Synthesis of bulky zirconocene dichloride compounds and their applications in olefin polymerization

Article abstract of DOI:10.1135/cccc20070747

The bulky substituted cyclopentadienyllithium derivatives, LiC ₅H₄(CHMeR) (R = C₆H₅ (1), 1-naphthyl (2), 9-anthryl (3)), were synthesized from the reaction of 6-phenylfulvene, 6-(1-naphthyl)fulvene or 6-(9-anthr

Full text of DOI:10.1135/cccc20070747

Zirconocene Dichloride Compounds
747
SYNTHESIS OF BULKY ZIRCONOCENE DICHLORIDE COMPOUNDS
AND THEIR APPLICATIONS IN OLEFIN POLYMERIZATION
Dorian POLO-CERÓN , Santiago GÓMEZ-RUIZ , Sanjiv PRASHARa3,*,
a1
a2
a4
b1
b2
Mariano FAJARDO , Antonio ANTIÑOLO and Antonio OTERO
a
Departamento de Química Inorgánica y Analítica, E.S.C.E.T.,
Universidad Rey Juan Carlos, 28933 Móstoles (Madrid), Spain; e-mail: dorian.polo@urjc.es,
santiago.gomez@urjc.es, sanjiv.prashar@urjc.es, mariano.fajardo@urjc.es
Departamento de Química Inorgánica, Orgánica y Bioquímica,
1
2
3
4
b
Facultad de Químicas, Campus Universitario, Universidad de Castilla-La Mancha,
1
2
1
3071-Ciudad Real, Spain; e-mail: antonio.antinolo@uclm.es, antonio.otero@uclm.es
Received March 28, 2007
Accepted April 17, 2007
Dedicated to our friend Dr Karel Mach on the happy occasion of his 70th birthday.
Th e bulky substituted cyclopen tadien yllith ium derivatives, LiC H (CHMeR) (R = C H (1),
5
4
6
5
1
6
-n aph th yl (2), 9-an th ryl (3)), were syn th esized from th e reaction of 6-ph en ylfulven e,
-(1-n aph th yl)fulven e or 6-(9-an th ryl)fulven e with LiMe. Th e ansa-bis(cyclopen tadien e)
ligan ds Me Si(C HMe ){C H (CHMeR)} (R = C H (4), 1-n aph th yl (5), 9-an th ryl (6)), an d
2
5
4
5
4
6
5
th eir lith ium derivatives Li (Me Si(C Me ){C H (CHMeR)}) (R = C H (7), 1-n aph th yl (8),
2
2
5
4
5
3
6
5
5
5
9
(
(
-an th ryl (9)) h ave been prepared. Th e zircon ocen e com plexes, [Zr(η -C H ){η -C H -
5 5 5 4
CHMeR)}Cl ] (R = C H (10), 1-n aph th yl (11), 9-an th ryl (12)) an d [Zr{η -C H (CHMeR)} Cl ]
2 6 5 5 4 2 2
R = C H5 (13), 1-n aph th yl (14), 9-an th ryl (15)), were syn th esized by th e reaction of lith ium
5
6
5
derivatives 1–3 an d [Zr(η -C H )Cl ] or ZrCl , respectively. Th e reaction of th e lith ium ansa-
5
5
3
4
derivatives 7–9 an d zircon ium tetrach loride yielded th e ansa-zircon ocen e com plexes,
5
5
[
Zr(Me Si(η -C Me ){η -C H (CHMeR)})Cl ] (R = C H (16), 1-n aph th yl (17), 9-an th ryl (18)).
2 5 4 5 3 2 6 5
Th e zircon ocen e com plexes h ave been tested in th e polym erization of eth en e an d propen e.
Th e polym erization of propen e with th e ansa-zircon ocen e catalysts 16–18 gave polypropy-
len e with 70% mmmm pen tads an d th e sym m etric zircon ocen e catalysts 13–15 30–60%
mmmm pen tads.
Keyw ord s: Metallocen es; Zircon ocen es; Zircon ium ; Polym erization ; Polyeth ylen e; Poly-
propylen e; Lewis acids.
Group 4 m etallocen e com plexes are well kn own as excellen t catalysts in
1
olefin polym erization . Th ey provide superior activity an d selectivity
2
com pared with oth er catalytic system s . Crucial in th e developm en t of
m etallocen e-based catalysts h as been th e direct relation sh ip foun d between
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763
©
2007 Institute of Organic Chemistry and Biochemistry
doi:10.1135/cccc20070747

7
48
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
3
com plex structure an d catalytic beh avior . Th erefore on e can see th e clear
im portan ce of m olecular arch itecture of th e m etallocen e com plex in ob-
4
tain in g polyolefin s with th e desired ph ysical properties . As a con tin uation
5
of our work in th e field of zircon ocen e catalysts , we presen t h ere th e syn -
th esis, ch aracterization an d catalytic beh avior of n ovel m etallocen e an d
ansa-m etallocen e com plexes.
RESULTS AND DISCUSSION
Synthesis of Cyclopentadienyllithium Derivatives 1–3
Th e lith ium com poun ds, LiC H (CHMeR) (R = C H (1), 1-n aph th yl (2),
5
4
6
5
9
-an th ryl (3)), were prepared by th e n ucleoph ilic addition of m eth yllith ium
on to th e exocyclic double bon d of th e correspon din g substituted fulven e
(
Sch em e 1).
SCHEME 1
1
13
Com poun ds 1–3 were ch aracterized by H an d C NMR spectroscopy (see
1
Experim en tal). Two m ultiplets at ca. 5.5 ppm were observed in th e H NMR
spectra for th e cyclopen tadien yl proton s. Th e doublet at ca. 1.7 ppm was
assign ed to th e m eth yl group. Th e proton bon ded to th e ch iral carbon
atom gave a quadruplet at 4.00, 4.89 an d 5.71 ppm for 1, 2 an d 3, respec-
tively. For 1, th ree m ultiplets (6.98, 7.12 an d 7.23 ppm ) were observed cor-
respon din g to th e ph en yl proton s. Th e 1-n aph th yl group in 2 exh ibited
sign als between 7.3 an d 8.3 ppm . Multiplets were recorded between 7.2 an d
8
.5 ppm for th e 9-an th ryl m oiety in 3. 13C NMR spectra of 1–3 sh owed th e
expected signals for the cyclopentadienyl m oiety (ca. 102, 103 and 125 ppm ).
Th e ch iral carbon atom gave a sign al at ca. 35 ppm an d th e m eth yl group at
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

Zirconocene Dichloride Compounds
749
ca. 25 ppm . Addition al sign als were observed correspon din g to th e arom atic
group presen t.
Synthesis of Bis(cyclopentadienyl) Derivatives 4–9
Th e reaction of 1–3 with Me SiCl(C HMe ) (Sch em e 2), followin g th e previ-
2
5
4
5
a
ously reported syn th etic protocols , yielded th e bis(cyclopen tadien e) com -
poun ds, Me Si(C HMe ){C H (CHMeR)} (R = C H (4), 1-n aph th yl (5),
2
5
4
5
4
6
5
9
-an th ryl (6)), as m ixtures of th e double bon d position isom ers, with on e
1
isom er bein g predom in an t. Com poun ds 4–6 were ch aracterized by H NMR
spectroscopy an d electron im pact m ass spectrom etry (see Experim en tal).
Th e dilith ium derivatives, Li (Me Si(C Me ){C H (CHMeR)}) (R = C H (7),
2
2
5
4
5
3
6
5
1
-n aph th yl (8), 9-an th ryl (9)), were obtain ed in th e usual m an n er by th e re-
action of 4-6 with butyllith ium (Sch em e 2).
SCHEME 2
Synthesis of Mixed-Ring Zirconocene Complexes 10–12
5
5
Th e zircon ocen e com plexes, [Zr(η -C H ){η -C H (CHMeR)}Cl ] (R = C H
5
5
5
5
4
2
6
(
10), 1-n aph th yl (11), 9-an th ryl (12)), were prepared by th e reaction of 1–3
with [Zr(η-C H )Cl ] (Sch em e 3). Com plexes 10–12 were isolated as wh ite
5
5
3
crystallin e solids an d ch aracterized spectroscopically.
Th e substituted cyclopen tadien yl m oiety exh ibited four m ultiplets (5.6–
1
6
.9 ppm ) in th e H NMR spectra of 10–12 because of th eir diastereotopic
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7
50
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
n ature of th e α an d β pairs of proton s due to th e presen ce of a ch iral sub-
stituen t. A sin glet at ca. 6.4 ppm was observed for th e un substituted cyclo-
pen tadien yl ligan d. A quadruplet (at 4.31, 5.20 an d 5.95 ppm for 10, 11
an d 12, respectively) an d doublet (at ca. 1.8 ppm ) were recorded an d as-
sign ed, respectively, to th e proton an d m eth yl group bon ded to th e ch iral
carbon atom . Th e arom atic system s gave th e expected sign als (see Experi-
1
3
1
m en tal). Th e C{ H}NMR spectra gave five sign als for th e substituted
cyclopen tadien yl ligan d (110–145 ppm ) an d on e sign al (ca. 115 ppm ) for
th e un substituted cyclopen tadien yl group. Sign als were observed for th e
m eth yl an d ch iral carbon at ca. 21 an d 37 ppm , respectively. Th e arom atic
system s, ph en yl, 1-n aph th yl an d 9-an th ryl, gave four, ten an d fourteen sig-
n als, respectively.
SCHEME 3
Synthesis of Zirconocene Complexes 13–15
Th e reaction of two m olar equivalen ts of 1–3 with ZrCl4 yielded th e
5
6
zircon ocen e com plexes, [Zr{η -C H (CHMeR)} Cl ] (R = C H (13) ,
5
4
2
2
6
5
1
-n aph th yl (14), 9-an th ryl (15)) (Sch em e 4). Com plexes 13–15 were iso-
lated as wh ite crystallin e solids an d ch aracterized. NMR spectroscopy re-
SCHEME 4
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Zirconocene Dichloride Compounds
751
vealed th e presen ce of th e expected rac an d meso isom ers due to th e
presen ce of two ch iral cen tres. In th e case of 15, th e separation of on e of
th e isom ers from th e m ixture was ach ieved. Th e NMR spectra of com plexes
1
3–15 were sim ilar to th ose observed for 9–12. For 13 an d 14, th e sign als
correspon din g to th e two isom ers in th e 1:1 ratio were observed.
Synthesis of ansa-Zirconocene Complexes 16–18
5
5
The ansa-m etallocene com plexes, [Zr(Me Si(η -C Me ){η -C H (CHMeR)})Cl ]
2
5
4
5
3
2
(
R = C H (16), 1-n aph th yl (17), 9-an th ryl (18)), were prepared by th e reac-
6 5
tion of 7–9 an d ZrCl (Sch em e 5).
4
SCHEME 5
In addition to th e ch iral cen tre in th e bulky substituen t, plan ar ch irality
exists in th e m on osubstituted cyclopen tadien yl rin g. Th us for 16–18, two
diastereoisom ers are possible (Fig. 1). In th e case of 16 an d 17 we were un -
able to separate th ese isom ers. However, for 18, on ly on e of th e possible
1
isom ers was foun d to be presen t in th e isolated product. Th e H NMR spec-
tra of 16–18 sh owed, for th e ansa-m etallocen e system , th ree m ultiplets for
th e proton s of th e m on osubstituted C rin g (5.2–7.1 ppm ), four sin glets for
5
th e m eth yl groups of th e C5 rin g (1.8–2.2 ppm ), an d two sin glets corre-
spon din g to th e m eth yl groups of th e SiMe bridgin g un it (at ca. 0.0 ppm ).
2
Addition al sign als were recorded for th e ch iral substituen ts, wh ich were
sim ilar to th ose in 9–15. In th e NMR spectra of 16 an d 17, th e sign als corre-
spon din g to th e two isom ers in th e 1:1 ratio were observed.
Polymerization of Ethene
Th e polym erization s of eth en e usin g th e zircon ocen e derivatives 10–18 as
catalyst (in th e case of 13, 14, 16 an d 17 1:1 isom eric m ixtures) with a
m eth ylalum in oxan e-m etal catalyst in th e ratio 1000:1, h ave been carried
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7
52
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
FIG. 1
Stereoisom ers of com plexes 16–18
out. Th e polym erization s were con ducted at 20 °C an d at an eth en e pres-
sure of 2 bar durin g 30 m in . Th e polym erization was also carried out with
5
th e referen ce com poun d [Zr(η -C H ) Cl ], un der th e sam e experim en tal
5
5 2
2
con dition s. Th e catalytic activities an d polym er m olecular weigh t an d dis-
tribution are given in Table I.
Th e activities of all th e catalysts tested proved to be lower th an th at re-
5
corded for th e referen ce catalyst [Zr(η -C H ) Cl ]. Th is m aybe due to th e
5
5 2
2
possible in tram olecular coordin ation of th e arom atic m oiety to th e zirco-
7
n ium cen tre durin g th e polym erization . Catalyst 10 sh owed th e h igh est
catalytic activity, far greater th an th e oth er zircon ocen e com plexes tested
an d com parable with th at observed for th e referen ce catalyst. Th e cata-
lytic activity decreased in depen den ce of th e arom atic substituen t presen t:
ph en yl > an th ryl > n aph th yl. Activities of differen t m etallocen e system s
with th e sam e arom atic substituen t were sim ilar (with th e exception of 10).
Som e of th e catalysts produced h igh m olecular weigh ts of polyeth ylen e
6
(
of th e order 10 ), such as 11 an d h om oleptic m etallocen e catalysts 13–15.
Catalysts 10–18 produced polym ers with broad m olecular weigh t distribu-
tion s, with polydispersity values between 4 an d 7. Th is ph en om en on h as
been explain ed previously con siderin g th e C5 rin g rotation to be slower
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

Zirconocene Dichloride Compounds
753
th an th e propagation of th e polym er ch ain , creatin g differen t rotam ers of
8
th e catalyst wh ich act as distin ct active cen tres .
TABLE I
5
a
Eth en e polym erization catalyzed with 10–18 an d [Zr(η -C H ) Cl ]
5
5
2
2
Catalyst
Activityb
Mw × 10–3
M /M
w
n
5
[
[
[
[
[
[
[
[
[
[
Zr(η -C H ) Cl ]
23300
21200
2567
3673
6100
3760
2000
5613
1933
3067
169
253
846
384
1054
987
716
197
79
2.3
5.8
5.1
4.4
4.8
4.1
4.0
7.1
4.4
7.5
5
5
2
2
5
5
Zr(η -C H ){η -C H (CHMeC H )}Cl ] (10)
5
5
5
4
6
5
2
5
5
Zr(η -C H ){η -C H (CHMeC H )}Cl ] (11)
5
5
5
4
10
7
2
5
5
Zr(η -C H ){η -C H (CHMeC H )}Cl ] (12)
5
5
5
4
14
9
2
5
Zr{η -C H (CHMeC H )} Cl ] (13)
5
4
6
5
2
2
5
Zr{η -C H (CHMeC H )} Cl ] (14)
5
4
10
7
2
2
5
Zr{η -C H (CHMeC H )} Cl ] (15)
5
4
14
9
2
2
5
5
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (16)
2
5
4
5
3
6
5
2
5
5
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (17)
2
5
4
5
3
10
7
2
5
5
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (18)
524
2
5
4
5
3
14
9
2
a
At 20 °C, ethene pressure 2 bar, 200 m l toluene, [Al] = 3 × 10 m ol l–1, [Zr] = 3 × 10–5 m ol l–1
–2
,
b
t = 15 m in . kg(PE)/m ol Zr h
Polymerization of Propene
Th e polym erization s of propen e usin g zircon ocen e derivatives 13–18 as
catalysts (in th e case of 13, 14, 16 an d 17 th e 1:1 m ixtures of isom ers) with
th e m eth ylalum in oxan e cocatalyst-m etal catalyst ratio 3000:1 h ave been
carried out. Th e polym erization s were con ducted at 0 °C for 60 m in an d at
a propen e pressure of 2.5 bar. Th e polym erization was also carried out with
5
th e referen ce com poun d [Zr(η -C H ) Cl ] un der th e sam e experim en tal
5
5 2
2
con dition s. Th e catalytic activities, polym er m olecular weigh ts, poly-
dispersity an d isotacticity are given in Table II. Pen tad distribution s for
1
3–15 are sh own in Table III.
Th e catalytic activities of th e catalysts tested were lower th an th at re-
corded for th e referen ce com plex. However, com plexes 16 an d 17 gave
activities sim ilar to th e referen ce com poun d. Th e an th ryl-substituted cata-
lysts, 15 an d 18, gave low activities in com parison with th e oth er catalysts.
Polypropylen e m olecular weigh ts were h igh er for th e m etallocen e system s
com pared with th e ansa-m etallocen e catalysts. Th e polydispersity values of
th e polypropylen es obtain ed with th e catalysts are also h igh an d again th is
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

7
54
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
can be explain ed by differen t rotam ers of th e sam e com plex actin g as active
8
cen tres in th e polym erization .
Th e isotacticity of th e polym ers was m easured by th e pen tad m eth od us-
in g 13C NMR spectroscopy. Th e mmmm pen tad con ten ts in polypropylen e
prepared with th e ansa-m etallocen e catalysts 16–18 are of th e order of 70%
an d are com parable with th ose reported previously for sim ilar C sym m etric
1
5
b,9
com plexes
.
Usin g th e Cossee–Arlm an site con trol m ech an ism , th e stereoselectivity of
th e C catalysts 16–18 can be explain ed. Four possible diastereom eric in ter-
1
m ediates (two at each bin din g site) are possible in th e polym erization of
propen e. Th e bin din g sites A an d B are isoselective with th e polym er ch ain
bein g located in th e less sterically h in dered position s, in term ediates A1 an d
B1 (Fig. 2). Th erefore, in a way sim ilar to th at predicted an d observed for C
ansa-m etallocen e catalysts , th e polym erization sh ould yield isotactic
polypropylen e.
2
1
0
A back-skip m ech an ism m ay also be used to in terpret th e stereoselectivity
of com plexes 16–18 in th e polym erization of propylen e. It h as previously
been put forward th at th e presen ce of a bulky cyclopen tadien yl substituen t
in th e β-position (with respect to th e carbon atom of th e C rin g lin ked to
5
th e ansa bridge) does n ot allow th e polym er ch ain to be located in th e
m ore sterically con gested position 11. In th e absen ce of m on om er m olecule,
as m ost likely occurs at th e en d of each in sertion step, th e steric pressure
im posed by th e ligan d m ay force th e growin g ch ain to skip back to th e less
crowded position . In sertion , th erefore, occurs with th e sam e relative posi-
TABLE II
5
a
Propen e polym erization catalyzed with com plexes 13–18 an d [Zr(η -C H ) Cl ]
5
5
2
2
b
–3
m m m m
%
Catalyst
Activity
Mw × 10
Mw/Mn
5
[
[
[
[
[
[
[
Zr(η -C H ) Cl ]
121
73
2
26
33
41
13
17
13
1.8
9.2
9.9
9.4
4.0
6.1
3.2
4.0
46.8
33.0
61.8
71.5
70.5
71.7
5
5
2
2
5
Zr{η -C H (CHMeC H )} Cl ] (13)
5
4
6
5
2
2
5
Zr{η -C H (CHMeC H )} Cl ] (14)
89
5
4
10
7
2
2
5
Zr{η -C H (CHMeC H )} Cl ] (15)
32
5
4
14
9
2
2
5
5
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (16)
115
113
30
2
5
4
5
3
6
5
2
5
5
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (17)
2
5
4
5
3
10
7
2
5
5
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (18)
2
5
4
5
3
14
9
2
a
–2
m ol l–1, [Zr] = 3 × 10–5
At 0 °C, propen e pressure 2.5 bar, 200 m l toluen e, [Al] = 9 × 10
–
1
b
m ol l , t = 60 m in . kg(PP)/m ol Zr h
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

Zirconocene Dichloride Compounds
755
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7
56
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
tion of th e m on om er an d th e polym er ch ain an d leads to isotactic poly-
propylen e (Fig. 3). Exam ples of th e back-skip m ech an ism in polym erization
of propen e h ave been reported5b,9b,12.
Th e n on -ansa catalysts 13 an d 14 give m arkedly lower mmmm pen tad
values com pared with th e ansa-m etallocen e com plexes 16–18. However,
th e polypropylen e produced usin g 15 gives an mmmm pen tad value wh ich
com petes in isotacticity with th at of its ansa-coun terparts.
FIG. 2
Diastereom eric in term ediates
FIG. 3
Back-skip m ech an ism
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

Zirconocene Dichloride Compounds
757
Con siderin g 13–15 as con form ation ally dyn am ic system s, for wh ich two
extrem es are described with th e cyclopen tadien yl substituen ts eclipsed or
in opposite direction , th en th e two possible rotam ers will produce eith er
n on selective (atactic) or isoselective coordin ation of th e m on om er (Fig. 4).
Th e greater steric dem an d of th e substituen t will m ake th e syn con form a-
tion less stable th an th e anti con form ation an d m ake th e catalyst m ore
isoselective. In deed, th e an th ryl com plex gives th e h igh est mmmm pen tad
value. In tercon version between th e stereoselective anti an d th e n on -
stereoselective syn con form ation s h as previously been proposed as a m ean s
of gen eratin g blocks of atactic an d isotactic stereosequen ces in a sin gle
1
3
polym er ch ain
.
An alysis of th e pen tad distribution sh ows th at th e stereodefects are de-
rived predom in an tly from mmmr, mmrr, mmrm an d mrmr pen tads. Th e pres-
en ce of a relatively h igh con cen tration of mmrm stereodefects is con sisten t
with th e m icrostructure con tain in g a sign ifican t fraction of isotactic se-
quen ces of opposite con figuration s separated by isolated r diads. Th ese re-
sults im ply th at isom erization takes place between th e two en an tiom eric
anti con form ation s, wh ich are oppositely isoselective. Th e n otable quan tity
of th e mrmr pen tad observed in dicates atactic sequen ces in th e polym er
ch ain wh ich m ost probably origin ate from th e ach iral syn rotam er.
FIG. 4
Stereoselectivity for differen t con form ation s in com plexes 13–15
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

7
58
Conclusion
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
Th e syn th esis an d ch aracterization of n ew zircon ocen e an d ansa-zircon ocen e
com plexes in corporatin g bulky substituen ts is reported. Th e com plexes
proved to be active as catalysts in th e polym erization of eth en e an d
propen e. Th e stereoselective polym erization of propen e gave in th e case of
th e C1 sym m etric ansa-m etallocen e system s isotacticity of 70%. Th e un -
bridged zircon ocen e com plex gave tacticities between 30–60% depen din g
on th e arom atic substituen t. Th is presen t study sh ould open up th e possi-
bility of m odelin g th e properties of polypropylen e by ration al design of th e
zircon ocen e catalyst.
EXPERIMENTAL
All reaction s were perform ed usin g stan dard Sch len k tube tech n iques in atm osph ere of dry
n itrogen . Solven ts were distilled from th e appropriate dryin g agen ts an d degassed before use.
Me SiCl(C HMe ), BuLi (1.6 M in h exan e), MeLi (1.6 M in Et O), MAO, an d ZrCl , were
2
5
4
2
4
purch ased from Aldrich an d used directly. 6-Ph en ylfulven e, 6-(1-n aph th yl)fulven e or
1
4
6
-(9-an th ryl)fulven e were prepared adaptin g th e previously reported syn th etic route . Th e
5
15
syn th esis of [Zr(η -C H )Cl ] was carried out usin g th e literature m eth od
.
5
5
3
1
13
1
H an d C{ H} NMR spectra (δ, ppm ; J, Hz) were recorded on a Varian Mercury FT-400
spectrom eter an d referen ced to th e residual deuterated solven t. Microan alyses were carried
out with a Perkin –Elm er 2400 or Leco CHNS-932 m icroan alyzer. Mass spectroscopic an alyses
were preform ed on a Hewlett–Packard 5988A (m/z 50–1000) in strum en t. Polym er m olecular
weigh ts an d distribution s were determ in ed by GPC (Waters 150C Plus) in 1,2,4-trich loro-
1
3
ben zen e at 145 °C. Polym er isotacticity was calculated from
solution in 1,2,4-trich loroben zen e/C D (1:1).
C NMR spectra of polym er
6
6
LiC H (CHMeC H ) (1). MeLi (1.6 M in Et O) (10.1 m l, 16.21 m m ol) was added dropwise
5
4
6
5
2
to a solution of 6-ph en ylfulven e (2.50 g, 16.21 m m ol) in Et O (50 m l) at –78 °C. Th e reac-
2
tion m ixture was allowed to warm to room tem perature an d stirred for 6 h . Th e solven t was
rem oved in vacuo. A wh ite solid wh ich was wash ed with h exan e (2 × 50 m l) an d dried un -
1
der vacuum to yield a free-flowin g powder. Yield 1.85 g (65%). H NMR (400 MHz, THF-d ):
8
1
6
4
.52 (d, 3 H, J(H,Me) = 7.6, CHMe), 4.00 (q, 1 H, CHMe), 5.55 (2 H), 5.57 (2 H) (m , C H ),
5 4
1
3
1
.98 (1 H), 7.12 (2 H), 7.23 (2 H) (m , C H ). C{ H} NMR (100 MHz, THF-d ): 25.4 (CHMe),
6
5
8
1.3 (CpC), 101.8, 102.2, 125.1 (C H ), 122.0, 128.1, 128.8, 134.7 (C H ). For C13H13Li
5
4
6
5
(
176.2) calculated: 88.62% C, 7.44% H; foun d: 88.31% C, 7.39% H.
LiC H (CHMeC H ) (2). Th e syn th esis of 2 was carried out in th e sam e way as 1: MeLi
5
4
10
7
(
1
1.6 M in Et O) (7.6 m l, 12.22 m m ol) an d 6-(1-n aph th yl)fulven e (2.50 g, 12.22 m m ol). Yield
2
.49 g (54%). 1H NMR (400 MHz, THF-d ): 1.67 (d, 3 H, J(H,Me) = 7.2, CHMe), 4.89 (q, 1 H,
8
CHMe), 5.56 (2 H), 5.58 (2 H) (m , C H ), 7.33 (3 H), 7.45 (1 H), 7.55 (1 H), 7.75 (1 H), 8.34
5
4
1
3
1
(
1 H) (m , C10H ). C{ H} NMR (100 MHz, THF-d ): 25.2 (CHMe), 36.0 (CpC), 101.9, 102.1,
7 8
1
24.7 (C H ), 124.6, 124.7, 124.8, 124.9, 125.5, 125.8, 128.8, 132.6, 134.7, 147.5 (C H ).
5 4 10 7
For C17H15Li (226.3) calculated: 90.25% C, 6.68% H; foun d: 90.17% C, 6.59% H.
LiC H (CHMeC H ) (3). Th e syn th esis of 3 was carried out in th e sam e way as 1: MeLi
5
4
14
9
(
1.6 M in Et O) (6.1 m l, 9.82 m m ol) an d 6-(9-an th ryl)fulven e (2.50 g, 9.82 m m ol). Yield
2
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

Zirconocene Dichloride Compounds
759
1
5
.35 g (50%). 1H NMR (400 MHz, THF-d ): 1.91 (d, 3 H, J(H,Me) = 7.2, CHMe), 5.53 (2 H),
8
.57 (2 H) (m , C H ), 5.71 (q, 1 H, CHMe), 7.26 (4 H), 7.89 (2 H), 8.22 (1 H), 8.52 (2 H) (m ,
5
4
1
3
1
C14H ). C{ H} NMR (100 MHz, THF-d ): 25.4 (CHMe), 34.3 (CpC), 102.3, 102.4, 124.7
9
8
(
C H ), 124.9, 125.4, 125.7, 129.6, 130.4, 132.5, 143.8 (C H ). For C21H17Li (276.3) calcu-
5 4 14 9
lated: 91.29% C, 6.20% H; foun d: 91.00% C, 6.18% H.
Me Si(C HMe ){C H (CHMeC H )} (4). Me SiCl(C HMe ) (1.22 g, 5.68 m m ol) in THF (50 m l)
2
5
4
5
4
6
5
2
5
4
was added to a solution of LiC H (CHMeC H ) (1) (1.00 g, 5.68 m m ol) in THF (50 m l) at
5
4
6
5
–
78 °C. Th e reaction m ixture was allowed to warm to room tem perature an d stirred for 15 h .
Th e solven t was rem oved in vacuo an d h exan e (150 m l) was added to th e resultin g dark
oran ge oil. Th e m ixture was filtered an d th e solven t rem oved un der reduced pressure to give
1
an oran ge oil. Yield 1.92 g (97%). H NMR (400 MHz, CDCl ; for th e predom in an t isom er):
3
0
2
.16 (s, 6 H, SiMe ), 1.59 (d, 3 H, J(H,Me) = 6.8, CHMe) 1.90 (6 H), 2.03 (6 H) (s, C Me ),
2 5 4
.97 (1 H), 3.29 (1 H) (m , HC ), 3.94 (m , 1 H, CHMe), 6.01 (1 H), 6.35 (1 H), 6.44 (1 H) (m ,
5
+
C H ), 7.22 (1 H), 7.28 (2 H), 7.31 (2 H) (m , C H ). MS-EI, m/z (rel.%): 348 (15) [M ], 243
5
3
6
5
+
+
+
(
41) [M – Me – C H ], 179 (55) [M – C H CHMeC H ], 105 (100) [M – Me Si(C HMe )(C H )].
6 5 5 4 6 5 2 5 4 5 3
For C24H32Si (348.6) calculated: 82.69% C, 9.25% H; foun d: 82.67% C, 9.25% H.
Me Si(C HMe ){C H (CHMeC H )} (5). Th e syn th esis of 5 was carried out in th e sam e way
2
5
4
5
4
10
7
as 4: Me SiCl(C HMe ) (0.95 g, 4.42 m m ol) an d LiC H (CHMeC H ) (2) (1.00 g, 4.42 m m ol).
2
5
4
5
4
10
7
1
Yield 1.73 g (98%). H NMR (400 MHz, CDCl ; for th e predom in an t isom er): –0.15 (s, 6 H,
3
SiMe ), 1.68 (d, 3 H, J(H,Me) = 8.0, CHMe), 1.84 (6 H), 1.98 (6 H) (s, C Me ), 2.90 (1 H),
2
5
4
3
.03 (1 H) (m , HC ), 4.72 (m , 1 H, CHMe), 6.30 (1 H), 6.33 (1 H), 6.42 (1 H) (m , C H ), 7.44
5 5 3
+
(
4 H), 7.73 (1 H), 7.86 (1 H), 8.15 (1 H) (m , C H ). MS-EI, m/z (rel.%): 398 (12) [M ], 243
10 7
+
+
+
(
39) [M – Me – C10H ], 219 (31) [M – Me Si(C HMe )], 179 (34) [M – C H CHMeC H ],
7 2 5 4 5 4 10 7
1
55 (100) [M+ – Me Si(C HMe )(C H )]. For C28H34Si (398.7) calculated: 84.36% C, 8.60% H;
2 5 4 5 3
foun d: 84.67% C, 8.62% H.
Me Si(C HMe ){C H (CHMeC H )} (6). Th e syn th esis of 6 was carried out in th e sam e way
2
5
4
5
4
14
9
as 4: Me SiCl(C HMe ) (0.78 g, 3.62 m m ol) an d LiC H (CHMeC H ) (3) (1.00 g, 3.62 m m ol).
2
5
4
5
4
14
9
1
Yield 1.54 g (95%). H NMR (400 MHz, CDCl ; for th e predom in an t isom er): 0.00 (s, 6 H,
3
SiMe ), 1.93 (d, 3 H, J(H,Me) = 6.8, CHMe), 1.84 (6 H), 1.98 (6 H) (s, C Me ), 2.90 (1 H),
2
5
4
3
.10 (1 H) (m , HC ), 5.40 (m , 1 H, CHMe), 6.14 (1 H), 6.22 (1 H), 6.32 (1 H) (m , C H ), 7.43
5 5 3
+
+
(
4 H), 8.01 (2 H), 8.39 (3 H) (m , C H ). MS-EI, m/z (rel.%): 448 (20) [M ], 269 (21) [M –
14 9
+
+
Me Si(C HMe )], 243 (35) [M – Me – C14H ], 205 (100) [M – Me Si(C HMe )(C H )]. For
2
5
4
9
2
5
4
5
3
C32H36Si (448.7) calculated: 85.65% C, 8.09% H; foun d: 85.67% C, 8.05% H.
Li (Me Si(C Me ){C H (CHMeC H )}) (7). BuLi (1.6 M in h exan e) (5.4 m l, 8.62 m m ol) was
2
2
5
4
5
3
6
5
added dropwise to a solution of 4 (1.50 g, 4.31 m m ol) in Et O (100 m l) at –78 °C. Th e m ix-
2
ture was allowed to warm to 25 °C an d stirred for 15 h . Th e solven t was rem oved in vacuo.
A wh ite solid wh ich was wash ed with h exan e (2 × 50 m l) an d dried in vacuum . Yield 1.39 g
(
90%). For C24H30Li Si (360.5) calculated: 79.97% C, 8.39% H; foun d: 79.67% C, 8.35% H.
2
Li (Me Si(C Me ){C H (CHMeC H )}) (8). Th e syn th esis of 8 was carried out in th e sam e
2
2
5
4
5
3
10
7
way as 7: BuLi (1.6 M in h exan e) (4.7 m l, 7.52 m m ol) an d 5 (1.50 g, 3.76 m m ol). Yield 1.37 g
(
89%). For C28H32Li Si (410.5) calculated: 81.92% C, 7.86% H; foun d: 81.77% C, 7.85% H.
2
Li (Me Si(C Me ){C H (CHMeC H )}) (9). Th e syn th esis of 9 was carried out in th e sam e
2
2
5
4
5
3
14
9
way as 7: BuLi (1.6 M in h exan e) (4.2 m l, 6.68 m m ol) an d 6 (1.50 g, 3.34 m m ol). Yield 1.34 g
87%). For C32 Li Si (460.6) calculated: 83.45% C, 7.44% H; foun d: 82.97% C, 7.39% H.
(
H
34
2
5
5
[
Zr(η -C H ){η -C H (CHMeC H )}Cl ] (10). LiC H (CHMeC H ) (1) (1.00 g, 5.58 m m ol) in
5 5 5 4 6 5 2 5 4 6 5
5
THF (50 m l) was added dropwise durin g 15 m in to a solution of [Zr(η -C H )Cl ] (1.47 g,
5
5
3
5
.58 m m ol) in THF (50 m l) at 0 °C. Th e reaction m ixture was allowed to warm to room tem -
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

7
60
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
perature an d stirred for 2 h . Th e solven t was rem oved in vacuo an d h exan e (125 m l) was
added to th e resultin g solid. Th e m ixture was filtered, th e filtrate con cen trated (20 m l) an d
cooled to –30 °C to give crystals of th e title com plex. Yield 0.85 g (38%). 1H NMR (400 MHz,
CDCl ): 1.60 (d, 3 H, J(H,Me) = 6.8, CHMe), 4.31 (q, 1 H, CHMe), 5.95 (1 H), 6.29 (1 H),
3
6
.42 (1 H), 6.57 (1 H) (m , C H ), 6.38 (s, 5 H, C H ), 7.19 (2 H), 7.35 (2 H), 7.42 (1 H) (m ,
5 4 5 5
1
3
1
C H ). C{ H} NMR (100 MHz, CDCl ): 21.0 (CHMe), 40.0 (CpC), 112.8, 113.5, 115.1,
6
5
3
1
16.0, 145.9 (C H ), 115.0 (C H ), 126.0, 127.4, 127.6, 128.7 (C H ). MS-EI, m/z (rel.%): 396
5 4 5 5 6 5
+
+
+
+
(
4) [M ], 319 (18) [M – C H ], 291 (90) [M – CHMeC H ], 255 (52) [M – CHMeC H – Cl].
6 5 6 5 6 5
For C18
H
Cl Zr (396.5) calculated: 54.53% C, 4.58% H; foun d: 54.71% C, 4.62% H.
18
2
5
5
[
Zr(η -C H ){η -C H (CHMeC H )}Cl ] (11). Th e syn th esis of 11 was carried out in th e
5
5
5
4
10
7
2
5
sam e way as 10: LiC H (CHMeC H ) (2) (1.20 g, 5.30 m m ol) an d [Zr(η -C H )Cl ] (1.39 g,
5
4
10
7
5
5
3
1
5
.30 m m ol). Yield 0.99 g (42%). H NMR (400 MHz, CDCl ): 1.74 (d, 3 H, J(H,Me) = 6.8,
3
CHMe), 5.20 (q, 1 H, CHMe), 5.90 (1 H), 6.37 (2 H), 6.73 (1 H) (m , C H ), 6.47 (s, 5 H,
5
4
C H ), 7.04 (1 H), 7.38 (1 H), 7.52 (2 H), 7.73 (1 H), 7.88 (1 H), 8.30 (1 H) (m , C H ).
5
5
10
7
1
3
1
C{ H} NMR (100 MHz, CDCl ): 22.0 (CHMe), 37.0 (CpC), 111.2, 113.6, 116.1, 119.0, 144.3
3
(
(
C H ), 116.0 (C H ), 125.5, 126.1, 126.4, 127.1, 128.2, 129.0, 130.3, 132.2, 134.0 136.1
5 4 5 5
+
+
+
C10H ). MS-EI, m/z (rel.%): 446 (12) [M ], 319 (18) [M – C10H ], 291 (90) [M
–
7
7
+
CHMeC10H ], 283 (51) [M – C10H7 – Cl]. For C22H20Cl Zr (446.5) calculated: 59.18% C,
7
2
4
.51% H; foun d: 58.88% C, 4.53% H.
5
5
[
Zr(η -C H ){η -C H (CHMeC H )}Cl ] (12). Th e syn th esis of 12 was carried out in th e
5 5 5 4 14 9 2
5
sam e way as 10: LiC H (CHMeC H ) (3) (1.00 g, 3.61 m m ol) an d [Zr(η -C H )Cl ] (0.95 g,
3
5
4
14
9
5
5
3
1
.61 m m ol). Yield 0.56 g (31%). H NMR (400 MHz, CDCl ): 1.99 (d, 3 H, J(H,Me) = 7.2,
3
CHMe), 5.93 (q, 1 H, CHMe), 5.61 (1 H), 6.10 (1 H), 6.57 (1 H), 6.90 (1 H) (m , C H ), 6.41
5
4
(
(
s, 5 H, C H ), 7.20 (1 H), 7.27 (1 H), 7.37 (1 H), 7.51 (1 H), 7.59 (1 H), 7.76 (1 H), 8.04
5 5
2 H), 8.56 (1 H) (m , C14H ). C{ H} NMR (100 MHz, CDCl ): 20.0 (CHMe), 34.0 (CpC),
9 3
1
3
1
1
1
10.3, 114.2, 116.0, 117.4, 141.0 (C H ), 115.6 (C H ), 124.1, 124.4, 125.4, 126.0, 126.1,
5 4 5 5
27.0, 127.5, 128.1, 129.0 129.4, 130.6, 131.8, 132.0, 137.2 (C H ). MS-EI, m/z (rel.%): 496
1
4
9
+
+
+
+
(
7) [M ], 319 (12) [M – C14H ], 283 (29) [M – C14H9 – Cl], 248 (50) [M – C14H9 – 2 × Cl].
9
For C26
H Cl Zr (496.6) calculated: 62.89% C, 4.47% H; foun d: 62.61% C, 4.41% H.
22 2
5
[
Zr{η -C H (CHMeC H )} Cl ] (13). Th e syn th esis of 13 was carried out in th e sam e way as
5 4 6 5 2 2
1
0: LiC H (CHMeC H ) (1) (1.50 g, 8.48 m m ol) an d ZrCl (0.98 g, 4.20 m m ol). Yield 0.89 g
5 4 6 5 4
1
(
(
42%). H NMR (400 MHz, CDCl ; two isom ers): 1.59 (d, 12 H, J(H,Me) = 6.8, CHMe), 4.32
q, 4 H, CHMe), 5.87 (4 H), 6.10 (2 H), 6.15 (2 H), 6.20 (2 H), 6.25 (2 H), 6.54 (4 H) (m ,
3
1
3
1
C H ), 7.16 (8 H), 7.29 (8 H), 7.30 (4 H) (m , C H ). C{ H} NMR (100 MHz, CDCl ; two iso-
5
4
6
5
3
m ers): 20.0, 21.0 (CHMe), 39.9, 40.0 (CpC), 111.0, 112.0, 112.2, 112.5, 112.6, 114.0, 114.5,
15.0, 146.0, 146.2 (C H ), 126.0, 126.4, 127.0, 127.1, 127.5, 127.9, 139.0, 139.5 (C H ).
1
5
4
6
5
+
+
+
MS-EI, m/z (rel.%): 500 (9) [M ], 423 (17) [M – C H ], 388 (100) [M – C H – Cl], 331 (14)
6
5
6
5
+
[
M
– C H CHMeC H ]. For C26H26Cl Zr (500.6) calculated: 62.38% C, 5.23% H; foun d:
5 4 6 5 2
6
2.08% C, 5.18% H.
5
[
Zr{η -C H (CHMeC H )} Cl ] (14). Th e syn th esis of 14 was carried out in th e sam e way
5 4 10 7 2 2
as 10: LiC H (CHMeC H ) (2) (1.50 g, 6.63 m m ol) an d ZrCl (0.77 g, 3.32 m m ol). Yield
5
4
10
7
4
1
0
7
.66 g (33%). H NMR (400 MHz, CDCl ; two isom ers): 1.76 (6 H), 1.77 (6 H) (d, J(H,Me) =
3
.2 an d 7.2, CHMe), 5.25 (q, 4 H, CHMe), 5.90 (4 H), 6.32 (8 H), 6.72 (4 H) (m , C H ), 7.04
5
4
1
3
1
(
(
4 H), 7.36 (4 H), 7.51 (8 H), 7.71 (4 H), 7.87 (4 H), 8.26 (4 H) (m , C10H ). C{ H} NMR
100 MHz, CDCl ; two isom ers): 21.0, 22.0 (CHMe), 31.0, 35.0 (CpC), 109.2, 109.8, 109.9,
7
3
1
1
10.0, 114.0, 114.5, 115.0, 115.8, 144.0, 144.5 (C H ), 117.0, 117.4, 123.0, 123.2, 125.0,
5 4
25.4, 126.0, 126.1, 126.4, 126.9, 128.0, 128.2, 130.0, 130.3, 133.0, 133.7, 139.0, 139.4,
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

Zirconocene Dichloride Compounds
761
+
+
1
3
5
42.0, 142.6 (C10H ). MS-EI, m/z (rel.%): 600 (21) [M ], 381 (70) [M – C H CHMeC H ],
7 5 4 10 7
+
41 (100) [M – C H CHMeC10H7 – Cl]. For C34H30Cl Zr (600.7) calculated: 67.98% C,
5
4
2
.03% H; foun d: 67.84% C, 4.96% H.
5
[
Zr{η -C H (CHMeC H )} Cl ] (15). Th e syn th esis of 15 was carried out in th e sam e way
5 4 14 9 2 2
as 10: LiC H (CHMeC H ) (3) (1.50 g, 5.43 m m ol) an d ZrCl (0.63 g, 2.71 m m ol). Yield
5
4
14
9
4
1
0
.74 g (39%). H NMR (400 MHz, CDCl ): 2.00 (d, 6 H, J(H,Me) = 7.2, CHMe), 5.95 (q, 4 H,
3
CHMe), 5.61 (2 H), 5.99 (2 H), 6.46 (2 H), 6.90 (2 H) (m , C H ), 7.27 (4 H), 7.39 (4 H), 7.73
5
4
1
3
1
(
2 H), 8.03 (4 H), 8.40 (2 H), 8.51 (2 H) (m , C14H ). C{ H} NMR (100 MHz, CDCl ): 20.0
9 3
(
CHMe), 33.0 (CpC), 110.0, 113.8, 116.2, 116.9, 143.7 (C H ), 124.5, 124.7, 124.9, 125.3,
5 4
1
26.2, 126.9, 128.0, 128.6, 128.7, 129.0, 129.5, 129.9, 137.5, 140.7 (C H ). MS-EI, m/z
14 9
+
+
+
+
(
rel.%): 700 (31) [M ], 523 (20) [M – C14H ], 495 (57) [M – CHMeC14H ], 488 (11) [M –
7 9
+
C14H9 – Cl], 352 (100) [M – C14H9 – 2 × Cl]. For C42H34Cl Zr (700.9) calculated: 71.98% C,
2
4
.89% H; foun d: 71.75% C, 4.86% H.
5
5
[
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (16). THF (50 m l) was added to a solid m ixture
2 5 4 5 3 6 5 2
of ZrCl4 (0.64 g, 2.77 m m ol) an d Li (Me Si(C Me ){C H (CHMeC H )}) (7) (1.00 g, 2.77 m m ol).
2
2
5
4
5
3
6
5
Th e resultin g solution was stirred for 15 h . Solven t was rem oved in vacuo an d m ixture of
toluen e (75 m l) an d h exan e (25 m l) added to th e resultin g solid. Th e m ixture was filtered
an d th e filtrate con cen trated (10 m l) an d cooled to –30 °C to yield crystals of th e title com -
1
plex. Yield 0.56 g (40%). H NMR (400 MHz, CDCl ; two isom ers): 0.74 (3 H), 0.86 (6 H),
3
0
1
4
.91 (3 H) (s, SiMe ), 1.55 (3 H), 1.65 (3 H) (d, J(H,Me) = 5.2 an d 6.8, CHMe), 1.87 (3 H),
2
.95 (3 H), 1.97 (3 H), 2.00 (3 H), 2.07 (3 H), 2.09 (3 H), 2.14 (6 H) (s, C Me ), 4.38 (1 H),
5
4
.45 (1 H) (q, CHMe), 5.23 (1 H), 5.57 (1 H), 5.61 (1 H), 5.72 (1 H), 6.29 (1 H), 6.99 (1 H)
1
3
1
(
m , C H ), 7.13 (2 H), 7.22 (4 H), 7.28 (4 H) (m , C H ). C{ H} NMR (100 MHz, CDCl ; two
5 3 6 5 3
isom ers): 0.1 (2 C), 0.2 (2 C) (SiMe ), 12.3, 12.4, 12.5, 12.6, 15.0, 15.1, 15.1, 15.2 (C Me ),
2
5
4
1
2
1
1
1.7, 21.8 (CMe), 39.6, 40.4 (CpC), 96.9, 105.0, 106.3, 110.3 (Si-C (Cp)), 112.1, 112.9,
13.9, 114.1, 114.3, 127.3, 127.5, 127.6 (C H ), 124.6, 124.7, 125.3, 125.9, 126.0, 126.1,
5
3
34.8, 135.1 (C H ), 128.2, 128.3, 136.0, 138.0, 144.1, 144.2, 146.5, 146.9 (C Me ). MS-EI,
6
5
5
4
+
+
+
+
m/z (rel.%): 506 (43) [M ], 471 (100) [M – Cl], 436 (21) [M – 2 × Cl], 331 (29) [M – 2 × Cl –
CHMeC H ]. For C24H30Cl SiZr (508.7) calculated: 56.67% C, 5.94% H; foun d: 56.57% C,
6
5
2
5
.89% H.
5
5
[
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (17). Th e syn th esis of 17 was carried out in
2 5 4 5 3 10 7 2
th e sam e way as 16: ZrCl (0.57 g, 2.44 m m ol) an d 8 (1.00 g, 2.44 m m ol). Yield 0.52 g
4
1
(
38%). H NMR (400 MHz, CDCl ; two isom ers): 0.69 (3 H), 0.87 (6 H), 0.95 (3 H) (s, SiMe ),
3
2
1
2
5
7
.68 (3 H), 1.75 (3 H) (d, J(H,Me) = 7.2 an d 7.2, CHMe) 1.84 (3 H), 1.95 (3 H), 2.02 (3 H),
.03 (3 H), 2.09 (3 H), 2.17 (3 H), 2.19 (6 H) (s, C Me ), 5.35 (q, 2 H, CHMe), 5.21 (1 H),
5
4
.63 (1 H), 5.72 (1 H), 5.79 (1 H), 6.34 (1 H), 7.12 (1 H) (m , C H ), 6.91 (2 H), 7.35 (2 H),
5
3
1
3
1
.51 (4 H), 7.69 (2 H), 7.87 (2 H), 8.36 (2 H) (m , C10H ). C{ H} NMR (100 MHz, CDCl ;
7
3
two isom ers): –0.4, –0.3, 0.0, 0.2 (SiMe ), 12.2, 12.4, 12.4, 12.6, 14.9, 15.0, 15.1, 15.2
2
1
(
C Me ), 21.0, 21.1 (CMe), 31.7, 35.5 (CpC), 97.0, 104.5, 106.6, 110.6 (Si-C (Cp)), 112.0,
5
4
1
1
1
1
6
12.9, 130.9, 133.7, 135.2, 135.9, 143.4, 144.5 (C H ), 124.7, 125.4, 125.5, 125.9, 126.0,
5 3
26.1, 126.5, 128.6, 128.7, 147.0 (C10H ), 114.9, 123.3, 123.9, 124.4, 126.4, 131.1, 134.5,
7
+
+
+
36.4 (C Me ). MS-EI, m/z (rel.%): 557 (26) [M ], 521 (100) [M – Cl], 485 (19) [M – 2 × Cl],
41 (87) [M – Zr{Me Si(C Me )(C H )}Cl – Me]. For C28H32Cl SiZr (558.8) calculated:
5
4
+
2
5
4
5
4
2
2
0.19% C, 5.77% H; foun d: 60.09% C, 5.66% H.
5
5
[
Zr(Me Si(η -C Me ){η -C H (CHMeC H )})Cl ] (18). Th e syn th esis of 18 was carried out in
2 5 4 5 3 14 9 2
th e sam e way as 16: ZrCl (0.51 g, 2.17 m m ol) an d 9 (1.00 g, 2.17 m m ol). Yield 0.46 g
4
1
(
35%). H NMR (400 MHz, CDCl ): 0.88 (3 H), 1.00 (3 H) (s, SiMe ), 1.84 (d, 3 H, J(H,Me) =
3
2
Collect. Czech. Chem. Commun. 2007, Vol. 72, Nos. 5–6, pp. 747–763

7
62
Polo-Cerón, Gómez-Ruiz, Prashar, Fajardo, Antiñ olo, Otero:
7
6
8
.2, CHMe), 1.92 (3 H), 2.05 (3 H), 2.07 (3 H), 2.21 (3 H) (s, C Me ), 5.51 (1 H), 5.84 (1 H),
5
4
.15 (1 H) (m , C H ), 6.18 (q, 1 H, CHMe), 7.25 (1 H), 7.36 (1 H), 7.48 (2 H), 7.69 (1 H),
5
3
1
3
1
.00 (2 H), 8.38 (1 H), 8.60 (1 H) (m , C14H ). C{ H} NMR (100 MHz, CDCl ): –0.3, –0.2
9
3
1
(
SiMe ), 12.0, 12.7, 15.3, 15.7 (C Me ), 21.0 (CMe), 33.8 (CpC), 99.2, 111.6 (Si-C (Cp)),
2 5 4
1
1
10.5, 114.7, 126.5, 145.9 (C H ), 124.9, 125.2, 125.4, 126.1, 126.7, 127.2, 127.6, 128.1,
5 3
29.6, 129.8, 130.7, 131.4, 132.8, 133.0 (C H ), 124.3, 129.4, 138.4, 141.9 (C Me ). MS-EI,
1
4
9
5
4
+
+
+
+
m/z (rel.%): 606 (24) [M ], 571 (93) [M – Cl], 536 (100) [M – 2 × Cl], 331 (17) [M – 2 × Cl –
CHMeC14H ]. For C32H34Cl SiZr (608.8) calculated: 63.13% C, 5.63% H; foun d: 63.03% C,
9
2
5
.49% H.
We gratefully acknowledge financial support from the Ministerio de Educación y Ciencia, Spain
grants No. CTQ2005-07918-C02-02/BQU and No. CTQ2006-11845/BQU), the Comunidad
(
de Madrid (S-0505/PPQ-0328) and the Universidad Rey Juan Carlos (graduate fellowship for
D. Polo-Cerón). We would also like to thank Repsol-YPF and LATEP (Universidad Rey Juan Carlos)
for their assistance in polymer analysis.
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