 126.2, 125.5, 123.8, 120.0, 40.2 (C9), 15.8 (CH2), 5.50 (CH3). 29Si NMR: 5.9 (s). Mass spectrum: m/z 316.0295
(M+, calcd. 316.0277), 236 (M+ − HBr), 221 (m/z 236 − CH4), 179 (C14H11+), 178 (C14H10+), 165 (C13H9+), 151 (Me2SiCH2Br+), 123
(SiCH2Br+). mp 77–79 ◦C (heptane), 61%. Anal. C, 60.6 (60.4); H, 5.4 (5.5).
Flu-SiMe2-CH2I (25): 1H NMR (CDCl3): 7.87 (d, 8, H4,5), 7.53 (d, 8, H1,8), 7.38 (t, 7, H3,6), 7.32 (td, 8, 1, H2,7), 4.13 (s, H9), 1.94 (s, CH2), 0.03 (s,
CH3). 13C NMR: 144.5, 140.4, 126.2, 125.5, 123.8, 120.0, 40.8 (C9), −4.5 (CH3), −14.7 (CH2). 29Si NMR: 7.2 (s). Mass spectrum: m/z 364.0190
(M+, calcd. 364.0139), 237 (M+ − I), 199 C3H8SiI+), 171 (CH4SiI+), 165 (C13H9+). mp 86–87 ◦C (heptane), 66%. Anal. C, 52.7 (53.1), H, 4.7 (4.8).
Flu-SiMe2-CH2-2,7-Cl2-flu (28): 1H NMR (CDCl3): 7.93 (d, 8, H4,5), 7.53 (d, 8, H4∗,5∗), 7.43 (t, 8, H3,6), 7.41 (d, 7, H1,8), 7.36 (t, 7, H2,7), 7.29
(dd, 8, 2, H3∗,6∗), 6.98 (bd, H1∗,8∗), 3.74 (t, 6, H9∗), 3.71 (s, H9), 0.77 (d, 6, CH2), −0.34 (CH3). 13C NMR: 149.8, 144.9, 140.3, 137.9, 132.7,
127.3, 126.1, 125.4, 124.7, 123.9, 120.5, 119.8, 43.1 and 42.6 (C9,9∗), 13.3 (CH2), −2.0 (CH3). 29Si NMR: 6.4 (s). Mass spectrum: m/z 470.0999
(M+, calcd. 470.1019), 305 (M+ − C13H9), 165 (C13H9+). mp 157–158.5 ◦C (heptane), 19%. Anal. C, 73.9 (74.2); H, 5.1 (5.1).
Flu-SiMe2-CPA (29): 1H NMR (CDCl3): 7.90 (s, H4∗,5∗), 7.90 (d, 8, H4,5), 7.85 (d, 7, H3∗,6∗), 7.68 (d, 7, H1∗,8∗), 7.65 (t, 7, H2∗,7∗), 7.58 (d, 8,
H1,8), 7.38 (t, 7, H3,6), 7.30 (td, 7, 1, H2,7), 4.65 (s, H9∗), 4.38 (s, H9), −0.46 (s, CH3). 13C NMR: 144.7, 143.5, 140.7, 137.3, 128.1, 126.84,
126.15, 125.52, 125.45, 124.1, 121.5, 120.37, 120.06, 41.2 and 40.6 (C9,9∗), −6.8 (CH3). Mass spectrum: m/z 412.1654 (M+, calcd. 412.1642). mp
153–154 ◦C (CH2Cl2–heptane), 47%. Anal. C, 87.4 (87.2); H, 5.8 (5.9).
Flu-SiMe2-H2CPA (30): 1H NMR (CDCl3): 7.89 (d, 8, H4,5), 7.56 (d, 8, H1,8), 7.37 (t, 8, H2,7), 7.33 (d, 8, H1∗,8∗), 7.29 (td, 8, 1, H3,6), 7.19 (t, 8,
H2∗,7∗), 7.12 (d, 7, H3∗,6∗), 4.28 (s, H9), 4.21 (H9∗), 3.20 (m, CH2), −0.46 (CH3). 13C NMR: 144.9, 142.1, 140.7, 138.6, 130.8, 126.88, 126.14,
125.5, 124.2, 123.5, 121.9, 120.0, 41.1 and 40.6 (C9,9∗), 26.4 (CH2), −6.8 (CH3). Mass spectrum: m/z 414.1740 (M+, calcd. 414.1798), 249
(C17H
17Si+), 221 (C15H13Si+). mp 155–156 ◦C (CH2Cl2–acetone), 58%. Anal. C, 87.0 (87.1); H, 6.3 (6.3).
Flu-SiPh2-H2CPA (31): 1H NMR (CDCl3): 7.65 (br d, 8, H1∗,8∗), 7.53 (d, 7, H4,5), 7.38 (br d, 8, H3∗,6∗), 7.24 (t, 7, H2,7 or H3,6), 7.20 (td, 7, 1, H3,6
or H2,7), 7.12 (tt, 8, 1, Ph Hpara), 7.10 (t, 8, H2∗,7∗), 6.96 (d, 7, H1,8), 6.86 (t,7, Ph Hmeta), 6.70 (d, 7, Ph Hortho), 4.98 and 4.96 (s, H9,9∗), 2.94 and
2.71 (AAꢀXXꢀ pattern, CH2). 13C NMR: 143.6, 140.99, 140.63, 138.8, 134.94, 130.6, 128.94, 128.78, 126.58, 126.18, 125.90, 125.35, 124.5, 123.2,
122.3, 119.6, 39.0 and 38.2 (C9,9∗), 26.1 (CH2). Mass spectrum: m/z 538.2160 (M+, calcd. 538.2111), 373 (M+ − C13H9). mp 220–221 ◦C
(heptane–toluene), 47%. Anal. C, 89.2 (89.0); H, 5.5 (5.5).
[Flu-C2H4-CPA]ZrCl2 (32): Mass spectrum (laser desorption) m/z 562.9804 (Na·M+, calcd. 562.9881), 528 (M+ − Cl), 493 (M+ − 2Cl), 362 (M+
−
C14H10), 338 (C14H9Cl2Zr+). 27% (CH2Cl2). Anal. C, 66.4 (66.2); H, 3.7 (3.9); Cl, 13.1 (13.5).
[Flu-C2H4-H2CPA]ZrCl2 (33): Mass spectrum: m/z 542.0184 (M+, calcd. 542.0140). 53% (CH2Cl2). Anal. C, 66.2 (61.9); H, 4.0 (4.2); Cl, 13.1 (13.3).
[Flu-C2H4-4,5-Me2-flu]ZrCl2 (34): Mass spectrum: m/z 544.0305 (M+, calcd. 544.0297). 38% (CH2Cl2). Anal. C, 65.9 (65.5); H, 4.4 (4.5); Cl, 13.0
(13.1).
[Flu-C2H4-2,7-Cl2-flu]ZrCl2 (35): 1H NMR (CD2Cl2): 7.82 (dt, 9, 1, H4,5), 7.80 (dd, 2, 1, H1∗,8∗), 7.79 (dt, 9, 1, H1,8), 7.64 (dd, 9, 1, H4∗,5∗), 7.36
(ddd, 8, 7, 1, H2,7), 7.25 (ddd, 9, 7, 1, H3,6), 7.24 (dd, 9, 2, H3∗,6∗), 4.45 and 4.39 (AAꢀBBꢀ pattern, CH2). Assignments for [H4,5 and H1,8] and for
[H2,7 and H3,6] may be reversed. Laser desorption mass spectrum: m/z 584 (M+), 549 (M+ − Cl), 514 (M+ − 2Cl), 24% (CH2Cl2). Anal. C, 57.2
(56.9); H, 3.1 (3.2); Cl, 24.2 (24.4).

194
A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
Table 3 (Continued )
[Flu-C2H4-2,7-F2-flu]ZrCl2 (36): 1H NMR (CD2Cl2): 7.80 (dm, 9, H4,5), 7.78 (dm, 9, H1,8), 7.69 (dd, 9, 5, H4∗,5∗), 7.39 (dd, 9, 2, H1∗,8∗), 7.35 (ddd,
9, 7, 1, H2,7), 7.23 (ddd, 9, 7, 1, H3,6), 7.08 (td, 9, 2, H3∗,6∗), 4.42 and 4.36 (AAꢀBBꢀ pattern, CH2). 19F NMR: −114.9 (td, 9, 5). Mass spectrum:
m/z 551.9730 (M+, calcd. 551.9735), 338 (M+ − C14H8F2), 214 (C14H8F2+). 23% (CH2Cl2). Anal. C, 60.7 (60.2); H, 3.2 (3.4); Cl, 12.8 (12.9).
[Flu-C2H4-4-Meflu]ZrCl2 (37): Mass spectrum: m/z 530.0131 (M+, calcd. 530.0140), 495 (M+ − Cl), 352 C15H12Cl2Zr+). 33% (CH2Cl2). Anal. C,
65.4 (65.0); H, 4.1 (4.2); Cl, 13.4 (13.6).
[Flu-C2H4-4-i-Prflu]ZrCl2 (38): Laser desorption mass spectrum: m/z 558 (M+), 523 (M+ − Cl). 52% (CH2Cl2). Anal. C, 66.4 (66.0); H, 4.6 (4.8);
Cl, 16.3 (15.9).
[Flu-C2H4-2,7-(p-tolyl)2-flu]ZrCl2 (39): 1H NMR (CD2Cl2): 7.95 (s, H1∗,8∗), 7.88 (d, 9, H4,5), 7.79 (d, 9, H4∗,5∗), 7.76 (d, 8, H1,8), 7.53 (dd, 8, 2,
H3∗,6∗), 7.52 (d, AAꢀXXꢀ pattern, d, 8, p-tolyl Hmeta to CH3), 7.35 (d, AAꢀXXꢀ pattern, d, 8, p-tolyl Hortho to CH3), 7.28 (tm, 8, H3,6), 7.14 (t, 8,
H2,7), 4.54 (s, CH2), 2.44 (s, CH3). Laser desorption mass spectrum: m/z 696 (M+), 661 (M+ − Cl). 35% (CH2Cl2). Anal. C, 72.2 (71.9); H, 4.6
(4.4); Cl, 10.2 (9.9).
[Flu-C2H4-2,7-t-Bu2-flu]ZrCl2 (40): 1H NMR (CD2Cl2): 7.84 (dt, 8, 1, H4,5), 7.73 (dt, 8, 1, H1,8), 7.69 (dd, 2, 1, H1∗,8∗), 7.61 (dd, 9, 1, H4∗5∗), 7.38
(dd, 9, 2, H3∗,6∗), 7.28 (ddd, 9, 7, 1, H3,6), 7.15 (ddd, 9, 7, 1, H2,7), 4.47 (s, CH2), 1.37 (s, CH3). 13C NMR: 150.7, 127.86, 127.81, 127.31, 124.84,
124.74, 124.69, 124.22, 122.8, 121.9, 119.8, 117.5, 105.3 (C9,9∗), 34.8 (CCH3), 30.7 (CCH3), 25.36 and 25.14 (CH2). Laser desorption mass
spectrum: m/z 628 (M+), 593 (M+ − Cl). 60% (toluene–hexane). Anal. C, 68.6 (67.6); H, 5.7 (6.0); Cl, 13.4 (13.7).
[Flu-C2H4-9-Mebenzo[c]flu]ZrCl2 (41): Mass spectrum: m/z 580.0386 (M+, calcd. 580.0297), 545 (M+ − Cl), 510 (M+ − 2Cl). 62% (CH2Cl2).
Anal. C, 68.0 (67.7); H, 4.1 (4.2); Cl, 12.2 (12.4).
[Flu-C2H4-2,7-t-Bu2-4-(␣-Np)flu]ZrCl2 (42): 1H NMR (CDCl3): 7.87 (dt, 9, 1, H4), 7.78 (dm, 8, Np H5), 7.77 (dm, 8, Np H4), 7.73 (dt, 9, 1, H5),
7.67 (dt, 8, 1, H1), 7.641 (dd, 7, 1, Np H2), 7.636 (dt, 9, 1, H8), 7.60 (m, H1∗,8∗), 7.37 (dd, 8, 7, Np H3), 7.30 (ddd, 8, 7, 1, Np H6), 7.27 (ddd, 8,
7, 1, H6), 7.190 (dm, 9, Np H8), 7.174 (d, 2, H3∗), 7.166 (ddd, 8, 7, 1, H2), 7.139 (ddd, 9, 7, 1, H3), 7.087 (ddd, 8, 7, 1, Np H7), 7.00 (ddd, 9, 7, 1,
H7), 6.76 (dd, 9, 2, H6∗), 6.04 (dd, 9, 1, H5∗), 4.53 and 4.36 (m, CH2), 1.27 and 1.15 (s, CH3). 13C NMR: 150.2, 149.8, 137.4, 136.6, 133.3, 131.7,
128.19, 128.06, 127.60, 127.48, 127.40, 127.33, 127.08, 126.73, 126.67, 125.99, 125.70, 125.39, 125.28, 124.82, 124.77, 124.62, 124.45, 124.19,
122.53, 123.38, 122.19, 120.0, 118.9, 104.64 and 104.49 (C9 and C9∗), 35.1 and 34.9 (CCH3), 30.71 and 30.53 (CH3), 29.65 and 29.49 (CH2). Mass
spectrum: m/z 754.1570 (M+, calcd. 754.1505), 576.0921 (M+ − C14H10). 45% (hexane). Anal C, 73.0 (72.5); H, 5.6 (5.5); Cl, 9.4 (9.7).
[(2,7-Cl2-flu)2C2H4]ZrCl2 (43): Laser desorption mass spectrum: m/z 652 (M+), 617 (M+ − Cl), 582 (M+ − 2Cl). 20% (CH2Cl2–hexane). Anal. C,
51.2 (50.7); H, 2.4 (2.5); Cl, 32.5 (32.8).
[Flu-SiMe2-CH2-flu]ZrCl2 (44): Mass spectrum: m/z 560.0017 (M+, calcd. 560.0066), 382 (M+ − C14H10), 237 (C13H9SiMe2CH2+). 30%
(CH2Cl2–toluene). Anal. C, 61.9 (61.5); H, 4.3 (4.5); Cl, 12.6 (12.9).
[Flu-SiMe2-CPA]ZrCl2 (45): Mass spectrum: m/z 569.9994 (M+, calcd. 569.9909) 247 (C17H15Si+), 223 (C15H15Si+). 21% (CH2Cl2). Anal. C, 62.9
(62.4); H, 3.8 (3.9); Cl, 12.4 (12.6).
[Flu-SiMe2-H2CPA]ZrCl2 (46): Laser desorption mass spectrum: m/z 572 (M+). 38% (CH2Cl2). Anal. C, 62.7 (62.2); H, 4.2 (4.3); Cl, 12.4 (12.7).
[Flu-SiPh2-H2CPA]ZrCl2 (47): Mass spectrum: m/z 696.0329 (M+, calcd. 696.0379). 62% (CH2Cl2). Anal. C, 68.8 (68.5); H, 4.0 (4.1); Cl, 10.7 (10.9).
[(2,7-t-Bu2-flu)2C2H4]ZrCl2 (48): 1H NMR (CDCl3): 7.59 (d, 9 H4,5), 7.46 (br d H1,8), 7.26 (dd, 9, 2, H3,6), 4.32 (s, CH2), 1.26 (s, CH3). 13C NMR:
150.3, 128.8, 124.6, 124.2, 120.3, 116.1, 105.3 (C9), 35.2 (CCH3), 30.9 (CH3), 29.4 (CH2). Laser desorption mass spectrum: m/z 740 (M+), 705
(M+ − Cl). 70% (toluene–hexane). Anal. C, 71.2 (70.4); H, 7.0 (7.2); Cl, 9.6 (9.4).
(2,7-t-Bu2-flu)2C2H4 (49): 1H NMR (CDCl3): 7.61 (d, 9, H4,5), 7.46 (br d, H1,8), 7.36 (dd, 8, 2, H3,6), 3.84 (m, H9), 2.04 (m, CH2), 1.38 (s, CH3).
13C NMR: 149.5, 147.3, 138.4, 124.0, 121.0, 118.9, 47.4 (C9), 34.8 (CMe3), 31.6 CCH3), 30.3 (CH2). Mass spectrum: m/z 582.4211 (M+, calcd.
582.4220), 525 (M+ − C4H9), 469 (M+ − C4H9 − C4H8). mp 271.5–273 ◦C (heptane), 47%. Anal. C, 90.7 (90.4); H, 9.3 (9.3).
9-HOC2H4-CPA (51): 1H NMR (CDCl3): 7.85 (s, H4,5), 7.68 (d, 7, H3,6 and H1,8), 7.64 (t, 7, H2,7), 4.67 (H9), 3.88 (CH2OH), 2.38 (CH2CH2).
GC/MS: m/z 234 (M+).
a
In listings of NMR chemical shifts, asterisk (*) refers to positions in the substituted fluorenyl ring. Peak multiplicities, coupling constants and
assignments are given in parentheses. Melting points are followed by solvent(s) used for recrystallization and yield. Combustion analytical data are given
as calcd. (found).
tions and molecular weights determined using polystyrene
standards.
first being discarded. After recrystallization from hexane,
colorless crystals, mp 69–70 ◦C (93%), were obtained.
2.7. 4-Methylfluorene
2.8. 4-i-Pr-fluorene
Reduction of 4-CO2H-fluorene (Lancaster Synthesis
Co.) with BH3·THF [36] afforded 4-HOCH2-fluorene,
mp 122–123 ◦C, νOH (Nujol) 3300, 3200 cm−1. Hydro-
genation using 10% Pd/C catalyst [37] produced crude
4-Me-fluorene. Purification was by vacuum sublimation at
60◦ with the small amount of oily material that sublimed
Treatment of 4-COCl-9-fluoreneone (Aldrich) with one
equivalent of pyridine in excess MeOH produced 4-CO2Me-
fluoreneone, mp 130.5–131.5 ◦C. Hydrogenation under
20 psi (above atmospheric) H2 using 10% Pd/C catalyst
produced 4-CO2Me-fluorene, mp 71–74 ◦C after recrystal-
lization from MeOH-H2O. Reaction of this ester with 5 eq.

A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
195
of Me3Al in refluxing toluene gave 4-Me2C(OH)-fluorene,
mp 99–105 ◦C, νOH 3310 cm−1 (Nujol) as colorless plates
after recrystallization from heptane. Reduction of this alco-
hol was carried out using Et3SiH and CF3CO2H in CH2Cl2
[38]. NMR analysis of the crude product disclosed a 1:3
mixture of 4-i-Pr-fluorene and 4-isopropenylfluorene. The
latter was converted to the former when the mixture was
hydrogenated (10% Pd/C, 6 psi H2) in 1:4 toluene–heptane.
GC analysis of the colorless liquid product indicated that it
was >98% pure 4-i-Pr-fluorene (56%).
room temperature and stirring overnight, the reaction mix-
ture was passed through a Schlenk filter. Solvents and any
unreacted CF3SO2F were removed under vacuum. There re-
mained 7.7 g (95%) of product as a colorless oil.
2.12. Fluorenyl-C2H4-cyclopentaphenanthrenyl (4)
2-(9-Fluorenyl)ethanol, 5 g, was converted to the triflate
as described above. Unreacted CF3SO2F was removed by
pumping but it was not necessary to remove LiF. A slurry of
the Li+ salt of cyclopentaphenanthrene, prepared by addi-
tion of 23.8 mmol of n-BuLi in hexane to 4.52 g (23.8 mmol)
cyclopentaphenanthrene in 1:1 toluene–ether, was added to
the triflate solution in portions by means of a wide bore
canula. After stirring overnight, solvents were removed un-
der reduced pressure and the residue recrystallized from
toluene–heptane to give 5.7 g (51%) colorless microcrystals.
2.9. Dihydrocyclopentaphenanthrene
A mixture of 2 g cyclopentaphenanthrene (Aldrich), 0.2 g
10% Pd/C and 50 ml toluene was stirred under 10 psi (above
atmospheric) H2. The reaction was monitored by GC. When
the reaction was nearly complete, catalyst was removed
by filtration and the filtrate evaporated. The crude product
weighed 1.97 g and was contaminated with a small amount
of octahydrocyclopentaphenanthrene, 49, in which one of
the benzene rings had also been reduced. Recrystalliza-
tion from hexane gave 1.8 g (90%) colorless plates, mp
136–137 ◦C, of >98% purity by GC analysis. Mass spec-
trum: m/z 192.0934 (M+, calcd. 192.0936). Repeated re-
crystallization from hexane of the material remaining in the
mother liquor gave 49 of 83 mol% purity.
2.13. 2,7-Cl2-9-Me3Si-fluorene (18)
n-BuLi, 34 ml of a 2.5 M solution in hexane, was added
dropwise to a solution of 20.0 g (85 mmol) 2,7-Cl2-fluorene
in 75 ml toluene. After stirring overnight, 9.23 g (85 mmol)
Me3SiCl was added with stirring. Twenty hours later, the
reaction mixture was filtered through celite and evaporated to
dryness. The residue was dissolved in 150 ml boiling hexane
and filtered. On cooling to room temperature, the filtrate
deposited 12.3 g (47 %) of product as long, colorless needles.
2.10. 1,2-di(9-Fluorenyl)ethane (1)
A solution of 41.5 g (0.25 mol) fluorene in 500 ml THF
was cooled, with efficient magnetic stirring, in a dry ice-
acetone bath until the mixture became very thick due to
the fluorene that had crystallized. BuLi, 100 ml of a 2.5 M
solution in hexane, was added by canula in one portion.
The cooling bath was removed and the reaction mixture
warmed to room temperature. The butane evolved was swept
with nitrogen into a hood. The reaction mixture was again
cooled with dry ice. As the Li(flu) crystallized, it became
very thick. Then, 23.5 g (0.125 mol) 1,2-Br2C2H4 was added
in one portion. The reaction mixture was allowed to warm to
room temperature overnight. Solvents were removed under
vacuum. The residue was washed with 250 ml 50% aqueous
ethanol then recrystallized from boiling xylenes from which
the product separated as colorless blades, 24 g (54%), mp
222–223 ◦C. Further concentration of the mother liquor gave
mixtures of fluorene, 1 and spiro-cyclopropane-9-fluorene.
2.14. 1,2-(2,7-Cl2-9-SiMe3-fluorenyl)2C2H4 (19)
To a solution of 12.4 g (40 mmol) 15 in 125 ml ether was
added with stirring 40 mmol n-BuLi in hexane. This was then
added dropwise to a suspension of 7.4 g (20 mmol) ethylene
glycol ditosylate (Aldrich) in 75 ml ether. After stirring for
10 h, the reaction mixture was filtered. The solid phase was
washed with 20% aqueous ethanol then absolute ethanol.
After air drying, 8.82 g (69 %) 16 was obtained as a white
powder.
2.15. 1,2-(2,7-Cl2-fluorenyl)2C2H4 (20)
[Bu4N]F, 28 ml of a 1 M solution in THF (Aldrich), was
deoxygenated by sparging with N2 then added to a solution
of 8.72 g (13.7 mmol) 15 in 90 ml THF. After 30 min, the
deep red solution was quenched by adding 3.2 g (28 mmol)
CF3CO2H by syringe. Solvent was removed under reduced
pressure and the residue washed with saturated aqueous
NaHCO3, water and then ethanol. The residue was vacuum
dried to afford 6.6 g (97%) of product.
In a similar reaction, the acid quench was omitted and
workup was carried out in air. THF was removed under re-
duced pressure. The residue was taken up in CH2Cl2 and
passed through a short column of neutral alumina. Ethanol
was added and the solution slowly concentrated on a ro-
tary evaporator. Compound 22 (7%) separated as colorless
2.11. 2-(9-Fluorenyl)ethyl triflate (2)
A 2.5 M solution of BuLi in hexane was added with
stirring to 5 g (23.8 mmol) 2-(9-fluorenyl)ethanol in 90 ml
toluene. Addition was terminated when the reaction mixture
developed a persistent, very pale orange color (due to depro-
tonation at carbon); about 10 ml was required. The result-
ing solution of 3 was cooled in a dry ice-acetone bath and
3.8 g CF3SO2F added by vacuum transfer. After warming to

196
A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
microcrystals. The filtrate was treated with aqueous HCl to
give a gum that was recrystallized from toluene–heptane to
afford 21 in 42% yield.
and 0.93 g (4 mmol) ZrCl4 were added. The reaction mix-
ture was stirred vigorously for 10 h then filtered through
celite. The filtrate was evaporated and the residue washed
with 10 ml hexane. There remained 2.1 g red, microcrys-
talline product (70%). Slow evaporation of a CHCl3–hexane
solution of 48 produced crystals of 48·CHCl3 that could be
freed of solvent by heating under vacuum. This metallocene
has high solubility in hydrocarbon solvents.
2.16. Fluorenyl-SiMe2-CH2I (25)
A solution of 43.8 g (0.26 mol) fluorene in 500 ml ether
was cooled with a dry ice bath and treated with an equimo-
lar quantity of n-BuLi in hexane. The solution of Li[flu] was
warmed to room temperature and added dropwise to 50 g
0.26 mol) ClSiMe2-CH2Br (Petrarch) in 100 ml toluene. Af-
ter 8 h, the reaction mixture was evaporated. The residue was
twice recrystallized from heptane to afford 50 g (61%) of
fluorenyl-SiMe2-CH2Br (24). 6.3 g 24 was added to a solu-
tion of 4 g NaI in 100 ml acetone. After stirring overnight, the
reaction mixture was filtered and the filtrate evaporated un-
der reduced pressure. The residue was extracted with 30 ml
boiling heptane. On cooling of this extract to −5 ◦C, 4.9 g
(66%) 25 separated as beige nodules.
2.19. Crystal structure determination
An orange needle of 48·CHCl3 was mounted on a glass
fiber in a random orientation. Preliminary examination and
data collection were performed on an Enraf-Nonius CAD4
computer-controlled kappa axis diffractometer having a
graphite crystal, incident beam monochromator.
Cell constants and an orientation matrix were obtained
from least-squares refinement using the setting angles of 25
reflections between 11 and 21◦ measured by the computer
controlled diagonal slit method of centering. As a check on
crystal quality, ω scans of several intense reflections were
measured; the width at half height was 0.65◦ with a take-off
angle of 3◦, indicating moderate crystal quality. The system-
atic absences h 0 l (l = 2n) and 0 k 0 (k = 2n) and subse-
quent least-squares refinement revealed the space group to
be P21/c (#14).
2.17. Flu-SiMe2-CH2-flu (23)
Di(fluorenyl)magnesium, flu2Mg, was synthesized by re-
fluxing and vigorously stirring for 8 h a mixture of 6 ml 1 M
Bu2Mg in heptane (Alfa), 1.66 g (10 mmol) fluorene and
10 ml heptane. The organomagnesium reagent separated as
a yellow powder. The air- and water-sensitive product was
isolated by filtration at room temperature, washed with 25 ml
heptane then vacuum dried; the yield was 1.4 g (76%).
THF, 20 ml, was added to a mixture of 0.71 g (2 mmol)
flu2Mg and 1.46 g (4 mmol) 25. After stirring for 8 h, the
reaction mixture was quenched with 5 ml MeOH. Solvents
were removed under reduced pressure and the residue ex-
tracted with 50 ml CH2Cl2. The filtered extract was concen-
trated on a rotary evaporator until crystals appeared and then
cooled to −78 ◦C. Pale yellow crystals were collected on a
filter; the yield was 1.01 g (63%).
Lorentz and polarization corrections were applied to the
data. The structure was solved using the Patterson heavy-
atom method that disclosed the position of the Zr atom.
The remaining atoms were located in succeeding difference
Fourier syntheses. Hydrogen atoms were included in the
Table 4
Crystal data and structure refinement for 48·CHCl3
Formula
C45H53Cl5Zr
Formula weight
Crystal size (mm)
Crystal system
Space group
T (K)
862.41
0.72 × 0.22 × 0.19
Monoclinic
P21/c
2.18. [(2,7-t-Bu2-flu)2C2H4]ZrCl2 (48)
295
A solution of 16.7 g (60 mmol) 2,7-t-Bu2-fluorene in
150 ml THF was cooled in a dry ice bath and treated with
60 mmol BuLi. After warming to room temperature, the
solution was added with stirring to 11.1 (30 mmol) ethy-
lene glycol ditosylate (Aldrich) in 100 ml THF. After 12 h,
the reaction mixture was quenched with 6 ml 70% aqueous
CF3CO2H. Solvents were removed under reduced pressure.
Washing the residue with ethanol afforded 14 g crude prod-
uct. This was recrystallized from hot heptane–toluene to
give 8.2 g (47%) of 1,2-(2,7-t-Bu2-flu)2C2H4 (50). Concen-
tration of the mother liquor afforded a mixture of 50 and
spiro-cyclopropane-9-(2,7-t-Bu2-fluorene).
Unit cell dimensions
a = 11.378(2) Å, β = 93.229(15)◦
b = 19.178(4)Å
c = 20.227(3)Å
V (Å3)
Z
4406(2)
4
1.300
0.71073
0.579
5.26–45.12
6331
ρcalcd. (gm cm−3
λ (Å)
)
µ (mm−1
)
2θ range for data collection (◦)
Reflections collected
Independent reflections
Minimum, maximum
transmission factors
GOF on F2
5765 [R(int) = 0.032]
0.64, 1.00
1.068
To 2.3 g (4 mmol) 50 in 50 ml ether was added 8 mmol
BuLi. An ice water bath was used to moderate the exotherm.
After 3 h, volatiles were removed on a vacuum line. The
residue was subjected to pumping for 4 h. Toluene, 90 ml,
R(F0)
0.048
0.112
0.60 and –0.60
Rw(F02)
Largest difference peak and
hole (e Å−3
)

A.R. Siedle et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 187–198
197
Fig. 1. ORTEP drawing of [t-Bu2-flu-C2H4-t-Bu2-flu]ZrCl2 (48).
[3] L.H. Sommer, N.S. Marans, J. Am. Chem. Soc. 73 (1951) 5135.
refinement but constrained to ride on the atoms to which
they are bonded. Crystallographic data are given in Table 4.
An ORTEP drawing showing the numbering scheme is
shown in Fig. 1. Selected bond distances and angles are
given in Table 2. Crystallographic data (excluding structure
factors) have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication number
CCDC 230530. Copies of the data can be obtained, free
of charge, on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK (fax +44-1223-336033 or e-mail:
deposit@ccdc.cam.ac.uk).
[4] E. Marechal, A. Lepert, Bull. Soc. Chim. Fr. (1967) 2954.
[5] H. Gilman, J.J. Goodman, J. Org. Chem. 22 (1957) 45.
[6] E.J. Greenhow, D. McNeil, J. Chem. Soc. (1956) 3204. The dilithium
salt was first reported by B. Becker, V. Enkelmann, K. Mullen,
Angew. Chem. Int. Ed. 29 (1989) 458.
[7] (a) F.W.R.P. Wild, L. Zsolnai, G. Huttner, H.H. Brintzinger, J.
Organometal. Chem. 232 (1982) 233;
(b) F.W.R.P. Wild, M. Wasiucionek, G. Huttner, H.H. Brintzinger, J.
Organometal. Chem. 288 (1985) 263;
(c) J.A. Ewen, L. Haspeslagh, J.L. Atwood, H. Zhang, J. Am. Chem.
Soc. 109 (1987) 6544;
(d) E. Hoel, US Patent 4,871,705;
(e) J.A. Ewen, US Patent 4,794,096.
[8] (a) V. Dolle, H.F. Herrman, A. Winter, European Patent Application
480,390;
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