The combination of mononuclear metallocene and phenoxyimine complexes to give trinuclear catalysts for the polymerization of ethylene

Article abstract of DOI:10.1016/j.jorganchem.2007.10.001

Trinuclear complexes were synthesized by combination of metallocene and phenoxyimine zirconium complexes. After activation with methylalumoxane (MAO), these catalysts polymerize ethylene with moderate and good activities. Due to the presence of different catalytic centers, polyethylenes with broad or bimodal molecular weight distributions were obtained.

Full text of DOI:10.1016/j.jorganchem.2007.10.001

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 692 (2007) 5727–5753
www.elsevier.com/locate/jorganchem
The combination of mononuclear metallocene and
phenoxyimine complexes to give trinuclear catalysts
for the polymerization of ethylene
*
Christian Gorl, Helmut G. Alt
¨
Laboratorium fu¨r Anorganische Chemie, Universita¨t Bayreuth, Postfach 10 12 51, Universita¨tsstraße 30, Bayreuth D-95440, Germany
Received 11 June 2007; received in revised form 21 September 2007; accepted 1 October 2007
Available online 6 October 2007
Abstract
Trinuclear complexes were synthesized by combination of metallocene and phenoxyimine zirconium complexes. After activation with
methylalumoxane (MAO), these catalysts polymerize ethylene with moderate and good activities. Due to the presence of different
catalytic centers, polyethylenes with broad or bimodal molecular weight distributions were obtained.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Metallocene complexes; Bis(phenoxyimine)zirconium complexes; Salicylaldehydes; Multinuclear complexes; Ethylene polymerization; Bimodal
molecular weight distribution
1. Introduction
to be attractive to produce polyethylenes with bimodal or
broad molecular weight distributions. In these complexes
the differently surrounded metal centers should be kept
separated from each other by the ligand frameworks. In
contrast to the results of Pronko [37], the combination of
bis(arylimino)pyridine iron complexes and metallocene
complexes failed [39]. Therefore, it was decided to combine
metallocene complex fragments and phenoxyimine moie-
ties applying only zirconium as metal center which is then
coordinated in different ligand spheres. Combinations of
different ligand precursors were performed employing pal-
ladium catalyzed Sonogashira coupling reactions.
In the past 20 years, a huge number of transition metal
complexes useful for the polymerization of ethylene and
other a-olefins was developed. Especially metallocene com-
plexes proved to be very active candidates [1–7]. New gen-
erations of catalyst precursors were presented by
Brookhart et al. [8–12] and Gibson et al. [13–15] employing
catalysts with late transition metals. In 1998, the group of
Fujita presented bis(phenoxyimine)zirconium and titanium
complexes [16–29] as ‘‘single site’’ catalysts for monomodal
polyethylenes. In contrast to numerous mononuclear com-
plexes, only a few papers dealing with multinuclear com-
plexes containing different active sites were published up
to now [30–38]. Multinuclear complexes should be able to
produce polyethylenes with bimodal or broad molecular
weight distributions. Since mixtures of different mononu-
clear catalyst precursors often lead to polyethylenes with
averaged molecular weights, the synthesis of multinuclear
complexes containing combined ligand frameworks seemed
2. Results and discussion
2.1. Synthesis of 3-substituted salicylaldehydes
Deprotonation of ortho substituted phenol derivatives
with Grignard reagents and subsequent reaction with para-
formaldehyde furnished 3-substituted salicylaldehydes [19]
(see Scheme 1).
*
The introduction of iodo substituents into aniline [42] or
phenol [43] derivatives can be easily accomplished at room
Corresponding author. Tel.: +49 921 552555; fax: +49 921 552044.
E-mail address: helmut.alt@uni-bayreuth.de (H.G. Alt).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.10.001

5728
OH
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
R3
H
O
OH
1. EtMgBr, THF, 0 ˚C, 1h
2. (CH2O)n, toluene, NEt3,
88 ˚C, 2h
N
OH
R2
O
OH
R2
R1
R1
R1
R1
H
H
toluene
+ R3 - NH2
3. HCl, H2O
p-TosOH
- H2O
R2
R2
R1 = Bu,
R2 = H:
R2 = H:
1
2
3
4
t
Scheme 3. Synthesis of phenoxyimine compounds.
R1 = phenyl,
R1 = cyclohexyl, R2 = H:
R1 = cyclohexyl, R2 = Cl:
2-Iodofluorene was reacted with 2-methylbut-3-yn-2-ol
under Sonogashira conditions. Deprotection using potas-
sium hydroxide furnished 2-ethynylfluorene (Scheme 6).
Scheme 1. Synthesis of 3-substituted salicylaldehydes (see [40,41]).
2.4. Synthesis of bridged indenyl and fluorenyl derivatives
temperature using benzyltrimethylammonium dichloro-
iodate. Therefore, 3-tert-butyl salicylaldehyde (1) was
reacted with benzyltrimethyl-ammonium dichloroiodate
to give 3-tert-butyl-5-iodosalicylaldehyde (5) (Scheme 2).
For the synthesis of alkynyl substituted bridged metallo-
cene type ligand precursors 5-hexyn-2-one (23) was pre-
pared. Reaction with freshly distilled cyclopentadiene or
indene in a mixture of pyrrolidine and methanol yielded
the alkynyl fulvenes 24 and 25 (see Scheme 7).
2.2. Preparation of phenoxyimine compounds
The reaction of indenyllithium or fluorenyllithium with
the fulvenes 24 or 25 and the subsequent hydrolysis gave
three C1 bridged ligand precursors (Schemes 8 and 9).
Condensation reactions of substituted salicylaldehydes
with aniline derivatives yielded the phenoxyimine com-
pounds 6–15 (see Scheme 3 and Table 1).
Due to its lower boiling point, condensation reactions
using propargylamine as amine component were per-
formed at room temperature using molecular sieves
2.5. Sonogashira coupling reactions of phenoxyimine
compounds with indene or fluorene derivatives
˚
(3 A) as water absorbing agent [45]. While toluene was
A Sonogashira coupling reaction of 2-ethynylfluorene
(22) and the phenoxyimine derivative 6 furnished com-
pound 29 (see Scheme 10).
applied as a solvent for reactions with propargylamine,
ethanol had to be used for the reaction of 4-ethynylani-
line with 3-tert-butyl salicylaldehyde due to the insolubil-
ity of the aniline in toluene. Due to steric reasons,
phenoxyimine compounds containing halogen substitu-
ents at the para positions of the iminophenyl rings
seemed to be most suitable for further Sonogashira cou-
pling reactions.
According to Scheme 10, Sonogashira reactions of
phenoxyimine compounds with unbridged indene deriva-
tives were performed leading to the coupling products
30–33 (see Table 2). Partial isomerization at the indenyl
rings occurred during the Sonogashira reactions caused
by the triphenylphosphine ligands of the palladium com-
plex [50]. The coupling products mostly exhibited 3-substi-
tution at the five-membered ring.
2.3. Synthesis of unbridged indenyl and fluorenyl derivatives
In the same manner, bridged metallocene type ligand
precursors were reacted with iodo substituted phenoxyi-
mine compounds applying Sonogashira conditions.
A total of eight combined phenoxyimine/metallocene
type ligand precursors were prepared according to Scheme
11 (see also Table 3).
Deprotonation of indene with n-butyllithium and subse-
quent alkylation furnished the substituted indene com-
pounds 16–18 (see Scheme 4).
While the bromo compound 17 did not undergo the pal-
ladium catalyzed coupling reaction with trimethylsilylacet-
ylene, the reaction of 18 proceeded smoothly at room
temperature. Removal of the trimethylsilyl group yielded
1-(4-ethynylbenzyl)indene (20) (see Scheme 5).
The 13C NMR spectra of compounds 29 and 36 are
shown in Schemes 12 and 13. In the 13C NMR spectrum
of 29, the imino carbon atom appears at d = 163.4 ppm.
O
OH
O
OH
H
H
CH2Cl2, MeOH
-
BzNMe3+ ICl2
+
- BzNMe3+ Cl-
- HCl
I
1
5
Scheme 2. Synthesis of 3-tert-butyl-5-iodosalicylaldehyde (5) (see [44]).

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5729
Table 1
The quaternary carbon atoms of the aromatic ring systems
give ten signals at d = 160.6, 147.8, 143.5, 143.2, 141.9,
141.0, 137.7, 121.9, 121.2 and 119.0 ppm, while the aro-
matic CH groups yield twelve resonance signals at
d = 132.7, 130.8 (2 signals), 130.5, 128.1, 127.2, 126.9,
125.1, 121.3, 120.2, 119.8 and 118.5 ppm. The signals at
d = 132.7 and d = 121.3 ppm with doubled intensity can
be assigned to the equivalent carbon atoms of the imin-
ophenyl ring (11/12). The quaternary alkynyl carbon atoms
(14/15) appear at d = 91.2 and d = 89.2 ppm. The methy-
lene group of the fluorenyl moiety produces the signal at
d = 36.2 ppm, while the residual signals at d = 34.9 ppm
(Cq) and d = 29.4 ppm (CH3) can be assigned to the tert-
butyl substituent.
Synthesized phenoxyimine compounds
Compound
R1
R2
H
R3
6
tBu
I
7 [45]
8 [45]
9
tBu
tBu
tBu
H
H
I
HC
HC
C
C
H2C
The chiral compounds 34–41 were obtained as racemic
mixtures. Due to this fact, the assignment of the NMR sig-
nals is more complicated.
The 13C NMR spectrum of 36 (see Scheme 13) shows the
imine carbon atom at d = 162.6 ppm. The quaternary car-
bon atoms of the aromatic ring systems appear at
d = 160.6, 151.7, 144.9, 144.7, 142.5, 141.9, 137.7, 118.3
and 113.0 ppm, while the signals at d = 134.9, 132.9,
132.7, 132.5, 128.0, 127.3, 127.1, 126.9, 126.2, 126.1,
126.0, 119.7 and 119.2 ppm can be assigned to the aromatic
CH groups. The quaternary alkynyl carbon atoms produce
the signals at d = 88.3 and d = 80.6 ppm. The carbon atom
C1 of the cyclopentyl ring (10) yields the resonance signal at
d = 69.9 ppm, the carbon atom C9 of the fluorenyl moiety
(32) appears at d = 56.1 ppm. The less intensive signal at
d = 58.3 ppm can be assigned to C1 of the allylic substi-
tuted cyclopentadienyl ring (19), while the methylene group
of the vinylic isomer produces the signal at d = 46.3 ppm.
The quaternary carbon atom of the tert-butyl substituent
appears at d = 35.0 ppm, the methylene groups of the hexy-
nyl moiety give the signals at d = 41.1 and d = 15.4 ppm.
The quaternary bridging atom (17) furnishes the signal at
d = 43.1 ppm. The CH2 groups of the cyclopentyl ring
appear as two signals with doubled intensity at d = 34.8
and d = 24.5 ppm. The methyl groups of the tert-butyl
function generate the intensive signal at d = 29.4 ppm,
10
11
12
13
14
15
tBu
I
Phenyl
H
H
H
Cl
Cl
I
Phenyl
HC
I
C
H2C
Cyclohexyl
Cyclohexyl
Cyclohexyl
I
HC
C
H2C
Br
toluene
16
- LiBr
n-BuLi
pentane
Li+
toluene
- LiBr
Br
X
17
18
X = Br:
X = I:
X
Scheme 4. Synthesis of 1-substituted indenes (see [46]).

5730
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Me Si
3
CH2Cl2, MeOH
K2CO3
r.t., 2h
(PPh3)2PdCl2
CuI, NEt3
I
19
18
20
Me3Si
Scheme 5. Synthesis of 1-(4-ethynylbenzyl)indene (20).
HO
I
OH
KOH
toluene
110 ˚C, 2h
(PPh3)2PdCl2
CuI, NEt3
21
22
Scheme 6. Synthesis of 2-ethynylfluorene (22) (see [47]).
cyclopentadiene
pyrrolidine
MeOH
Cl
O
O
O
24
K2CO3
+
EtOH
23
indene
pyrrolidine
MeOH
25
+ isomer
Scheme 7. See [48,49].
while the terminal methyl group of the hexynyl moiety (18)
produces the signal at d = 17.4 ppm.
The mass spectrum of 36 shows the molecular ion at
m/z = 553. Loss of the fluorenyl moiety yields the base peak
at m/z = 388. Partial degradation of the hexynyl function
including the Cp ring leads to m/z = 282 (see Scheme 14).
1. FluLi
2. H2O
2.6. Synthesis of mononuclear zirconium complexes
24
+ isomer
26
Deprotonation of the phenolic hydroxy group of the
Scheme 8. See [49].
phenoxyimine compounds 6–15 and 29–33 with 1 equiv.

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5731
these compounds with 2 equiv. of potassium hydride and
subsequent reactions with zirconium tetrachloride only
produced polymeric products. Therefore, 1.5 equiv. of the
half sandwich complex cyclopentadienylzirconium trichlo-
ride were used instead of zirconium tetrachloride, but
defined complexes could not be obtained.
25
1. IndLi
2. H2O
1. FluLi
2. H2O
2.7. Synthesis of trinuclear zirconium complexes
The reaction of the combined metallocene/phenoxyi-
mine ligand precursors 34–41 with 3 equiv. of potassium
hydride and 1.5 equiv. of zirconium tetrachloride furnished
the trinuclear zirconium complexes 57–64, wherein the zir-
conium centers are differently coordinated. The central
bis(phenoxyimine) moiety contains octahedrally coordi-
nated zirconium, while the metallocene fragments show
tetrahedral coordination for the metal centers (see Scheme
16).
27
28
The prepared trinuclear complexes are listed in Table 5.
All of the synthesized bis(phenoxyimine)zirconium com-
plexes were characterized by mass spectrometry and ele-
mental analysis. Due to the presence of at least three
isomers of the phenoxyimine moieties in solutions and their
poor solubilities in deuterated solvents, the characteriza-
tion of the trinuclear complexes by NMR spectroscopy
was quite difficult. Despite of the broad signals found in
all 1H NMR spectra, assignments of the signal groups were
still possible. As can be seen from the MS data, the forma-
tion of indenyl and fluorenyl cations is highly favored over
all other cleavage reactions since the positive charge can be
delocalized easily. Therefore, the molecular ions are not
visible for most of the complexes. However, the elemental
analysis data agree very well with the theoretical predic-
Scheme 9. Synthesis of C1 bridged ligand precursors from fulvene 25.
I
N
OH
+
H
22
6
(PPh3)2PdCl2
CuI, NEt3
- HNEt3I
r.t., 20 h
1
tions. The MS, H NMR and elemental analysis data of
the trinuclear complexes are collected in Table 10.
N
OH
H
2.8. Results of ethylene polymerization
The zirconium complexes 42–64 were used as catalyst
precursors for the homogeneous polymerization of ethyl-
ene. The complexes were activated with methylalumoxane
(MAO) applying a ratio Zr:Al = 1:500. The polymerization
runs were routinely performed at a temperature of 35 ꢁC
over 1 h employing an ethylene pressure of 10 bar. As a sol-
vent n-pentane was used. The polymerization results are
given in Table 6. The values for the activities of the trinu-
clear complexes 57–64 are always related to 1 mol of the
catalyst precursor.
The phenoxyimine ligands of complexes 42, 47, 49 and
50 were prepared from 4-iodoaniline and differently substi-
tuted salicylaldehydes. Therefore, the substituents at the
salicylaldehyde rings are exclusively responsible for differ-
ences in polymerization activities and polymer properties
(see Scheme 17). The highest activity (8320 kg PE/mol Zr
h) was obtained for complex 42 containing a tert-butyl sub-
stituent at position 3 of the aldehyde ring. Exchange of the
tert-butyl group against a cyclohexyl rest (49) slightly
29
Scheme 10.
of potassium hydride and subsequent reaction with half an
equivalent of zirconium tetrachloride resulted in the forma-
tion of the mononuclear bis(phenoxyimine)zirconium
dichloride complexes 42–56 (see Scheme 15 and Tables 4
and 9). In the complexes, the metal center is octahedrally
coordinated by two chelating phenoxyimine ligands and
two chloro ligands. The complexes 42–51 obtained from
the ligand precursors 6–15 were already described in a pre-
vious paper [51].
The cis configuration of the chloro ligands is necessary
for a high activity of the catalyst after activation with
MAO and can be found in the three isomers with the lowest
energy (five isomers are possible) [21].
Attempts to prepare trinuclear zirconium complexes
starting with compounds 29–33 failed. Deprotonation of

5732
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Table 2
Coupling products of phenoxyimines and unbridged indenyl compounds
R–I R0C„CH Product
R–I R0C„CH Product
18
6
16
7
N
OH
N
OH
H
H
30
32
18
8
10 20
N
OH
N
OH
H
H
31
33
(50) leads to a further decrease of the activity due to its
electron withdrawing effect. Exchange of alkyl or cyclo-
alkyl groups at position 3 of the aldehyde ring against a
more electron withdrawing phenyl substituent (47) destabi-
lizes the cationic active center resulting in a reduced activity
of 1760 kg PE/mol Zr h.
N
OH
N
OH
H
H
10
(PPh3)2PdCl2
CuI, NEt3
While the polymerization activity decreases with
increasing electronegativity of the substituents at the alde-
hyde ring, the molecular weights of the polyethylenes
increase in the same order. Finally, the polyethylene pro-
duced with 47/MAO could not be dissolved in 1,2,4-tri-
chlorobenzene (for GPC analysis) due to its high
molecular weight.
I
+
RT, 20 h
- HNEt3I
The complexes 43, 44, 48 and 51 are the first ones con-
taining terminal alkynyl groups, that are active in the poly-
merization of ethylene [51]. Therefore, the affinity of the
cationic zirconium centers towards ethylene is high enough
to produce polyethylene instead of polyacetylene deriva-
tives. As expected, complexes 43 and 44 containing 3-tert-
butyl substituted aldehyde rings showed higher activities
than 48 and 51 bearing electron withdrawing substituents
at the aldehyde rings. The very high molecular weights
Mw of the resulting polyethylenes are noticeable compared
26
34
Scheme 11.
decreases the polymerization activity, since the steric bulk
at the a-carbon atom bonded to the aldehyde ring is low-
ered. An additional chloro substituent at the para position

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5733
Table 3
Synthesized ligand precursors for trinuclear complexes
R–I
R0C„CH
Product
R–I
R0C„CH
Product
10
26
14
26
N
OH
H
N
OH
Cl
H
38
34
10
28
6
26
N
OH
H
N
OH
H
39
35
9
26
6
27
N
OH
H
N
OH
H
40
36
(continued on next page)

5734
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Table 3 (continued)
R–I R0C„CH Product
R–I R0C„CH Product
11
26
6
28
N
OH
N
OH
H
H
41
37
4
6
8
22
19
23
24
18
16
21
12
20
17
18
23
24
25
15
12
11
26
25
13
28
17
11
27
14
11
12
8
7
N
9
OH
10
8
2
3
H
1
6
8
4
19+22
5
29
9
5
10
3
14+15
2
1;13;16
7
20;21
27
26;28
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
ppm (f1)
Scheme 12. 13C NMR spectrum of 29.
to the very low ones obtained with 45 and 46 having cyclo-
alkyl groups at the imino moieties. The complexes 43, 44
and 48 produced polyethylenes with very broad molecular
weight distributions (PD = 44.0/55.4/21.4). As expected,
complex 48 containing phenyl substituted phenoxyimine
ligands yielded the highest molecular weight polyethylene
in this series.
Due to the stronger electron withdrawing effect of the
alkynyl groups, the mononuclear bis(phenoxyimine)zirco-
nium dichloride complexes 52–57 containing indenylalky-

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5735
12
11
12
11
26
27
36
10
H
28
31
1
25
24
35
N
29
30
9
2
34
32
14
3
8
33
18
23
OH
17
16
15
20
13
7
4
6
5
19
6
6
21
22
36
6
7 / 9 / 20
22
23 – 26
29 - 31
27
28
10
1
32
18
13
14
16
8
3
4 /19
15 / 17
21
2
33 -36
5
12
11
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
ppm (t1)
Scheme 13. 13C NMR spectrum of 36.
nyl or fluorenylalkynyl substituents on their ligand frame-
works consistently showed lower polymerization activities
compared to their iodo substituted ‘‘precursor’’ complexes
(see Scheme 18).
56/MAO are nearly identical to that obtained from 46/
MAO.
In most cases, the polymerization activities of the trinu-
clear complexes 57–64 are lower compared to the summa-
rized activities of their mononuclear ‘‘precursor’’
complexes (see Scheme 20). Since zirconocene complexes
containing terminal alkynyl groups are inactive in ethylene
polymerization [52], the analogously structured x-alkenyl
substituted complexes A [4] (activity: 3950 [kg PE/mol Zr
h]) and B [53] (activity: 2200 [kg PE/mol Zr h]) are used
for comparison purposes (see Scheme 19).
However, comparison of the activities of 43 (2080 kg
PE/mol Zr h) containing a terminal ethynyl function and
52–54 displays similar values. Since the steric bulk caused
by the indenyl substituents in complex 55 is significantly
higher than that of the propynyl groups of complex 44, it
is more difficult for the ethylene molecules to reach the
active metal center leading to a reduced activity. In con-
trast to this result, the activity is less influenced, if the alky-
nyl substituent is introduced at position 5 of the aldehyde
ring. The properties of the polyethylene produced with
While the system 57/MAO displayed an activity similar
to the summarized activities of the mononuclear com-
plexes, the analogous complexes 58 and 59 were inactive

5736
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Scheme 14. Mass spectrum of 36 (ions with m/z < 150 were omitted).
R2
R1
R3
R3
H
OH
N
1. 2 KH, THF
r.t., 1h
O
Zr
O
H
R1
N
N
- H2
H
R3
Cl
Cl
2. ZrCl4, THF
r.t., 20h
R2
- 2 KCl
2 equiv.
R1
R1 = H, alkyl, cycloalkyl, phenyl
R2 = H, halogen
R2
R3 = alkynyl, cycloalkyl, substituted phenyl
Scheme 15. Synthesis of mononuclear bis(phenoxyimine)zirconium dichloride complexes.
or less active compared to the summarized activities of the
single-site compounds (see Scheme 20). The decrease in
activity of the complexes 60–62 may be explained by the
electron withdrawing effect of the introduced alkynyl
groups. On the other hand, the steric hindrance, also
caused by the MAO cages, around the central phenxyimine
moiety is dramatically increased resulting in lower activi-
ties. Considering the ethynyl substituted complex 43 as
phenoxyimine ‘‘precursor’’, the activity values obtained
for 62/MAO and 64/MAO are comparable with the sum-
marized values of the mononuclear compounds.
Analogously to mononuclear phenoxyimine zirconium
complexes, polymerization activity decreases when electron
withdrawing substituents (R1 and R2) are introduced into
the aldehyde rings (see Table 7).
While the polymerization activities of the trinuclear
complexes are somewhat lower than expected, the resulting
polyethylenes displayed the desired broad or bimodal
molecular weight distributions. The PD values varied
between 15 and 40. The GPC spectra of polyethylenes pro-
duced with the trinuclear complexes are compared to those
of the ‘‘single-site precursors’’. The molecular weights of

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5737
Table 4
Synthesized mononuclear bis(phenoxyimine)zirconium complexes 42–56
Complex
R1
R2
H
R3
42
tBu
I
43
tBu
H
HC
C
44
45
tBu
tBu
H
I
HC
C
H2C
46
47
tBu
I
Phenyl
H
I
48
49
Phenyl
H
H
HC
I
C
H2C
Cyclohexyl
50
51
52
Cyclohexyl
Cyclohexyl
tBu
Cl
Cl
H
I
HC
C
H2C
53
tBu
H
(continued on next page)

5738
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Table 4 (continued)
Complex
R1
R2
H
R3
54
tBu
55
56
tBu
H
tBu
Cl
Cl
Zr
N
OH
H
O
H
1. 6 KH, THF
r.t., 2h
N
N
Zr
- 3 H2
Cl
Cl
H
O
2. 3 ZrCl4,
r.t., 20h
- 6 KCl
Cl
Cl
34
Zr
2 equivs.
57
Scheme 16. Synthesis of the trinuclear zirconium complex 57.

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5739
Table 5
Synthesized trinuclear complexes
Complex
Complex
Cl
Zr
Cl
Cl
H
O
Zr
Cl
ZrCl2
N
N
O
ZrCl2
H
2
57
Cl
2
61
Cl
Zr
Cl
Cl
Cl
H
Zr
Zr
Zr
ZrCl2
ZrCl2
ZrCl2
N
O
N
N
N
O
O
O
ZrCl2
H
2
2
58
62
Cl
Zr
Cl
Cl
Cl
H
N
O
ZrCl2
H
2
2
59
63
Cl
Zr
Cl
Cl
Cl
ZrCl2
N
O
H
H
2
2
64
60

5740
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Table 6
Results of the ethylene polymerization with bis(phenoxyimine)zirconium dichloride complexes (polymerization conditions: 250 ml n-pentane, 35 ꢁC, 10 bar
ethylene, 1 h, Zr:Al 1:500)
Complex
Activity (kg PE/mol Zr h)
Mn (g/mol)
Mw (g/mol)
PD
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
8320
2080
4105
15600
14650
1760
168
7780
5100
–
1900
–
–
1030
10300
24500
–
2840
710
7260
5830
4280
3370
10700
41700
256700
237000
9500
5.74
44.0
55.4
2.83
3.00
32150
Polymer insoluble in 1,2,4-trichlorobenzene
24700
5420
8770
–
527900
75850
361480
–
21.4
14.0
41.2
–
Polymer insoluble in 1,2,4-trichlorobenzene
–
–
–
–
–
–
7380
86200
30700
134750
–
125600
292900
418500
255400
173500
702550
11.7
2.97
17.3
–
43.1
44.3
38.7
35.1
34.6
72.9
10350
7800
–
2915
6620
10810
7270
5000
9640
2580
7770
1060
5630
400000
300000
200000
100000
361480
75850
41700
polymer
insoluble
0
42
49
50
47
Scheme 17. Increase of Mw at decreasing electron density in the aldehyde ring.
16000
14650
indenylalkynyl or fluorenylalkynyl
iodo "precursor"
14000
12000
10000
8000
6000
4000
2000
0
10300
8320
8320
8320
4105
1900
52
1030
0
0
42
53 42
54 42
55 44
56 46
Scheme 18. Comparison of the polymerization activities of the complexes 52–56 with their iodo substituted ‘‘precursor’’ complexes.

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5741
Table 7
Influence of the substituents R1 and R2 on the polymerization activities of
analogously structured trinuclear complexes
A
B
Complex
R1
R2
Activity (kg PE/mol Zr h)
Cl
Cl
Cl
Cl
Zr
Zr
62
61
60
tert-Butyl
Cyclohexyl
Phenyl
H
Cl
H
7770
2580
710
Scheme 19. x-Alkenyl substituted zirconocene complexes [4,53].
Considering complex 43 containing terminal ethynyl
groups as the ‘‘single-site precursor‘‘ for the trinuclear
complexes 62 and 64, the GPC spectra are better compara-
ble (see Scheme 23).
The values for Mpeak (51100 g/mol) and Mw (237000 g/
mol) of the polyethylene obtained with 43/MAO are com-
parable to those for 62/MAO (Mpeak = 50170 g/mol,
Mw = 255400 g/mol), but are significantly lower than those
of the polyethylene produced with 64/MAO.
While the mononuclear complex 47 produced very high
molecular weight polyethylene that could not be dissolved
in 1,2,4-trichlorobenzene, the trinuclear complex 60 yielded
a polyethylene with an almost bimodal molecular weight
distribution (see Scheme 24).
Since the metallocene moieties produce a polyethylene
with Mw = 140000 g/mol [4], the solubility in 1,2,4-trichlo-
robenzene is increased, and GPC spectroscopy can be
performed.
The influence of alkynyl substituents at position 5 of the
former aldehyde rings on the molecular weight Mw is sig-
nificantly lower. The Mn and Mw values of the polyethyl-
enes obtained with 46/MAO and 56/MAO agree very
well with each other (see Table 6). Therefore, comparisons
of the polyethylenes obtained from the iodo containing
‘‘precursor’’ complexes 45 and 46 to those obtained from
the trinuclear complexes 59 and 57 are useful. The iodo
substituted complexes 45 and 46 produced polyethylenes
with narrow molecular weight distributions (45:
the polyethylenes resulting from A/MAO and B/MAO are
140000 g/mol and 210000 g/mol, respectively [4,53]. There-
fore, it could be estimated which zirconium center of the
trinuclear complexes produced the higher molecular weight
fraction.
The GPC spectrum of the polyethylene produced with
42/MAO exhibits a quite narrow molecular weight distri-
bution with PD = 5.74 (see Scheme 21). Contrary to this
behaviour, the trinuclear complex 62 yields a polyethylene
with a broad molecular weight distribution (PD = 35.1).
While Mn remains nearly constant (42: 7240 g/mol; 62:
7270 g/mol), Mw increases from 40200 g/mol (42) to
255400 g/mol (62). The curve maximum (Mpeak) is shifted
from 12070 g/mol to 50170 g/mol. Therefore, in this case
the phenoxyimine moiety produced the lower molecular
weight fraction, while the metallocene fragments yielded
the higher molecular weight component.
The differences of the molecular weight distributions are
more obvious when the GPC spectra of the polyethylenes
produced with 42/MAO and 64/MAO are compared. In
case of 64/MAO, the introduction of indenyl rings instead
of cyclopentadienyl rings lead to the production of higher
molecular weight polyethylene by the metallocene moieties
(see Schemes 21 and 22). The molecular weights Mpeak and
Mw are shifted up to 81700 g/mol and 702550 g/mol,
respectively.
30000
trinuclear complex
24500
25000
23500
sum "precursors"
22550
20000
16850
15000
10000
13000
9980
7770
6480
5630
64
5000
2840
2580
61
0
58
0
57 46
+ 2A
59
62
46
+ 2B
45
+ 2A
50
43
43
+ 2A
+ 2A
+ 2B
Scheme 20. Comparison of the polymerization activities of the trinuclear complexes 57–64 and their ‘‘precursor’’ complexes.

5742
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Scheme 21. GPC spectrum of the polyethylene produced with 42/MAO.
Scheme 22. GPC spectrum of the polyethylene obtained with 64/MAO.
Mw = 9500 g/mol; 46: Mw = 32150 g/mol; PD’s < 3). By
introduction of the metallocene moieties into the ligand
frameworks (complexes 59 and 57), these metal centers
produce a higher molecular weight polyethylene resulting
in broad or bimodal molecular weight distributions. This
effect is clearly visible in the GPC spectra (see Schemes
25 and 26).
visible in the spectrum corresponding to the metallocene
catalyzed part. Mw increases from 9500 g/mol (45) to
125600 g/mol (59), the polydispersity index PD also
increases from 2.83 (45) to 43.1 (59).
A better separation of the peaks in the GPC spectra may
be accomplished using metallocene moieties containing 4,5-
disubstituted fluorenyl fragments. Such zirconocene com-
plexes are known to produce very high molecular weight
polyethylenes [54].
The polyethylene produced with 59/MAO still contains
a low molecular weight fraction. Additionally, a shoulder is

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5743
Scheme 23. GPC spectrum of the polyethylene produced with 43/MAO.
Scheme 24. GPC spectrum of the polyethylene resulting from 60/MAO.
3. Experimental
were dried over molecular sieves. Deuterated solvents
(CDCl3, CDCl2) for NMR spectroscopy were stored over
molecular sieves (3 A).
Methylalumoxane (30% in toluene) was purchased from
Crompton (Bergkamen) and Albemarle (Baton Rouge,
USA/Louvain – La Neuve, Belgium). Ethylene (3.0) and
argon (4.8/5.0) were supplied by Rießner Company (Lich-
tenfels). All other starting materials were commercially
available and were used without further purification.
˚
All experimental work was routinely carried out using
Schlenk technique. Dried and purified argon was used as
inert gas. n-Pentane, diethyl ether, toluene and tetrahydro-
furan were purified by distillation over Na/K alloy. Diethyl
ether was additionally distilled over lithium aluminum
hydride. Methylene chloride was dried with phosphorus
pentoxide and calcium hydride. Methanol and ethanol

5744
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Scheme 25. GPC spectrum of the polyethylene produced with 45/MAO.
Scheme 26. GPC spectrum of the polyethylene produced with 59/MAO.
3.1. NMR spectroscopy
solvent signal (d = 77.0 ppm for CDCl3, d = 53.5 ppm
for CD2Cl2).
The spectrometer Bruker ARX 250 was available
for the recording of the NMR spectra. The samples
were prepared under inert atmosphere (argon) and
routinely recorded at 25 ꢁC. The chemical shifts in the
1H NMR spectra are referred to the residual proton
signal of the solvent (d = 7.24 ppm for CDCl3, d =
5.32 ppm for CD2Cl2) and in 13C NMR spectra to the
3.2. Mass spectrometry
Mass spectra were routinely recorded at the Zentrale
Analytik of the University of Bayreuth with a VARIAN
MAT CH-7 instrument (direct inlet, EI, E = 70 eV) and a
VARIAN MAT 8500 spectrometer.

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5745
Table 8
NMR and MS data for compounds 1–41
Compound 1H NMR
13C NMR
MS [m/z]
1
2
3
4
11.84 s (1H, OH), 9.72 s (1H, O@C–H), 7.43–7.47 m (1H, 197.2 (O@C–H), 161.1, 138.0, 120.7 (Cq), 134.1, 132.0, 178 Mꢀ+ (26)
Ar–H), 7.25–7.29 m (1H, Ar–H), 6.86 t (1H, Ar–H), 1.38 s 119.3 (Ar–CH), 34.8 (Cq), 29.2 (tBu–CH3)
163 MꢁMe (100)
t
(9H, Bu–CH3)
135 MꢁC3H7 (39)
11.53 s (1H, OH), 9.94 s (1H, O@C–H), 7.36–7.62 m (7H, 196.8 (O@C–H), 158.9, 136.3, 130.5, 120.9 (Cq), 137.8, 198 Mꢀ+ (100)
Ar–H), 7.09 t (1H, Ar–H)
133.2, 128.3, 127.7, 119.9 (Ar–CH)
197 MꢁH (53)
169 MꢁH–C@O (21)
11.38 s (1H, OH), 9.83s (1H, O@C–H), 7.41–7.45m (1H, Ar– 196.9 (O@C–H), 159.2, 136.3, 120.1 (Cq), 134.1, 131.2, 204 Mꢀ+ (100)
H), 7.34–7.37 m (1H, Ar–H), 6.95 t (1H, Ar–H), 2.96-3.02 m 119.6 (Ar–CH), 36.2 (CH), 32.8, 26.9, 26.4 (CH2)
(1H, CH), 1.80–1.89 m (4H, CH2), 1.33–1.42 m (6H, CH2)
186 MꢁH2O (69)
135 MꢁC5H9 (96)
11.26 s (1H, OH), 9.79 s (1H, O@C–H), 7.35 d (1H, Ar– 195.9 (O@C–H), 157.8, 138.9, 124.5, 120.6 (Cq), 134.2, 238 Mꢀ+ (100)
H), 7.31 d (1H, Ar–H), 2.91–3.00 m (1H, CH), 1.82–1.86 m 129.7 (Ar–CH), 36.2 (CH), 32.6, 26.7, 26.1 (CH2)
(4H, CH2), 1.19–1.50 m (6H, CH2)
220 MꢁH2O (36)
203 MꢁCl (98)
169 MꢁC5H9 (70)
5
6
11.71 s (1H, OH), 9.75 s (1H, O@C–H), 7.67 d (1H, Ar– 195.9 (O@C–H), 160.8, 141.2, 122.4 (Cq), 142.5, 139.9 304 Mꢀ+ (58)
t
H), 7.66 d (1H, Ar.H), 1.36 s (9H, Bu–CH3)
(Ar–CH), 80.7 (Cq, C-I), 35.0 (Cq), 29.0 (tBu–CH3)
289 MꢁMe (100)
261 MꢁC3H7 (30)
13.67 s (br, 1H, OH), 8.58 s (1H, N@C–H), 7.70–7.73 m 163.7 (N@C–H), 160.5, 148.1, 137.7, 118.9, 91.3 (Cq), 379 Mꢀ+ (66)
(2H, Ar–H), 7.39 dd (1H, Ar–H), 7.23 dd (1H, Ar–H),
7.01–7.04 m (2H, Ar–H), 6.87 t (1H, Ar–H), 1.45 s (9H,
tBu–CH3)
138.4, 130.8, 130.7, 123.2, 118.5 (Ar–CH), 34.9 (Cq), 364 MꢁMe (100)
29.3 (tBu–CH3)
336 MꢁC3H7 (79)
7
8
9
13.71 s (br, 1H, OH), 8.60 s (1H, N@C–H), 7.21–7.55 m 163.8 (N@C–H), 160.6, 148.6, 137.7, 120.3, 118.9 (Cq), 277 Mꢀ+ (74)
(6H, Ar–H), 6.87 t (1H, Ar–H), 3.13 s (1H, „CH), 1.46 s 133.3, 130.8, 130.7, 121.2, 118.5 (Ar–CH) 83.3 (Cq,
(9H, Bu–CH3)
262 MꢁMe (100)
t
C„C), 77.9 („CH), 34.9 (Cq), 29.3 (tBu–CH3)
234 MꢁC3H7 (84)
13.56 s (br, 1H, OH), 8.67 s (1H, N@C–H), 7.36 dd (1H, 166.5 (N@C–H), 160.0, 137.4, 118.6 (Cq), 130.1, 129.8, 215 Mꢀ+ (54)
Ar–H), 7.19 dd (1H, Ar–H), 6.85 t (1H, Ar–H), 4.52 t (2H, 118.1 (Ar–CH), 76.7 (Cq, C„C), 76.2 („CH), 45.2
CH2), 2.56 t (1H, „CH), 1.47 s (9H, Bu–CH3)
200 MꢁMe (100)
t
(CH2), 34.9 (Cq), 29.3 (tBu–CH3)
172 MꢁC3H7 (66)
14.22 s (br, 1H, OH), 8.21 s (1H, N@C–H), 7.48 d (1H,
161.6 (N@C–H), 160.4, 140.4, 120.8, 79.1 (Cq), 137.6, 371 Mꢀ+ (100)
Ar–H), 7.36 d (1H, Ar–H), 3.71–3.76 m (1H, N–CH),
1.67–1.95 m (8H, CH2), 1.38 s (9H, Bu–CH3)
137.5 (Ar–CH), 69.9 (N–CH), 34.9 (Cq), 34.7, 24.4
356 MꢁMe (81)
328 MꢁC3H7 (87)
244 MꢁI (6)
t
(CH2), 29.1 (tBu–CH3)
10
11
12
13
14.36 s (br, 1H, OH), 8.24 s (1H, N@C–H), 7.48 d (1H,
161.6 (N@C–H), 160.7, 140.5, 120.8, 78.9 (Cq), 137.7, 385 Mꢀ+ (100)
Ar–H), 7.37 d (1H, Ar–H), 3.17–3.21 m (1H, N–CH), 1.24- 137.6 (Ar–CH), 67.4 (N–CH), 34.9 (Cq), 34.2, 24.4,
1.82 m (10H, CH2), 1.39 s (9H, Bu–CH3)
370 MꢁMe (64)
t
22.7 (CH2), 29.1 (tBu–CH3)
342 MꢁC3H7 (73)
13.73 s (br, 1H, OH), 8.64 s (1H, N@C–H), 7.64–7.74 m 163.0 (N@C–H), 158.5, 147.7, 137.4, 130.1, 119.1, 91.7 399 Mꢀ+ (100)
(4H, Ar–H), 7.36–7.50 m (5H, Ar–H), 7.00–7.04 m (3H,
(Cq) 138.5, 134.4, 131.9, 129.3, 128.2, 127.3, 123.1,
398 MꢁH (42)
Ar–H)
119.2 (Ar–CH)
272 MꢁI (18)
13.57 s (br, 1H, OH), 8.73 s (1H, N@C–H), 7.64–7.68 m 166.0 (N@C–H), 158.0, 137.7, 129.8, 118.9 (Cq), 133.6, 235 Mꢀ+ (100)
(2H, Ar–H), 7.32-7.49 m (5H, Ar–H), 6.99 t (1H, Ar–H), 131.2, 129.8, 128.3, 127.1, 118.8 (Ar–CH), 77.4 (Cq,
4.52 d (2H, CH2), 2.57 t (1H, „CH) C„C), 76.6 („CH), 45.3 (CH2)
196 M-propynyl (23)
13.42 s (br, 1H, OH), 8.57 s (1H, N@C–H), 7.69–7.73 m 163.4 (N@C–H), 158.6, 148.1, 135.8, 118.3, 91.3 (Cq), 405 Mꢀ+ (100)
(2H, Ar–H), 7.31 dd (1H, Ar–H), 7.21 dd (1H, Ar–H),
138.4, 130.7, 129.9, 123.1, 118.9 (Ar–CH), 36.6 (CH), 404 MꢁH (39)
6.99–7.03 m (2H, Ar–H), 6.90 t (1H, Ar–H), 3.01–3.06 m 32.9, 27.0, 26.4 (CH2)
(1H, CH), 1.74-1.93 m (4H, CH2), 1.24-1.50 m (6H, CH2)
350 MꢁC4H7 (24)
278 MꢁI (3)
14
15
16
13.39 s (br, 1H, OH), 8.45 s (1H, N@C–H), 7.68–7.73 m 162.0 (N@C–H), 157.2, 147.5, 138.1, 123.7, 119.0, 91.6 439 Mꢀ+ (100)
(2H, Ar–H), 7.23 d (1H, Ar–H), 7.16 d (1H, Ar–H), 6.97– (Cq), 138.5, 130.6, 128.6, 123.8 (Ar–CH) 36.6 (CH),
404 MꢁCl (24)
384 MꢁC4H7 (40)
312 MꢁI (6)
7.01 m (2H, Ar–H), 2.97–3.03 m (1H, CH), 1.74–1.90 m
(4H, CH2), 1.24-1.43 m (6H, CH2)
32.7, 26.9, 26.3 (CH2)
13.20 s (br, 1H, OH), 8.58 s (1H, N@C–H), 7.17 d (1H,
165.0 (N@C–H), 156.7, 137.7, 123.2, 118.8 (Cq), 129.7, 275 Mꢀ+ (81)
Ar–H), 7.12 d (1H, Ar–H), 4.51 d (2H, CH2), 2.93–3.02 m 128.1 (Ar–CH), 77.1 (Cq, C„C), 76.8 („CH), 36.6
(1H, N–CH), 2.55 t (1H, „CH), 1.79–1.87 m (4H, CH2), (CH), 45.3, 32.7, 26.8, 26.3 (CH2)
1.20–1.40 m (6H, CH2)
240 MꢁCl (29)
236 M-propynyl
(100)
7.68–7.71 m (1H, Ar–H), 7.36–7.50 m (3H, Ar–H), 6.98– 146.3, 144.4 (Cq), 138.4, 131.9, 127.3, 125.2, 123.2,
7.01 m (1H, Ar–H), 6.72–6.75 m (1H, Ar–H), 3.76 dt (1H, 121.4 (Ar–CH), 82.8 (Cq, C„C), 69.5 („CH), 48.9
Ind-H1), 2.73–2.82 m (1H, CH2), 2.43-2.54 m (1H, CH2), (CH, Ind-C1), 21.2 (CH2)
2.19 t (1H, „CH)
154 Mꢀ+ (69)
115 M-propynyl
(100)
(continued on next page)

5746
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Table 8 (continued)
Compound 1H NMR
13C NMR
MS [m/z]
17
7.11–7.48 m (8H, Ar–H), 6.84 dd (1H, Ar–H), 6.45 dd (1H,
Ar–H), 3.68-3.76 m (1H, Ind-H1), 3.09 dd (1H, CH2), 2.75 dd 124.8, 123.2, 121.3 (Ar–CH), 131.4, 130.9 (je 2 Ar–
(1H, CH2)
CH), 51.5 (CH, Ind-C1), 37.3 (CH2)
146.7, 144.3, 139.2, 120.1 (Cq), 138.5, 131.4, 126.9,
284/286 Mꢀ+ (58)
169/171 M-
indenyl (100)
18
7.61–7.65 m (2H, Ar–H), 7.19-7.35 m (4H, Ar–H), 6.97–7.00 m 146.7, 144.3, 139.8 (Cq), 138.4, 131.3, 126.8, 124.8,
332 Mꢀ+ (48)
(2H, Ar–H), 6.79–6.81 m (1H, Ar–H), 6.39-6.42 m (1H, Ar–H), 123.1, 121.3 (Ar–CH), 137.3, 131.2 (je 2 Ar–CH), 91.5 217 M-indenyl
3.66-3.72 m (1H, Ind-H1), 3.02–3.10 dd (1H, CH2), 2.66-2.74 (Cq, C-I), 51.4 (CH, Ind-C1), 37.4 (CH2)
dd (1H, CH2)
(100)
19
(1H NMR data for the vinylic, 3-substituted isomer) 7.19–7.47
m (8H, Ar–H), 6.10–6.12 m (1H, Ind-H2), 3.88 d (2H, CH2,
Ind-H1), 3.35 d (2H, CH2), 0.25 s (9H, SiMe3)
(
13C NMR data for the vinylic, 3-substituted isomer) n. d.
144.8, 144.5, 142.9, 140.0, 120.8 (Cq), 132.0, 128.8 (je 2
Ar–CH), 130.3, 126.0, 124.7, 123.8, 119.3 (Ar–CH),
105.2, 93.6 (Cq, C„C), 37.7, 34.4 (CH2), 0.0 (SiMe3)
20
21
22
23
7.16–7.48 m (8H, Ar–H), 6.14 m (1H, Ind-H2), 3.90 d (2H,
144.8, 144.5, 142.8, 140.3, 119.8 (Cq), 132.2, 128.9 (je 2 230 Mꢀ+ (51)
CH2, Ind-H1), 3.35 d (2H, CH2), 3.04 s (1H, „CH)
Ar–CH), 130.3, 126.0, 124.7, 123.8, 119.3 (Ar–CH),
84.3 (Cq, C„C), 76.8 („CH), 37.7, 34.4 (CH2)
115 M-indenyl
(100)
7.30–7.72 m (7H, Ar–H), 3.82 s (2H, CH2), 2.43 s (br, 1H,
OH), 1.67 s (6H, CH3)
143.5, 143.1, 141.8, 141.0, 120.7, 65.7 (Cq), 130.5,
248 Mꢀ+ (72)
128.2, 127.1, 126.9, 125.1, 120.2, 119.7 (Ar–CH), 93.8, 233 MꢁMe (100)
82.8 (Cq, C„C), 36.7 (CH2), 31.6 (CH3)
7.35-7.78 m (7H, Ar–H), 3.87 s (2H, CH2), 3.11 s (1H, „CH) 143.6, 143.1, 142.3, 140.9, 120.0 (Cq), 131.0, 128.7,
127.3, 126.9, 125.1, 120.2, 119.7 (Ar–CH), 84.4 (Cq,
190 Mꢀ+ (100)
189 MꢁH (98)
C„C), 76.9 („CH), 36.7 (CH2)
2.65 t (2H, CH2), 2.36–2.43 m (2H, CH2), 2.13 s (3H, CH3),
1.91 t (1H, „CH)
206.3 (Cq), 82.8 (Cq, C„C), 68.7 („CH), 42.1, 12.9
(CH2), 29.8 (CH3)
96 Mꢀ+ (7)
95 MꢁH (60)
81 MꢁHꢁMe
(67)
24
25
6.53–6.56 m (4H, Cp), 2.79 t (2H, CH2), 2.43–2.50 m (2H,
CH2), 2.26 s (3H, CH3), 2.04 t (1H, „CH)
150.2, 143.6 (Cq), 131.5, 131.2, 120.8, 120.4 (Cp–CH), 144 Mꢀ+ (11)
83.1 (Cq, C„C), 69.7 („CH), 35.5, 18.5 (CH2), 20.9
(CH3)
143 MꢁH (18)
129 MꢁMe (100)
7.72–7.75 m (1H, Ar–H), 7.25–7.38 m (3H, Ar–H), 6.83–6.89 m 144.8/144.2, 144.17143.8, 138.0/ 137.5, 135.8/134.9
(2H, Ar–H), 3.05/2.85 t (2H, CH2), 2.51–2.63 m (2H, CH2), (Cq), 129.5/ 129.3, 127.8/127.2, 126.5/126.4, 125.2/
2.46/2.33 s (3H, CH3), 2.14/2.07 t (1H, „CH) (signals for the 124.9, 123.9/123.3, 121.3/ 121.2 (Ar–CH), 84.9/83.5
isomers 1:1)
194 Mꢀ+ (65)
179 MꢁMe (98)
155 M-propynyl
(Cq, C„C), 69.4/69.2 („CH), 23.0/21.0 (CH3), 37.2/ (100)
34.8, 18.5/17.3 (CH2) (signals for the isomers 1:1)
26
27
7.63–7.84 m (3H, Ar–H), 7.36–7.50 m (3H, Ar–H), 7.17–7.20 m 153.8/151.6, 144.9/144.6, 144.5, 142.5/142.4, 141.9 (Cq), 310 Mꢀ+ (100)
(1H, Ar–H), 6.83–7.00 m (1H, Ar–H), 6.57–6.73 m (2H, Cp), 135.1, 132.8, 132.3, 131.6, 129.8, 128.1, 127.4, 127.3,
6.22–5.99 m (1H, Cp), 4.19/ 4.13 s (1H), 3.14 m (2H, Cp), 2.30- 127.3, 127.2, 126.9, 126.4, 126.3, 126.2, 126.1, 126.1,
2.39 m (2H, CH2), 2.07-2.10 m (3H, CH2/„CH), 0.68 s (3H, 125.7, 119.8, 119.4, 119.3 (Ar–CH) 85.3/85.1 (Cq, C„
295 MꢁMe (21)
165 Fluorenyl
(42) (vinylic
CH3)
C), 68.6/68.5 („CH), 58.2/56.0 (CH), 43.0, 41.1, 41.0, isomer)
40.3, 38.7, 14.5/14.4 (CH2/Cq/Bru¨cke), 17.8/17.3 (CH3)
6.79–7.88 m (8H, Ar–H), 6.08-6-63 m (4H, Ar–H), 4.19–4.23 m 153.0, 146.1, 146.0, 145.9, 145.9, 145.8, 145.8, 145.0,
(1H), 3.41–3.54 m (1H), 2.77–3.02 m (2H, CH2), 1.90–2.17 m 145.0, 144.3, 144.2, 143.7, 143.5, 143.5, 143.4, 143.2
310 Mꢀ+ (46)
295 MꢁMe (36)
195 M-fluorenyl
(100)
(3H, CH2/„CH), 0.71/0.80/ 0.86/0.88 s (3H, CH3)
(Cq), 143.3, 138.2, 137.1, 134.2, 132.7, 132.0, 131.9,
131.6, 131.2, 126.8, 126.7, 126.5, 126.5, 126.5, 126.4,
126.2, 126.0, 125.4, 125.4, 125.3, 125.0, 124.9, 124.6,
124.5, 124.4, 124.3, 124.2, 124.1, 123.9, 123.7, 123.6,
123.4, 122.3, 122.2, 122.2, 122.1, 122.0, 122.0, 121.8,
121.7, 121.7, 121.6, 121.4, 121.3, 121.2, 121.0, 120.8,
120.5 (Ar–CH), 84.9/84.7 (Cq, C„C), 68.6/68.5
(„CH), 58.3, 57.9, 57.3, 56.8, 55.7, 55.4, 55.2, 54.8
(CH), 43.4, 43.0, 39.3, 39.2, 38.9, 37.5, 29.0, 22.5
(CH2/Cq/Bru¨cke), 20.4/19.5/19.3/19.0 (CH3), 15.0/14.8/
14.6/14.5 (CH2)
28
7.55–7.96 m (4H, Ar–H), 7.19-7.43 m (6H, Ar–H), 6.92–7.03 m 153.1, 150.3, 148.6, 148.1, 146.4, 145.4, 144.9, 144.6,
360 Mꢀ+ (30)
(1H, Ar–H), 6.22–6.35 m (1H, Ar–H), 4.70–4.76 m (1H), 3.38– 143.3, 142.6, 142.5, 141.9 (Cq), 143.9, 143.8, 131.8, 131.4, 195 M-fluorenyl
3.52 m (1H), 2.28–3.18 m (2H, CH2), 1.88–2.17 m (3H, CH2/ 128.5, 127.3, 127.0, 126.8, 126.7, 126.7, 126.7, 126.4,
„CH) 0.66/0.60 s (3H, CH3) 126.3, 126.3, 126.1, 126.0, 125.8, 125.6, 125.4, 125.3,
(100)
165 Fluorenyl
125.0, 124.9, 124.7, 124.6, 123.5, 122.3, 121.8, 121.7 (Ar– (78)
CH), 85.0/84.9(Cq, C„C), 68.4/68.2(„CH), 54.9/54.8,
54.1/54.0 (CH), 52.8, 44.1, 42.7, 39.7, 37.3, 28.8 (CH2/
Cq/Brucke), 19.7 (CH3), 14.9/14.4 (CH2)

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5747
Table 8 (continued)
Compound 1H NMR
13C NMR
MS [m/z]
29
30
31
32
13.80 s (br, 1H, OH), 8.62 s (1H, N@C–H), 7.71–7.79 m 163.4 (N@C–H), 160.6, 147.8, 143.5, 143.2, 141.9,
(3H, Ar–H), 7.53–7.61 m (4H, Ar–H), 7.22–7.43 m (6H, 141.0, 137.7, 121.9, 121.2, 119.0 (Cq), 132.7, 130.8,
Ar–H), 6.88 t (1H, Ar–H), 3.90 s (2H, CH2), 1.49 s (9H, 130.8, 130.5, 128.1, 127.2, 126.9, 125.1, 121.3, 120.2,
441 Mꢀ+ (32)
426 MꢁMe (10)
400 MꢁC3H5 (9)
280 Flu–C„C–Ph–
NH (100)
tBu–CH3)
119.8, 118.5 (Ar–CH), 91.2, 89.2 (Cq, C„C), 36.2
(CH2), 34.9 (Cq), 29.4 (tBu–CH3)
13.88 s (br, 1H, OH), 8.62 s (1H, N@C–H), 7.24–7.55 m 163.4 (N@C–H), 160.6, 147.7, 144.5, 144.2, 139.1,
(10H, Ar–H), 6.91 t (1H, Ar–H), 6.48-6.63 m (1H, @CH), 137.7, 122.2, 119.0 (Cq), 132.8 (2C), 130.8, 130.6,
405 Mꢀ+ (26)
390 MꢁMe (22)
3.75 m (2H, Ind-CH2), 3.53–3.61 m (1H, CH2), 3.48–3.52 129.9, 126.2, 125.0, 123.9, 121.2 (2C), 118.9, 118.5
362 MꢁC3H7 (26)
t
m (1H, CH2), 1.53 s (9H, Bu–CH3)
(Ar–CH), 87.5, 82.0 (Cq, C„C), 37.7, 19.2 (CH2), 35.0 290 Mꢁindenyl (25)
(Cq), 29.4 (tBu–CH3)
115 Indenyl (100)
419 Mꢀ+ (88)
13.65 s (br, 1H, OH), 8.61 s (1H, N@C–H), 6.98–7.38 m 163.1 (N@C–H), 160.6, 147.8, 145.0, 141.6, 138.0,
(10H, Ar–H), 6.85 t (1H, Ar–H), 6.10-6.16 m (1H, @CH), 136.2, 122.2, 118.5 (Cq), 133.0 (2C), 130.4, 130.3, 128.7 404 MꢁMe (28)
4.51 t (2H, CH2), 3.79–3.83 m (2H, CH2), 3.75 m (2H, Ind- (2C), 126.1, 125.7, 124.3, 123.6, 121.3, 119.4 (Ar–CH), 376 MꢁC3H7 (25)
t
CH2), 1.47 s (9H, Bu–CH3)
89.5, 83.5 (Cq, C„C), 48.3, 38.3, 33.8 (CH2), 34.9
128 Ind@CH2 (100)
(Cq), 29.7 (tBu–CH3)
13.81 s (br, 1H, OH), 8.63 s (1H, N@C–H), 7.25–7.58 m 163.4 (N@C–H), 160.6, 147.9, 144.9, 144.5, 142.9,
481 Mꢀ+ (100)
(14H, Ar–H), 6.88 t (1H, Ar–H), 6.13–6.16 m (1H, @CH), 139.9, 137.7, 121.8, 120.9, 119.0 (Cq), 132.7 (2C), 131.7 466 MꢁMe (52)
3.91 m (2H, CH2), 3.36 m (2H, CH2), 1.47 s (9H, tBu–CH3) (2C), 131.0, 130.8, 130.6, 130.3, 129.0 (2C), 126.1,
124.7, 123.8, 121.3 (2C), 119.3, 118.5 (Ar–CH), 90.4,
88.7 (Cq, C„C), 37.8, 34.4 (CH2), 34.9 (Cq), 29.3
438 MꢁC3H7 (52)
(tBu–CH3)
33
34
14.69 s (br, 1H, OH), 8.30 s (1H, N@C–H), 7.23–7.52 m 162.4 (N@C–H), 161.8, 144.9, 144.5, 143.0, 139.3,
(10H, Ar–H), 6.13-6.17 m (1H, @CH), 3.91 m (2H, CH2), 138.1, 121.4, 118.5, 112.0 (Cq), 132.9, 132.5, 131.5
487 Mꢀ+ (100)
472 MꢁMe (22)
3.37 m (2H, CH2), 3.18–3.28 m (1H, N–CH), 1.81–1.85 m (2C), 130.3, 129.0 (2C), 126.1, 124.7, 123.8, 119.4 (Ar– 436 MꢁC3H5 (25)
t
(4H, CH2), 1.26–1.69 m (6H, CH2), 1.46 s (9H, Bu–CH3) CH) 89.5, 87.3 (Cq, C„C), 67.2 (N–CH), 34.4 (Cq),
404 M-cyclohexyl
37.8, 35.0, 34.3 (2C) 25.5, 24.5 (2C) (CH2), 29.3 (CH3) (13)
14.50 s (br, 1H, OH), 8.26 s (1H, N@C–H), 7.66–7.73 m 162.4 (N@C–H), 160.9, 151.6, 144.9, 144.6, 142.4,
567 Mꢀ+ (34)
(4H, Ar–H), 7.22–7.44 m (4H, Ar–H), 6.92–7.14 m (2H,
Ar–H), 6.46–6.77 m (3H, Ar–H), 4.17 s (1H, Flu–H9),
3.17–3.26 m (1H, N–CH), 3.05–3.13 m (2H, Cp–CH2),
141.8, 137.7, 118.4, 112.6 (Cq), 134.9, 132.8, 132.6,
132.4, 128.0, 127.1, 127.0, 126.8, 126.1, 126.0, 125.9,
119.6, 119.1 (Ar–CH), 88.2, 80.4 (Cq, C„C), 67.3 (N– (43)
402 MꢁFlu (89)
346 MꢁFlu–C4H8
2.12–2.38 m (4H, CH2), 1.78–1.84 m (4H, CH2), 1.22–1.70 CH), 56.0 (Flu–CH) 43.0, 34.8 (Cq), 46.0, 41.0, 34.3
165 Flu (100)
t
m (6H, CH2), 1.40 s (9H, Bu–CH3), 0.59 s (3H, CH3)
(2C), 25.5, 24.4 (2C), 15.3 (CH2), 29.2, 17.2 (CH3)
35
14.48 s (br, 1H, OH), 8.24 s (1H, N@C–H), 7.45–7.84 m 162.6 (N@C–H), 160.6, 151.8, 144.9, 144.7, 144.5,
617 Mꢀ+ (16)
(5H, Ar–H), 7.27–7.40 m (4H, Ar–H), 6.89-7.21 m (5H, 143.9, 142.1, 141.5, 137.7, 118.9, 104.9 (Cq), 132.4,
Ar–H), 6.26 m (1H, @CH), 4.18 s (1H, Flu–H9), 3.87–3.94 131.4, 128.5, 127.0, 126.8, 126.7, 126.3, 126.1, 125.5,
m (1H, N–CH), 3.05–3.24 m (2H, Ind-CH2), 2.60–2.91 m 125.4, 125.3, 124.5, 122.2, 119.3, 118.7 (Ar–CH), 87.8, C(Ind)–CH2 (18)
452 MꢁFlu (59)
296 MꢁFlu–Me–
(2H, CH2), 2.05–2.17 m (2H, CH2), 1.77–1.85 m (4H,
CH2), 1.16–1.70 m (6H, CH2), 1.39 s (9H, tBu–CH3), 0.56 s 34.8 (Cq), 44.0, 39.7, 34.3 (2C), 25.5, 24.4 (2C), 15.9
(3H, CH3) (CH2), 29.2, 14.9 (CH3)
80.6 (Cq, C„C), 67.3 (N–CH), 54.9 (Flu–CH), 44.1, 165 Flu (100)
36
37
14.46 s (br, 1H, OH), 8.26 s (1H, N@C–H), 7.64–7.88 m 162.6 (N@C–H), 160.6, 151.7, 144.9, 144.7, 142.5,
553 Mꢀ+ (37)
(4H, Ar–H), 7.28–7.50 m (5H, Ar–H), 6.52-7.17 m (4H,
Ar–H), 4.22 s (1H, Flu–H9), 3.77 m (1H, N–CH), 3.13–
141.9, 137.7, 118.3, 113.0 (Cq), 134.9, 132.9, 132.7,
132.5, 128.0, 127.3, 127.1, 126.9, 126.2, 126.1, 126.0,
388 MꢁFlu (100)
332 MꢁFlu–C4H8
3.20 m (2H, Cp–CH2), 2.57–2.73 m (2H, CH2), 2.18–2.51 119.7, 119.2 (Ar–CH), 88.3, 80.6 (Cq, C„C), 69.9 (N– (48)
t
m (2H, CH2), 1.65–2.13 m (8H, CH2), 1.51 s (9H, Bu–
CH3), 0.69 s (3H, CH3)
CH), 56.1 (Flu–CH) 43.1, 35.0 (Cq), 46.3, 41.1, 34.8
282 MꢁFlu–Me–
(2C), 24.5 (2C), 15.4 (CH2), 29.4, 17.4 (CH3)
C(Cp)–CH2 (30)
13.91 s (br, 1H, OH), 8.66 s (1H, N@C–H), 7.59–7.79 m 162.5 (N@C–H), 158.5, 151.6, 147.0, 144.8, 144.6,
581 Mꢀ+ (19)
(6H, Ar–H), 7.18–7.53 m (12H, Ar–H), 6.91–7.14 m (3H, 142.4, 141.9, 137.6, 130.1, 122.9, 119.3 (Cq), 135.0,
134.3, 132.8, 132.7, 131.8, 129.4 (2C), 128.2 (2C),
3.13–3.22 m (2H, Cp–CH2), 2.18–2.37 m (4H, CH2), 0.65 s 128.1, 127.3, 127.2, 127.2, 127.1, 126.8, 126.2, 126.1,
416 MꢁFlu (71)
Ar–H), 6.50–6.82 m (2H, Ar–H), 4.20 s (1H, Flu–H9),
310 MꢁFlu–
MeꢁC(Cp)–CH2 (18)
165 Flu (100)
(3H, CH3)
126.0, 121.2 (2C), 119.7, 119.2 (2C) (Ar–CH), 91.8,
80.2 (Cq, C„C), 56.0 (Flu–CH), 38.6 (Cq), 43.0, 41.1,
15.3 (CH2) 17.3 (CH3)
38
13.62 s (br, 1H, OH), 8.46 s (1H, N@C–H), 7.53–7.80 m 161.5 (N@C–H), 157.3, 151.6, 146.8, 144.8, 144.6,
621 Mꢀ+ (20)
456 MꢁFlu (39)
165 Flu (100)
(4H, Ar–H), 6.50–7.46 m (13H, Ar–H), 4.18 s (1H, Flu–
H9), 2.89–3.18 m (3H, CH/Cp–CH2), 2.13-2.45 m (4H,
142.4, 141.9, 138.0, 123.6, 123.1, 119.2 (Cq), 135.0,
132.8, 132.7 (2C), 130.4, 128.6, 127.3, 127.2, 127.1,
CH2), 1.78-1.98 m (4H, CH2), 1.18-1.57 m (6H, CH2), 0.65 126.8, 126.2, 126.1, 126.0, 121.2 (2C), 119.7, 119.2
s (3H, CH3)
(Ar–CH), 92.2, 80.1 (Cq, C„C), 56.0 (Flu–CH), 38.6
(Cq), 43.0, 41.0, 32.8 (2C), 26.9 (2C), 26.4, 15.4 (CH2),
36.7 (CH), 17.3 (CH3)
(continued on next page)

5748
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
Table 8 (continued)
Compound 1H NMR
13C NMR
MS [m/z]
39
40
41
13.93 s (br, 1H, OH), 8.60 s (1H, N@C–H), 7.59–7.82 m 163.2 (N@C–H), 160.6, 151.6, 147.4, 144.9, 144.6,
561 Mꢀ+ (24)
(4H, Ar–H), 7.28–7.53 m (8H, Ar–H), 7.09-7.22 m (2H,
Ar–H), 6.54–7.01 m (4H, Ar–H), 4.21 s (1H, Flu–H9),
142.5, 141.9, 137.7, 122.6, 119.1 (Cq), 135.0, 132.9,
132.7 (2C), 130.8, 127.3, 127.2, 127.1, 126.8, 126.6,
396 MꢁFlu (100)
290 MꢁFlu–
3.07–3.21 m (2H, Cp–CH2), 2.18–2.46 m (4H, CH2), 1.56 s 126.3, 126.1, 126.0, 121.5, 121.2 (2C), 119.7, 118.5
MeꢁC(Cp)–CH2 (14)
t
(9H, Bu–CH3), 0.69 s (3H, CH3)
(Ar–CH), 91.9, 80.3 (Cq, C„C), 56.1 (Flu–CH), 38.7, 165 Flu (30)
35.0 (Cq), 43.1, 41.1, 15.5 (CH2), 29.5, 17.4 (CH3)
13.73 s (br, 1H, OH), 8.58 s (1H, N@C–H), 7.67–7.82 m 163.7 (N@C–H), 160.5, 153.0, 150.1, 148.1, 146.1,
(2H, Ar–H), 6.70–7.54 m (14H, Ar–H), 6.45 t (1H, Ar–H), 145.0, 143.3, 137.7, 118.9, 105.1 (Cq), 143.3, 138.4
561 Mꢀ+ (18)
546 MꢁMe (4)
446 MꢁInd (26)
290 MꢁMe–C(Ind)2–
4.55–4.70 m (2H, Cp–CH2), 3.39-3.56 m (2H, Cp–CH2),
2.66–3.01 m (2H, CH2), 2.09–2.41 m (2H, CH2), 1.46 s
(9H, Bu–CH3), 1.25 s (3H, CH3)
(2C), 132.6, 131.9, 131.6, 130.8, 126.8, 126.7, 126.1,
125.2, 123.9, 123.6, 123.1 (2C), 122.0, 121.2, 118.5
(Ar–CH), 91.3, 80.5 (Cq, C„C), 57.8 (Ind-CH), 38.8, CH2 (27)
34.9 (Cq), 51.9, 39.3, 26.9 (CH2), 29.3, 20.3 (CH3)
t
115 Ind (37)
13.84 s (br, 1H, OH), 8.60 s (1H, N@C–H), 7.90–8.10 m 163.2 (N@C–H), 160.6, 153.1, 148.2, 145.5, 144.7,
(1H, Ar–H), 7.52–7.79 m (4H, Ar–H), 7.06-7.48 m (13H, 143.6, 142.5, 141.9, 137.7, 122.5, 119.0, 105.0 (Cq),
Ar–H), 6.89 t (1H, Ar–H), 6.07–6.14 m (1H, @CH), 4.21 s 132.8, 132.6 (2C), 131.9, 130.7, 130.6, 127.3, 127.0,
611 Mꢀ+ (7)
446 MꢁFlu (31)
431 MꢁFlu–Me (15)
290 MꢁFlu–Me–
(1H, Flu–H9), 2.60–3.50 m (4H, CH2), 2.06–2.37 m (2H,
CH2), 1.50 s (9H, Bu–CH3), 0.72 s (3H, CH3)
126.7, 126.4, 126.3, 126.1, 125.9, 124.9, 124.6, 121.9,
t
121.2, 121.1 (2C), 119.8, 119.1, 118.5 (Ar–CH), 91.7, C(Ind)–CH2 (26)
80.2 (Cq, C„C), 54.2 (Flu–CH), 44.1, 34.9 (Cq), 39.7, 165 Flu (100)
37.3, 15.5 (CH2), 29.4, 14.2 (CH3)
3.3. GC/MS
3.6. Elemental analysis
GC/MS spectra were recorded with a HP 5890 gas chro-
matograph in combination with a HP 5971A mass detec-
tor. A 12 m J&W Scientific fused silica column (DB1,
diameter 0.25 mm, film 0.33 lm, flow 1 ml/min) respec-
tively 25 m J&W Scientific fused silica column (DB5ms,
diameter 0.25 mm, film 0.33 lm, flow 1 ml/min) were used,
helium (4.6) was applied as carrier gas. Using a 12 m col-
umn the routinely performed temperature program started
at 70 ꢁC (2 min). After a heating phase of 11 min (20 K/
min, final temperature 290 ꢁC) the end temperatur was held
for a variable time (plateau phase).
Some of the analyses were performed by the Mikroanal-
ytisches Labor Pascher at Remagen.
The residual analyses were performed with at a VarioEl
III CHN instrument. For this purpose 4–6 mg of the com-
plex were weight into a standard tin pan. The tin pan was
carefully closed and introduced into the auto sampler of
the instrument.
The raw values of the carbon, hydrogen, and nitrogen
contents were multiplied with calibration factors (calibra-
tion compound: acetamide).
At the Zentrale Analytik of the University of Bayreuth,
GC/MS spectra were routinely recorded with a HP5890 gas
chromatograph in combination with a MAT 95 mass
detector.
3.7. Synthesis of the substituted salicylaldehydes 1–4
To 50 mmol of the appropriate phenol derivative in
40 ml of tetrahydrofuran was added dropwise a 3-molar
methylmagnesium bromide solution (18.5 ml; 55.5 mmol)
in diethyl ether. After 2 h of stirring at room tempera-
ture, gas evolution ceased. About 90% of the solvent
were removed in vacuo and toluene (100 ml), triethyl-
amine (10 ml), and paraformaldehyde (3.75 g; 125 mmol)
were added. The mixture was heated to 88 ꢁC and held
at this temperature for 2 h. After cooling to room tem-
perature, the yellow solution was poured into cold
hydrochloric acid (1 M, 250 ml). The organic phase was
separated and dried over sodium sulfate. After removal
of the solvent in vacuo, 3-tert-butyl salicylaldehyde (1)
and 3-cyclohexyl salicylaldehyde (3) were purified by
high vacuum distillation. 3-Phenyl salicylaldehyde (2)
and 3-cyclo-hexyl-5-chlorosalicylaldehyde (4) were recrys-
tallized from ethanol or n-pentane at ꢁ20 ꢁC. Yields: 59–
88%.
3.4. Gas chromatography
For the analysis of organic compounds, especially oligo-
mer mixtures, a PERKIN ELMER Auto System gas chro-
matograph (column: HP1, 28 m, diameter 0.32 mm/carrier
gas helium, flow 5.7 ml/min, split 3.5 ml/min) was used.
The standard temperature program contained a starting
phase at 50 ꢁC (3 min), a heating phase of 50 min (heating
rate 4 K/min, final temperature 250 ꢁC) and a plateau
phase at 250 ꢁC (37 min).
3.5. Gel permeation chromatography (GPC)
GPC measurements were routinely performed by
SABIC Company (Riyadh, Saudi Arabia).

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
5749
3.8. Synthesis of 3-tert-butyl-5-iodosalicylaldehyde (5)
3.12. Synthesis of 1-(4-ethynylbenzyl)indene (20) and 2-
ethynylfluorene (22)
3-tert-Butyl salicylaldehyde (8.4 mmol) was dissolved in
100 ml of a mixture of methanol and methylene chloride
(3:7). Benzyltrimethylammonium dichloroiodate (3.23 g;
9.2 mmol) and water free calcium carbonate (1.1 g;
11 mmol) were added. After 2 h, the excess calcium car-
bonate was filtered off. After removal of about 80% of
the solvent, 20 ml of a sodium hydrogensulfite solution
(5%) was added decolourizing the mixture. Extraction
with diethyl ether, drying over sodium sulfate and
removal of the solvent yielded the aldehyde as raw prod-
uct. Purification by recrystallization from n-pentane fur-
nished 3-tert-butyl-5-iodosalicylaldehyde in a 48% yield
as yellow crystals which are slightly light sensitive and
should be stored in the dark.
1-(4-Iodobenzyl)indene (6 mmol) or 2-iodofluorene
(6 mmol) were dissolved in 30 ml of triethylamine. Bis(trip-
henylphosphino)palladium dichloride (83 mg, 0,12 mmol),
copper(I) iodide (45 mg, 0.24 mmol), and trimethylsilyl-
acetylene (7 mmol) or 2-methylbut-3-yne-2-ol (1 ml,
7 mmol) were added, and the reaction mixture was stirred
for 20 h at room temperature. After removal of the solvent,
water (50 ml) and n-pentane (50 ml) were added. The
organic phase was separated, and the aqueous phase was
extracted with n-pentane. The combined organic phases
were dried over sodium sulfate. Removal of the solvent
in vacuo and recrystallization from n-pentane furnished
1-(4-trimethylsilylethynylbenzyl)indene (19), respectively,
4-(2-fluorenyl)-2-methylbut-3-yn-2-ol (21). Yields: 85–90%.
The protected compounds 19 or 21 (5 mmol) were dis-
solved in 100 ml of a mixture of methanol and methylene
chloride (4:1). Anhydrous potassium carbonate (7.5 mmol)
was added. After 2 h of stirring at room temperature, the
mixture was filtered over sodium sulfate, and the solvent
was removed in vacuo. The raw products were purified
by column chromatography (ethyl acetate/n-pentane 3:7).
Yields: 80–85%.
3.9. Synthesis of the alkyl or halogen substituted
phenoxyimine compounds
An amount of 15 mmol of the appropriate aldehyde
derivative was dissolved in 150 ml of toluene. After addi-
tion of a substituted amine or aniline (1.2 equiv.) and a
few crystals of para-toluenesulfonic acid, the reaction mix-
ture was stirred under reflux for 3 h applying a Dean-Stark-
trap. After cooling to room temperature, sodium hydrog-
encarbonate (150 ml) was added. The organic phase was
separated and filtered over sodium sulfate and silica.
Removing the solvent and recrystallization from ethanol
at ꢁ20 ꢁC yielded the phenoxyimine compounds. Yields:
70–98%.
3.13. Synthesis of 5-hexyn-2-one (23)
2,4-Pentanedione (100 g, 103 ml, 1 mol), anhydrous
potassium carbonate (152 g, 1,1 mol), and propargylchlo-
ride (71 g, 69 ml, 0,95 mol) were dissolved in 500 ml of eth-
anol. The reaction mixture was stirred under reflux for
24 h. After cooling to room temperature, 300 ml of water
were added. The mixture was then extracted with diethyl
ether, and the organic phase was washed with brine and
dried over sodium sulfate. Removal of the solvent and sub-
sequent vacuum distillation yielded 5-hexyn-2-one as col-
ourless liquid in 48% yield.
3.10. Synthesis of the alkynyl functionalized phenoxyimine
compounds
The substituted salicylaldehyde (15 mmol), propargyl-
˚
amine (17 mol), and molecular sieves (3 A, 15 g) were dis-
solved in 100 ml of toluene and stirred at room
temperature for 3 days. After filtration over sodium sulfate
and removal of the solvent, the residue was extracted sev-
eral times with n-pentane. The solution was filtered again
over sodium sulfate, and the solvent was removed. The
phenoxyimine compounds were obtained as yellow or
brownish powders. Yields: 24–40%. If 4-ethynylaniline
was used as amine component, ethanol was applied as a
solvent. Yield: 65%.
3.14. Synthesis of the alkynyl fulvenes 24 and 25
Cyclopentadiene (125 mmol) or indene was dissolved in
50 ml of methanol. 5-Hexyn-2-one (50 mmol) and pyrroli-
dine (75 mmol) were added. The mixture was stirred for
24 h at 40 ꢁC. Glacial acetic acid (100 mmol), water
(150 ml) and n-pentane (150 ml) were introduced into the
reaction mixture. The organic phase was separated and
dried over sodium sulfate. Vacuum distillation yielded the
desired compounds as yellow oils (47–75%).
3.11. Synthesis of the indene derivatives 16–18
Indenyllithium (50 mmol) was suspended in 200 ml of
toluene. The appropriate alkylation reagent (50 mmol)
was added, and the reaction mixture was stirred at room
temperature over night. Filtration over sodium sulfate
and removal of the solvent in vacuo yielded the title com-
pounds as bright yellow viscous oils (90–95%). Compound
18 was obtained as a white powder and purified by recrys-
tallization from n-pentane. Yield: 89%.
3.15. Synthesis of the C1-bridged ligand precursors 26–28
Indene or fluorene (30 mmol) was dissolved in 100 ml of
diethyl ether and reacted with n-butyllithium (1.6 M,
18.75 ml, 30 mmol). After 8 h, the desired fulvene deriva-
tive (30 mmol) was added, and the mixture was stirred
for 2 h at room temperature. Hydrolysis was performed

Table 9
MS and elemental analysis data of the zirconium complexes 42–56
Complex
42
MS (m/z)
Cexp (%)
44.3
64.0
56.3
42.2
43.2
47.8
60.1
47.8
43.5
54.6
72.8
n.b.
Ctheor (%)
44.5
63.8
56.9
42.6
43.9
47.6
60.9
47.0
43.9
54.0
73.7
71.7
74.8
72.1
74.0
Hexp (%)
3.79
5.07
5.54
4.78
4.94
2.81
3.93
3.90
3.40
4.69
5.16
n.b.
Htheor (%)
3.73
5.08
5.46
4.69
4.98
2.73
3.84
3.95
3.49
4.82
5.02
5.40
5.38
5.65
6.39
Nexp (%)
3.00
3.83
4.87
3.07
2.92
2.89
4.38
2.77
2.63
3.94
2.79
n.b.
Ntheor (%)
3.05
3.92
4.74
3.10
3.01
2.92
4.44
2.89
2.69
3.94
2.68
2.88
2.49
2.80
2.47
918 Mꢀ+ (67), 881 MꢁCl (99), 866 MꢁCl–Me (29)
43
714 Mꢀ+ (54), 677 MꢁCl (11), 661 MꢁCl–H–Me (100)
590 Mꢀ+ (66), 553 MꢁCl (42) 537 Mꢁ(N-propynyl)/MꢁCl–H–Me (100)
902/904 Mꢀ+ (5), 865 MꢁCl (6), 777 MꢁI (11), 742 MꢁI–Cl (12)
930 Mꢀ+ (43), 895 MꢁCl (13), 879 MꢁCl–H–Me (14) 545 M-ligand (20)
958 Mꢀ+ (60), 921 MꢁCl (97), 832 MꢁI (68), 795 MꢁI–Cl (100)
630 Mꢀ+ (2), 595 MꢁCl (2), 553 M-phenyl (3)
44
45
46
47
48
49
970 Mꢀ+ (88), 933 MꢁCl (59), 566 M-ligand (33)
50
1038 Mꢀ+ (100), 1003 MꢁCl (50), 912 MꢁI (13), 600 M-ligand (69)
710 Mꢀ+ (100), 675 MꢁCl (43), 637 Mꢁ2Cl–H (25), 436 M-ligand (44)
1042 Mꢀ+ (1), 1027 MꢁMe (1), 951 MꢁCl–C4H8 (2), 601 Mꢁ1 ligand–H (100)
970 Mꢀ+ (2), 955 MꢁMe (5), 935 MꢁCl (2), 115 indenyl (100)
1122 Mꢀ+ (5), 957 Mꢁ2 indenyl–Cl (6), 641 Mꢁ1 ligand–H (8)
998 Mꢀ+ (1), 883 M-indenyl (2), 735 Mꢁ2 indenyl–Cl (2)
1134 Mꢀ+ (1), 1078 MꢁC4H8 (2), 630 M-ligand–Me (2), 487 ligand (19)
51
52
53
54
73.9
71.5
73.3
5.45
5.74
6.52
2.56
2.74
2.48
55
56

Table 10
MS, 1H NMR, and elemental analysis data of the zirconium complexes 57–64
Complex 1H NMR (ppm)
MS (m/z)
Cexp
(%)
Ctheor
(%)
Hexp
(%)
Htheor
(%)
Nexp
(%)
Ntheor
(%)
57
8.30, 8.28, 8.26 s (2H, N@C–H), 7.68–8.01 m (4H, Ar–H), 7.43–7.51 m 1616 Mꢀ+ (0), 1451 MꢁFlu (2), 1403 MꢁZr–3 Cl– 61.2
60.9
5.31
5.24
1.68
1.73
(4H, Ar–H), 7.31–7.08 m (3H, Ar–H), 6.48–6.81 m (2H, Ar–H), 5.75–
Me (2), 1286 Mꢁ2 Flu (2), 1049 M-ligand (3), 165
6.03 m (4H, Cp), 5.27–5.59 m (4H, Cp), 3.64–3.78 m (2H, N–CH), 2.94– Flu (100)
3.23 m (6H, CH2), 2.60–2.77 m (2H, CH2), 2.19 s (br, 6H, CH3), 1.80–
1.93 m (8H, CH2), 1.48–1.74 m (12H, CH2), 1.40, 1.38, 1.36, 1.29, 1.24 s
t
(18H, Bu–CH3)
58
59
8.27 s (br, 2H, N@C–H), 7.87–8.14 m (4H, Ar–H), 7.51–7.76 m (8H, Ar– 1718 Mꢀ+ (0), 1198 Mꢁ2 Zr–4 Cl–Flu (2), 1004 M- 62.5
63.0
60.4
5.12
5.40
5.17
5.32
1.53
1.85
1.63
1.76
H), 6.97–7.48 m (12H, Ar–H), 6.42–6.61 m (4H, Ar–H), 5.63–5.89 m
ligand–cyclohexyl–Me (3), 967 MꢁCl-ligand–
(4H, Cp), 5.17–5.48 m (4H, Cp), 3.54–3.81 m (2H, N–CH), 2.62–3.06 m cyclohexyl–Me (4), 165 Flu (100)
(8H, CH2), 2.13 s (br, 6H, CH3), 1.76–2.11 m (16H, CH2), 1.40, 1.24, 1.21
t
s (br, 18H, Bu–CH3)
8.24 s (br, 2H, N@C–H), 7.51–8.07 m (4H, Ar–H), 7.14–7.43 m (10H,
1588 Mꢀ+ (0), 1431 MꢁFlu (2), 1264 Mꢁ2 Zr–4 Cl 61.0
Ar–H), 6.91–7.06 m (4H, Ar–H), 6.46–6.72 m (2H, Ar–H), 5.92–6.19 m (2), 1035 M-ligand (2), 870 M-ligand–ZrCl2 (3), 165
(4H, Cp), 5.47–5.64 m (4H, Cp), 3.72 m (2H, N–CH), 2.87–3.10 m (4H, Flu (100)
CH2), 2.48–2.69 m (4H, CH2), 1.61–2.37 m (8H, CH2), 2.19 s (br, 6H,
t
CH3), 1.38, 1.24 s (br, 18H, Bu–CH3)
60
61
62
8.73, 8.71, 8.67 s (2H, N@C–H), 7.54–7.93 m (12H, Ar–H), 7.18–7.49 m 1642 Mꢀ+ (0), 1318 Mꢁ2 Zr–4 Cl (2), 1291 MꢁZr– 62.9
(18H, Ar–H), 6.79–7.08 m (8H, Ar–H), 6.50–6.78 m (2H, Ar–H), 5.69– 3 Cl–2 phenyl (2), 1248 Mꢁ2 Zr–6 Cl (2), 1167
6.03 m (4H, Cp), 5.21–5.52 m (4H, Cp), 2.61–3.07 m (4H, CH2), 2.18– Mꢁ3 Cl–Zr–(Me)C(Flu)(Cp)CH2 (5)
2.39 m (4H, CH2), 2.15 s (br, 6H, CH3)
62.8
59.9
61.4
4.05
4.41
4.66
3.92
4.32
4.53
1.61
1.59
1.64
1.70
1.62
1.75
8.55, 8.52 s (2H, N@C–H), 7.60–7.98 m (8H, Ar–H), 7.12–7.43 m (18H, 1726 Mꢀ+ (0), 1448 MꢁZr–3Cl–C6H9 (2), 1412
Ar–H), 6.52–7.09 m (2H, Ar–H), 5.93-6.27 m (4H, Cp), 5.28–5.33 m (4H, MꢁZr–4Cl–C6H10 (2), 165 Flu (100)
Cp), 2.89–3.10 m (4H, CH), 2.48–2.83 m (4H, CH2), 2.15, 2.22, 2.30 s
59.6
(6H, CH3), 1.74–1.88 m (8H, CH2), 1.21–1.48 m (12H, CH2)
8.61, 8.59 s (br, 2H, N@C–H), 7.85–8.17 m (2H, Ar–H), 7.53–7.83 m
1602 Mꢀ+ (0), 1587 MꢁMe (2), 816 MꢁZrCl2-
62.0
(6H, Ar–H), 7.22–7.29 m (12H, Ar–H), 6.78–7.15 m (8H, Ar–H), 6.43– ligand–C4H8 (2), 803 MꢁZr–4 Cl-ligand (3), 734
6.72 m (2H, Ar–H), 5.85–6.14 m (4H, Cp), 5.44–5.57 m (4H, Cp), 3.08– MꢁZr–4 Cl-ligand–C4H8 (2), 165 Flu (100)
3.24 m (4H, CH2), 2.49–3.06 m (4H, CH2), 2.23, 2.21, 2.18 s (br, 6H,
CH3), 1.46, 1.44, 1.43, 1.42, 1.39, 1.30, 1.28, 1.25, 1.23 s (18H, tBu–CH3)
63
64
8.56 s (br, 2H, N@C–H), 7.63–7.74 m (4H, Ar–H), 7.09–7.54 m (16H,
1600 Mꢀ+ (1), 1585 MꢁMe (2), 720 Mꢁ2 Zr–4 Cl- 62.1
61.4
63.4
4.61
4.58
4.53
4.50
1.66
1.57
1.75
1.64
Ar–H), 6.69–7.03 m (10H, Ar–H), 6.29–6.51 m (4H, Ar–H), 5.91–6.17 m ligand (2)
(2H, Ar–H), 2.97–3.22 m (6H, CH2), 2.26–2.51 m (2H, CH2), 2.13 s (6H,
CH3), 1.46, 1.42, 1.39, 1.38, 1.36, 1.33, 1.26, 1.23, 1.22 s (18H, tBu–CH3)
8.35, 8.33, 8.19 s (2H, N@C–H), 7.76–7.79 m (2H, Ar–H), 7.52–7.74 m 1706 Mꢀ+ (0), 1117 MꢁZr–3 Cl–Flu–2 Ind (2), 1050 62.8
(8H, Ar–H), 7.06–7.36 m (22H, Ar–H), 6.61–7.02 m (6H, Ar–H), 6.38- Mꢁ2 Zr–4 Cl–2 Flu (3) 165 Flu (100)
6.53 m (2H, Ar–H), 6.16-6.28 m (2H, @CH), 2.41–3.45 m (6H, CH2),
2.03-2.29 m (2H, CH2), 2.11 s (6H, CH3), 1.53, 1.50, 1.46, 1.45, 1.43,
t
1.40, 1.32, 1.26, 1.22 s (18H, Bu–CH3)
If there are more signals for the same group of protons in the 1H NMR spectra due to the presence of isomers, the sum of the corresponding integral values is given.

5752
C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
adding 50 ml of water. Separation of the organic phase and
removal of the solvent yielded raw products which were
recrystallized from n-pentane at ꢁ20 ꢁC. Yields: 32–73%.
complexes were washed with n-pentane (3 · 15 ml) and
dried in vacuo furnishing yellow or brownish powders.
Yields: 30–92%. MS and elemental analysis data of the
complexes 42–64 are given in Table 9.
3.16. General procedure for the Sonogashira coupling
reactions of phenoxyimine compounds with indene and
fluorene derivatives
3.19. Polymerization of ethylene in the 1l Bu¨chi autoclave
The desired zirconium complex (1–5 mg) was suspended
in 5 ml of toluene. The mixture was transferred to a 1l
Schlenk flask filled with 250 ml n-pentane. This mixture
In 15 ml of triethylamine, an amount of 1.0 mmol of the
phenoxyimine compound, 1.0 mmol of a substituted indene
or fluorene derivative, bis(triphenylphosphino)-palladium
dichloride (0.01 mmol) and copper(I) iodide (0.02 mmol)
were dissolved. The mixture was stirred for 20 h at room
temperature. After removal of the solvent, water (50 ml)
and n-pentane (50 ml) were added. The organic phase
was separated, and the aqueous phase was extracted several
times with n-pentane. The combined organic phases were
dried over sodium sulfate. Removal of the solvent in vacuo,
purification by column chromatography, and recrystalliza-
tion from n-pentane gave the coupling products as yellow-
ish or orange brown powders (yields: 68–95%).
was transferred to a 1l Buchi laboratory autoclave under
¨
inert atmosphere. An ethylene pressure of 1 bar was
applied for 5 min. Methylalumoxane (30% in toluene,
Zr:Al = 1:500) was added via a cannula, and the autoclave
was thermostated to 35 ꢁC applying an ethylene pressure of
10 bar over 1 h. The resulting polymer was filtered off over
a glass frit, washed with diluted hydrochloric acid, water,
and acetone, and finally dried in vacuo.
Acknowledgements
We thank Saudi Basic Industries Corporation (SABIC)
for the financial support.
3.17. Synthesis of the mononuclear zirconium complexes 42–
56
References
An amount of 1.2 mmol of the desired phenoxyimine
compound was dissolved in 30 ml of tetrahydrofuran.
Potassium hydride (48 mg; 1.2 mmol; 1 equiv.), suspended
in 10 ml of tetrahydrofuran, was added, and the mixture
was stirred at room temperature for 1 h till the hydrogen
evolution had ceased. Zirconium tetrachloride (140 mg;
0,6 mmol; 0.5 equiv.) was added and stirring was continued
for 20 h. After the solvent was removed in vacuo, methy-
lene chloride (30 ml) was added, and the solution was fil-
tered over sodium sulfate. Removal of about 25 ml of the
solvent in vacuo and subsequent addition of 50 ml of n-
pentane resulted in the precipitation of the zirconium com-
plexes. Decantation of the mother liquor, washing with n-
pentane (3 · 15 ml), and drying in vacuo furnished the
complexes as yellow or brownish powders. Yields: 57–
92% (Table 8).
[1] D.S. Breslow, N.R. Newburg, J. Am. Chem. Soc. 79 (1957) 5072.
[2] H.-H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, R. Way-
¨
mouth, Angew. Chem. 107 (1995) 1255.
[3] H. Alt, S.J. Palackal, J. Organomet. Chem. 472 (1994) 113.
[4] B. Peifer, W. Milius, H.G. Alt, J. Organomet. Chem. 553 (1998) 205.
[5] H.G. Alt, M. Jung, J. Organomet. Chem. 568 (1998) 87.
[6] E.H. Licht, H.G. Alt, M.M. Karim, J. Organomet. Chem. 599 (2000)
275.
[7] H.G. Alt, A. Ko¨ppl, Chem. Rev. 100 (2000) 1205, and references
therein.
[8] M. Brookhart, L.K. Johnson, C.M. Kilian, S. Mecking, D.J. Temple,
Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 37 (1996) 254.
[9] L.K. Johnson, C.M. Kilian, M. Brookhart, J. Am. Chem. Soc. 117
(1995) 6414.
[10] L.K. Johnson, S. Mecking, M. Brookhart, J. Am. Chem. Soc. 118
(1996) 267.
[11] B.L. Small, M. Brookhart, J. Am. Chem. Soc. 120 (1998) 7143.
[12] B.L. Small, M. Brookhart, A.M.A. Bennett, J. Am. Chem. Soc. 120
(1998) 4049.
[13] G.J.P. Britovsek, V.C. Gibson, B.S. Kimberley, P.J. Maddox, S.J.
McTavish, G.A. Solan, A.J.P. White, D.J. Williams, Chem. Com-
mun. (1998) 849.
[14] G.J.P. Britovsek, V.C. Gibson, B.S. Kimberley, P.J. Maddox, S.J.
McTavish, G.A. Solan, A.J.P. White, D.J. Williams, J. Am. Chem.
Soc. 121 (1999) 8728.
[15] G.J.P. Britovsek, V.C. Gibson, S. Mastroianni, D.C.H. Oakes, C.
Redshaw, G.A. Solan, A.J.P. White, D.J. Williams, Eur. J. Inorg.
Chem. (2001) 431.
[16] T. Fujita, Y. Tohi, M. Mitani, S. Matsui, J. Saito, M. Nitabaru, K.
Sugi, H. Makio, T. Tsutsui (Mitsui Chemicals Inc.), EP 0874005,
1998.
[17] S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, H. Tanaka, T.
Fujita, Chem. Lett. (1999) 1065.
[18] S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsukawa,
Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H. Tanaka, N.
Kashiwa, T. Fujita, J. Am. Chem. Soc. 123 (2001) 6847.
[19] N. Matsukawa (Mitsui Chemicals Inc.), EP 1013674, 2000.
3.18. Synthesis of the trinuclear zirconium complexes 57–64
An amount of 0,4 mmol of the appropriate ligand pre-
cursor 34–41 was dissolved in 30 ml of tetrahydrofuran.
Potassium hydride (48 mg; 1.2 mmol; 3 equiv.), suspended
in 10 ml of tetrahydrofuran, was added, and the mixture
was stirred at room temperature for 1 h till the hydrogen
evolution had ceased. Zirconium tetrachloride (140 mg;
0.6 mmol; 1.5 equiv.) was added and stirring was continued
for 20 h. After the solvent was removed in vacuo, methy-
lene chloride (30 ml) was added, and the solution was fil-
tered over sodium sulfate. Removal of about 25 ml of the
solvent in vacuo and subsequent addition of 50 ml of n-
pentane resulted in the precipitation of the zirconium com-
plexes. The overstanding solution was decantated. The

C. Go¨rl, H.G. Alt / Journal of Organometallic Chemistry 692 (2007) 5727–5753
[20] M. Mitani, Y. Yoshida, J. Mohri, K. Tsuru, S. Ishii, S. Kojoh, T. [37] L. Pronko, WO 2004067586, 2004.
5753
Matsugi, J. Saito, N. Matsukawa, S. Matsui, T. Nakano, H. Tanaka,
N. Kashiwa, T. Fujita (Mitsui Chemicals Inc.), WO 01/55231, 2001.
[21] S. Matsui, T. Fujita, Catal. Today 66 (2001) 63.
[22] H. Makio, N. Kashiwa, T. Fujita, Adv. Synth. Catal. 344 (2002) 477.
[23] M. Mitani, N. Matsukawa, J. Saito, M. Nitabara, K. Tsuru, S.
Matsui, T. Fujita, JP 2000230010, 2000.
[38] J. Kuwabara, D. Takeuchi, K. Osakada, Organometallics 24 (2005)
2705.
[39] C. Go¨rl, H.G. Alt, J. Organomet. Chem. 692 (2007) 4580.
[40] G. Casnati, G. Casiraghi, G. Puglia, G. Sartori, G. Terenghi, DE
2736523, 1978.
[41] Y. Shan, J. Sun, Y. Xu, Y. Cui, Cuihua Xuebao 25 (2004) 735.
[42] S. Kajigaeshi, T. Kakinami, H. Yamasaki, S. Fujisaki, T. Okamoto,
Bull. Chem. Soc. Jpn. 61 (1988) 600.
[24] S.-I. Ishii, M. Mitani, J. Saito, S. Matsuura, S.-I. Kojoh, N. Kashiwa,
T. Fujita, Chem. Lett. (2002) 740.
[25] S. Matsui, K. Tsuru, M. Nitahara, M. Mitani, T. Fujita, JP 11199592,
1999.
[43] S. Kajigaeshi, T. Kakinami, H. Yamasaki, S. Fujisaki, M. Kondo,
T. Okamoto, Chem. Lett. (1987) 2109.
[26] Y. Tohi, T. Nakano, H. Makio, S. Matsui, T. Fujita, T. Yamaguchi,
Macromol. Chem. Phys. 205 (2004) 1179.
[44] M. Nielsen, K.V. Gothelf, J. Chem. Soc. Perkin Trans. 1 (2001)
2440.
[27] Y. Nakayama, H. Bando, Y. Sonobe, T. Fujita, Bull. Chem. Soc.
Jpn. 77 (2004) 617.
[45] S.M.A. Karim, R. Nomura, T. Masuda, J. Polym. Sci. A, Polym.
Chem. 40 (2002) 2458.
[28] H. Makio, T. Fujita, Macromol. Symp. 213 (2004) 221.
[29] M. Mitani, J. Mohri, Y. Yoshida, J. Saito, S. Ishii, K. Tsuru, S.
Matsui, R. Furuyama, T. Nakano, H. Tanaka, S. Kojoh, T. Matsugi,
N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 124 (2002) 3327.
[30] M. Riedel, G. Erker, B. Bosch, A. Bertuleit, DE 19632919, 1998.
[31] Y. Wakabayashi, O. Yoshida, M. Sato, JP 2000159829, 2000.
[32] J.C. Tsai, K. Liu, S. Chan, S. Wang, M. Young, US 6297392, 2001.
[33] S. Nagy, WO 0240552, 2002.
[34] H.G. Alt, R. Ernst, Inorg. Chim. Acta 350 (2003) 1.
[35] H.G. Alt, R. Ernst, J. Mol. Cat. A: Chem. 195 (2003) 11.
[36] M. Deppner, R. Burger, H.G. Alt, J. Organomet. Chem. 689 (2004)
1194.
[46] M.E. Fessler, J.T. Spencer, J.F. Lomax, R.N. Grimes, Inorg. Chem.
27 (1988) 3069.
[47] G.T. Crisp, Y.-L. Jiang, Synth. Commun. 28 (1998) 2571.
[48] J. Flahaut, P. Miginiac, Helv. Chim. Acta 61 (1978) 2275.
[49] M.B. Welch, H.G. Alt, B. Peifer, US 5631203, 1997.
[50] M.T. Reetz, M. Willuhn, C. Psiorz, R. Goddard, Chem. Commun.
(1999) 1105.
[51] C. Go¨rl, H.G. Alt, J. Mol. Catal. A: Chem. 273 (2007) 118.
[52] B. Peifer, Dissertation, Universita¨t Bayreuth, 1995.
[53] H.G. Alt, M. Jung, G. Kehr, J. Organomet. Chem. 562 (1998)
153.
[54] H.G. Alt, R. Zenk, W. Milius, J. Organomet. Chem. 514 (1996) 25.