Syn hesis o B idged and Unb idged G oup (lV) Me allocene
Complexes as Ca alys P ecu so s o
E hylene Polyme iza ion
Disse a ion
zu E langung des akademischen G ades eines
Dok o s de Na u wissenscha en (D . e . na .) de Fakul ä ϋ
Biologie, Chemie und Geowissenscha en de
Uni e si ä Bay eu h
Vo geleg on
Mohamed Elnaiem Mohamed Abdelbagi
aus Kha oum, Sudan
Bay eu h, Ge many
2011
This hesis ul ils he equi emen s o he doc o al deg ee o he Facul y o Biology,
Chemis y and Geological Sciences a he Uni e si y o Bay eu h.
Thesis submi ed: 11.10.2011
Da e o Scien i ic Colloquium: No embe 22, 2011
Examina ion Commi ee:
P o . D . Helmu G. Al (1. Re e ee)
P o . D . Jü gen Senke (2. Re e ee)
P o . D . Raine Schobe (Vo si zende )
P o . D . Pe e S oh iegl
The ollowing wo k was pe o med du ing he pe iod om Ap il 2008 o Ma ch 2011
unde he supe ision o P o . D . Helmu G. Al a he Leh s uhl ϋ Ano ganische
Chemie ll and a he Leh s uhl ϋ Mak omolekula e Chemie I de Uni e si ä Bay eu h.
My since e acknowledgemen o my supe iso
He n P o esso D . Helmu G. Al
o his guidance, encou agemen and en husias ic suppo du ing he cou se o his
esea ch wo k.
I am g a e ul o he DAAD o he inancial suppo
Acknowledgemen
I am e y g a e ul o D . Ch is ian Gö l o his guidance and help in esea ch wo k and
hesis w i ing. Thanks a e also due o his aluable sugges ions and he wonde ul
leisu e ime ac i i ies we sha ed.
My hanks a e also due o D . Ma hias Dö e l o ansla ing he summa y.
I am g a e ul o D . Khalil Ahmed o his assis ance in GC/MS and NMR measu emen s
du ing he i s s ages o my esea ch.
I would like o exp ess my deep hanks and g a i ude o my labma es in he “Al g oup”:
D . Ch is ine Denne , D . Hai Alshamma i, D . Hamdi Elagab, D . Julian Lang, D .
And ea Rimkus, D . Tanja Englmann and F ank Lϋdel o hei help, suppo and
aluable sugges ions.
I would like o exp ess my g a i ude o all membe s in AC ll and MC I a he Uni e si y o
Bay eu h o p o iding a iendly and coope a i e a mosphe e.
To all my iends in Bay eu h, I wish o exp ess my since e hanks o genuine ela ions
and wonde ul ime I spen wi h hem.
Finally I would like o ex end my deepes hanks and g a i ude o my amily membe s in
Sudan o hei cons an encou agemen and mo al suppo h oughou he pe iod o my
s udy.
To
My Pa en s
&
My Child en Ahmed & Raha
Wi h my Lo e

Abb e ia ions___________________________________________________________
Abb e ia ions
[1,2-3] Re e ence numbe
α- alpha-
Å Angs om
β- be a-
n-Bu n-Bu yl
°C Deg ee Celsius
ca . ca alys
CDCl3 deu e a ed chlo o o m
CD2Cl2 deu e a ed me hylene chlo ide
C6D6 deu e a ed benzene
Cen Cen oid
Cp Cyclopen adienyl
Cq qua e na y ca bon
δ chemical shi in ppm
d double in NMR spec oscopy
dd double o double in NMR spec oscopy
E e hyl
Flu Fluo enyl
g g am
GC gas ch oma og aphy
h hou
Hz He z
Ind Indenyl
i-P isop opyl
kg kilog am
M me al
M+ Molecula ion
MAO me hylaluminoxane
Me me hyl
Abb e ia ions___________________________________________________________
mg millig am
min minu e
ml millili e
mol mol
mmol millimol
m/e mass/elemen al elec ic cha ge
Mn numbe a e age mola mass
Mw weigh a e age mola mass
MS mass spec ome y
NMR Nuclea Magne ic Resonance
n.d. no de e mined
PE polye hylene
Ph phenyl
PP polyp opylene
ppm pa s pe million
q qua e in NMR spec oscopy
. . oom empe a u e
s single in NMR spec oscopy
THF e ahyd o u an
TMA ime hylaluminum
iple in NMR spec oscopy
X halide
Con en s______________________________________________________________
Con en s
1 In oduc ion 1
1.1 Gene al 1
1.2 Resea ch goal 7
2 Gene al Pa 8
2.1 Unb idged 1- and 2-subs i u ed bis(silylindenyl) zi conium (IV)
and ha nium (IV) complexes
8
2.1.1 Gene al ema ks 8
2.1.2 P epa a ion o he 1-subs i u ed silylindenyl compounds 5-8 9
2.1.3 P epa a ion o he 2-subs i u ed silylindenyl compounds 9-12 11
2.1.4 Cha ac e iza ion o compounds 1-12 12
2.1.5 Syn hesis o he ansi ion me al complexes 20
2.1.6 Cha ac e iza ion o he complexes 22
2.1.7 E hylene polyme iza ion expe imen s 32
2.1.7.1 Gene al aspec s and mechanism 32
2.1.7.2 E hylene polyme iza ion ac i i ies o complexes 13-18 34
2.1.7.3 E hylene polyme iza ion ac i i ies o complexes 19-24 35
2.1.7.4 Compa ison be ween he polyme iza ion ac i i ies o 1- and 2-
subs i u ed zi conocenes
37
2.1.7.5 Polyme analysis 38
2.2 1,2-Bis(dime hylsilyl)phenylidene-b idged zi conocene and
ha nocene dichlo ide complexes
40
2.2.1 Gene al ema ks 40
2.2.2 Syn hesis o he ligand p ecu so 41
2.2.3 Cha ac e iza ion o compound 27 42
2.2.4 Syn hesis and cha ac e iza ion o compounds 29 and 30 44
2.2.5 Syn hesis and cha ac e iza ion o he 1,3-bis(dime hylsilyl)
phenylidene b idged bis(indenyl) compound 33
46
2.2.6 Syn hesis o 1,2-phenylidene-bis(inden-1-yldime hylsilyl)
complexes o zi conium (34) and ha nium (35)
49
Con en s______________________________________________________________
2.2.7 Cha ac e iza ion o he complexes 34 and 35 49
2.2.8 C ys al s uc u es o complexes 34 and 35 54
2.2.9 Reac ions o compounds 29, 30 and 33 wi h zi conium
e achlo ide
59
2.2.10 E hylene polyme iza ion expe imen s wi h complexes 34 and
35
60
2.3 2,2’-Bis(me hylene)biphenylidene-b idged 1-indenyl
complexes o g oup (IV) me als
63
2.3.1 Gene al ema ks 63
2.3.2 P epa a ion o he ligand p ecu so s 38 and 39 63
2.3.3 Cha ac e iza ion o compounds 38 and 39 65
2.3.4 Syn hesis o he i anium, zi conium and ha nium complexes
40-42
68
2.3.5 Cha ac e iza ion o he complexes 40-44 69
2.3.6 C ys al s uc u e o complex 41 73
2.3.7 E hylene polyme iza ion s udies o complexes 40-44 76
2.4 9-Subs i u ed silyl luo enyl complexes o zi conium and
ha nium
80
2.4.1 Gene al ema ks 80
2.4.2 Syn hesis o he po en ial ligand 45 80
2.4.3 Cha ac e iza ion o compound 45 80
2.4.4 Syn hesis o complexes 46 and 47 83
2.4.5 Cha ac e iza ion o complexes 46 and 47 84
2.4.6 E hylene polyme iza ion expe imen s wi h complexes 45 and
46
86
3. Expe imen al Pa 87
3.1 Gene al 87
3.2 NMR spec oscopy 87
3.3 GC/MS 87
3.4 Mass spec ome y 88
In oduc ion and esea ch goals ____________________________________________
6
The publica ion o Waymou h’s complex has opened up a pa h o ex ensi e ongoing
s udies di ec ed o explo e he ela ionships be ween ca alys ac i i y, polyme
p ope ies and subs i uen e ec s a he 1- and 2-posi ions o he indenyl ings o
unb idged me allocene complexes.[40-44]
2-Subs i u ed bis(indenyl) me allocene ca alys s ha e me pa icula in e es in he
p oduc ion o linea low densi y polye hylene (LLDPE) due o hei high comonome
inco po a ion a e in he copolyme iza ion o e hylene wi h α-ole ins (pa icula ly 1-
hexene).[45-48] On he o he hand, he ac i i ies o 1-subs i u ed me allocene ca alys s in
he polyme iza ion o ole ins a e signi ican ly highe han he 2-subs i u ed analogues
bea ing he same ligands.
Elec on dona ing g oups, when connec ed di ec ly o indenyl o cyclopen adienyl
ligands, a e known o ha e a a ou able e ec on he ca alys ac i i y in e hylene
polyme iza ion eac ions by s abilizing he me al coo dina ion si e, while he p esence o
elec on wi hd awing g oups leads o he opposi e e ec p o iding less ac i e ca alys s.

In oduc ion and esea ch goals ____________________________________________
7
1.2 Resea ch goals
As indica ed in chap e 1.1, he ligand s uc u e plays a key ole in e ms o he ac i i y
and selec i i y o a ca alys . Mino changes in he ligand s uc u e o he b idging moie y
can lead o d ama ic e ec s on he p oduc i i y and selec i i y o a ca alys .
Keeping his in ocus, ou p ima y in e es is o syn hesize new b idged me allocene
complexes and unb idged me allocene complexes wi h unc ionalized silyl subs i uen s
a he 1- and 2- posi ions o he indenyl ing. The p oposed po en ial ligands include:
- 1,2-bis(dime hylsilyl)phenylidene b idged bis(indenyl) compounds.
- 2,2’-dime hyl-1-1’-biphenylidene b idged bis (indenyl) compounds.
- 2-silyl subs i u ed indenyl compounds.
- 1-silyl subs i u ed indenyl compounds.
- 9-silyl subs i u ed luo enyl compounds.
G oup (IV) me al complexes de i ed om he abo e men ioned po en ial ligands should
be syn hesized and hei ca aly ic ac i i y in e hylene polyme iza ion, in combina ion wi h
me hylaluminoxane (MAO) as a coca alys , should be es ed. We we e also in e es ed in
he ex en o which he s e ic and elec onic p ope ies o hese subs i uen s a ec he
subsequen ca alys pe o mance and he con ol o e polyme p ope ies h ough
”s uc u e-p ope y ela ionships”.
Gene al pa ___________________________________________________________
8
2. Gene al Pa
2.1 Unb idged 1- and 2-subs i u ed bis(silylindenyl) zi conium (IV) and ha nium
(IV) complexes
2.1.1 Gene al ema ks
Me allocene complexes ecei ed subs an ial a en ion in indus y and esea ch due o
hei capabili y o being highly ac i e ca alys p ecu so s o e hylene
homopolyme iza ion, copolyme iza ion and s e eospeci ic polyme iza ion o highe α-
ole ins. Unlike adi ional Ziegle and Na a[8-10] ca alys s, he acile ligand modi ica ion
wi h a ious subs i uen s has led o he p epa a ion o a la ge numbe o me allocene
complexes o imp o e he ac i i y o he ca alys s and he p ope ies o he p oduced
polyole ins. The size, na u e and posi ion o he subs i uen s a ached o he
cyclopen adienyl, indenyl, o luo enyl moie ies play a key ole on he ca aly ic ac i i y as
well as on he molecula weigh and molecula weigh dis ibu ion o he p oduced
polyme .[49-56]
Since Waymou h e al.[35,57] ha e epo ed he success ul applica ion o unb idged
bis(η5-2-phenylindenyl) zi conium dichlo ide, ac i a ed wi h MAO, in he p oduc ion o
elas ome ic polyp opylene (ePP), a wide ange o unb idged bis(2-indenyl) me allocene
complexes bea ing siloxy, amino, a yl, alkyl and alkenyl subs i uen s a he 2-posi ion o
he indenyl moie y ha e been syn hesized and in es iga ed as ca alys p ecu so s o
he polyme iza ion o ole ins.[58-67] The symme ic me allocene complexes de i ed om
subs i u ed indenes exis in wo con o ma ions: ac- and meso-dias e eome s. The a io
ac/meso depends on he bulkiness o he subs i uen .[68]
Silyl g oups ha e been ex ensi ely used as b idging g oups in ansa-me allocene
complexes.[25] Howe e , li le has been epo ed on he ca aly ic beha io o unb idged
indenyl complexes con aining silyl subs i uen s a ached di ec ly o he ligand. The
syn hesis o ac- and meso-bis(1-dime hylsilylindenyl)-zi conium dichlo ide was b ie ly
desc ibed in a e iew[69], while he syn heses o 1- and 2-subs i u ed
bis[( ialkylsilyl)indenyl]-zi conium dichlo ides we e only ecen ly epo ed in he
li e a u e.[70-73]
Gene al pa ___________________________________________________________
9
In his s udy, no el complexes o he ype [1-(4-XC6H4SiMe2)-η5-Ind]2MCl2 and [2-(4-
XC6H4SiMe2)-η5-Ind]2MCl2 (whe e X = Me, MeO, F; M = Z and H ) a e epo ed. The
cha ac e is ic ea u es o hese ligands a e he bulky silyl g oups unc ionalized wi h an
elec on dona ing g oup (Me), a he e o a om wi h a lone pai o elec ons (MeO) o an
elec on wi hd awing g oup (F). The subs i uen s we e chosen o co e a wide ange o
elec onic p ope ies and loca ed a he 4-posi ion o he a yl moie y. The beha io o
hese complexes owa ds e hylene polyme iza ion, a e ac i a ion wi h MAO, is
in es iga ed.
2.1.2 P epa a ion o he 1-subs i u ed silylindenyl compounds 5-8
The eac ions o he a ylchlo odime hylsilanes 1-4 wi h s oichiome ic amoun s o
indenylli hium, eshly p epa ed ia dep o ona ion o indene wi h n-bu ylli hium (n-BuLi),
a o ded he 1-silyl subs i u ed indenyl compounds 5-8 (Scheme 5). The
a ylchlo odime hylsilanes 1-4 as in e media es we e p epa ed acco ding o published
me hods[74,75] h ough eac ions o 4-subs i u ed b omobenzene de i a i es wi h
magnesium and a wo old excess o dichlo odime hylsilane in THF (Scheme 5).
In hese eac ions, a la ge excess o dichlo odime hylsilane was used o a oid he
p oblems a ising om subs i u ion eac ions o bo h chlo ine a oms a he Si a om
leading o he o ma ion o bisa yldime hylsilyl compounds as hea ie byp oduc s as
de ec ed by GC/MS analysis in some eac ions. The e o e, cleane eac ions and be e
yields we e only achie ed when using a la ge excess o dichlo odime hylsilane.
Scheme 5: P epa a ion o silane p ecu so s 1-4 and po en ial ligands 5-8.
Gene al pa ___________________________________________________________
10
Table 1: O e iew o he silyl compounds 1-8
Compound R S uc u e
1 Me hyl
Si Cl
2 Me hoxy
MeO Si Cl
3 Fluo o
FSi Cl
4 T i luo o
F
3
CSi Cl
5 Me hyl
Si
6 Me hoxy
MeO Si
7 Fluo o
FSi
8 T i luo o
F
3
CSi
Gene al pa ___________________________________________________________
11
2.1.3 P epa a ion o he 2-subs i u ed silylindenyl compounds 9-12
The 2-silyl subs i u ed indenyl compounds 9-12 we e eadily p epa ed ia a syn he ic
ou e ha comp ises he eac ion o he G igna d eagen o 2-b omoindene and he
co esponding a yldime hylchlo osilanes 1-4. The e o e, 2-b omoindene, p epa ed
acco ding o he li e a u e[76] by he eac ion o indene wi h N-b omosuccinimide (NBS)
ollowed by dehyd a ion (Scheme 6), was eac ed wi h magnesium powde in THF o
yield he co esponding deep ed G igna d eagen . Subsequen addi ion o a THF
solu ion o an equi alen amoun o he a yldime hylchlo osilanes 1-4 a o ded he 2-
subs i u ed silylindenyl compounds 9-12 in 65-80% yields (Scheme 7).
NBS
H
2
O / DMSO / 0°C B
p-TosOH
oluene
-H
2
O
B
OH
Scheme 6: P epa a ion o 2-b omoindene.
RSi Cl RSi
1-4 9-12
+B Mg
THF / e lux
-MgB Cl
No. R
9 Me
10 OMe
11 F
12 CF3
Scheme 7: P epa a ion o he ligand p ecu so s 9-12.

Gene al pa ___________________________________________________________
12
2.1.4 Cha ac e iza ion o compounds 1-12
Silyl subs i u ed indenes 5-12 and hei pa en chlo osilanes 1-4 we e cha ac e ized by
1H and 13C NMR spec oscopy, he comple e da a a e gi en in Table 2. The 1H and 13C
NMR spec a o compounds 7 and 9 a e discussed as examples. The 1H NMR spec um
o compound 7 (Scheme 8) shows wo double s a δ = 7.28 (d, 3J = 8.3 Hz, 2H) and δ =
7.24 (d, 3J = 7.2 Hz, 2H) ppm which can be assigned o he a oma ic p o ons H11 and
H10. The indene six-membe ed ing p o ons H7, H6, H5 and H4 display signals a δ =
7.09 ( , 1H), 7.03 (d, 3J = 7.4 Hz, 1H), 6.98 (d, 3J = 7.3 Hz, 1H) and 6.90 ( , 1H) ppm.
The wo double s a δ = 6.75 ppm (3J = 5.2 Hz, 1H) and 6.42 ppm (3J = 5.2 Hz, 1H) a e
assigned o he p o ons H3 and H2 o indene, while he signal co esponding o he
p o on a he 1-posi ion o indene (H1) appea s a δ = 3.54 ppm (s, 1H). The six p o ons
o he me hyl g oups (H8 and H9) p oduce he wo single s a δ = 0.03 and 0.00 ppm
(6H, Si(CH3)2).
Scheme 8: 1H NMR spec um o compound 7.
Gene al pa ___________________________________________________________
13
The 13C NMR spec um o compound 7 (Scheme 9) shows a double signal a δ = 163.9
ppm iden i ying he qua e na y ca bon a om C15 bea ing he luo ine a om; he spli ing
o he signal is due o he 1J coupling wi h he luo ine a om [1J(19F-13C = 249 Hz)] which
was obse ed also o C12, C13, and C14. The o he qua e na y ca bon a oms in he
molecule (C8, C9 and C12 (d)) display signals a δ = 144.6, 144.2 and 132.7(d) ppm.
The signals a ising a δ = 135.7, 135.2, 129.4, 125.0, 123.6, 122.8, 121.1, 114.9 ppm
a e assigned o he CH- ype ca bon a oms (C14 (d), C2, C3, C4, C5, C6, C7, and C13
(d)). The signal a δ = 45.7 ppm co esponds o he ca bon a om a he 1-posi ion o he
indenyl moie y (C1) while he silyl me hyl g oups (C10 and C11) display he high ield
shi ed signals a δ = -4.2 and -4.8 ppm.
Scheme 9: 13C NMR spec um o compound 7.
Gene al pa ____________________________________________________________
14
The 1H NMR spec um o compound 9 (Scheme 10) shows wo signals a δ = 7.36 (b ,
2H) and 7.32 (b , 2H) ppm co esponding o he a yl a oma ic p o ons H9 and H10 while
he p o on a ached a he 3-posi ion o indene (H2) gi es a mul iple a δ = 7.29 ppm.
The ou a oma ic p o ons o indene (H3, H4, H5, and H6) display a mul iple a δ =
7.12-7.07 (m, 4H) ppm while he p o ons a he 1-posi ion o indene (H1) gi e ise o he
single a δ = 3.36 (s, 2H) ppm. A δ = 2.26 ppm, he me hyl g oup p o ons (H11) appea
(s, 3H) while he wo equi alen me hyl g oups a ached o he silicon a om (H7, H8)
display a single a δ = 0.40 ppm. A se o signals appea ing beside he main signals
(H1-H11) is assigned o he 1-subs i u ed isome which exis s in app oxima ely 10-15%.
Scheme 10: 1H NMR spec um o compound 9.
Gene al pa ____________________________________________________________
15
The 13C NMR spec um o compound 9 (Scheme 11) shows h ee signals shi ed o
down ield a δ = 147.3, 146.9 and 145.4 ppm ha co espond o he qua e na y ca bon
a oms in he indenyl moie y (C8, C9, and C2) while he signals esul ing om he phenyl
ing, he qua e na y ca bon a oms (C11 and C14) appea a δ = 138.9 and 134.6 ppm.
The signal a δ = 142.1 ppm is assigned o he ca bon a om C3. The CH g oups’ ca bon
a oms in he phenyl ing (C12 and C13) a e cha ac e ized by he doubly in ensi e
signals appea ing a δ = 133.9 and 128.6 ppm. The ou signals a δ = 126.2, 124.8,
123.6, and 120.9 ppm can be assigned o he a oma ic CH ca bon a oms in he indene
six membe ed ing (C4, C5, C6, and C7). The signal a δ = 42.6 ppm co esponds o he
indenyl CH2 g oup (C1). The signal a δ = 21.5 ppm is assigned o he olyl ca bon a om
C15 while he signal a δ = -2.4 ppm ep esen s he wo iden ical me hyl g oups
a ached o he silicon a om (C10).
Scheme 11: 13C NMR spec um o compound 9.
Gene al pa ____________________________________________________________
22
Si
RSi
R
Si
R
M
Cl Cl
2
1) 2 n-BuLi, E
2
O, -78°C -
-2 BuH
2) MCl
4
, E
2
O, -78°C -
-2LiCl
9-12 19-24
No. R M
19 Me Z
20 Me H
21 OMe Z
22 OMe H
23 F Z
24 F H
Scheme 15: Syn hesis o he me allocene complexes 19-24.
2.1.6 Cha ac e iza ion o he complexes
The complexes 13-24 we e cha ac e ized wi h NMR spec oscopy, mass spec oscopy,
and elemen al analysis (see expe imen al pa ).
The silyl subs i u ed bis(indenyl) me allocene complexes we e cha ac e ized wi h 1H and
13C NMR spec oscopy (Table 3). The NMR spec a o ew complexes exhibi ed he
exis ence o wo o mo e isome s. The 1H and 13C NMR spec a o complexes 15 and
20 a e discussed as examples.
The 1H NMR spec um o complex 15 (Scheme 16) shows wo o e lapping double s a δ
= 7.50 ppm [3J = 7.8 Hz, 4H] co esponding o he indene six-membe ed ing p o ons
H3 and H6, while he signals o p o ons H4 and H5 appea a δ = 7.16-7.10 ppm (dd,
4H). The a oma ic phenyl p o ons H9 and H10 exhibi wo signals: a double a δ = 7.33

Gene al pa ____________________________________________________________
23
ppm (3J =7.9 Hz, 4H) co esponding o H9 and a double a δ = 6.83 ppm (3J =7.9 Hz,
4H) which could be assigned o H10. The p o ons a he 2-posi ion o he indene ing
(H1) gi es ise o he double appea ing a δ = 6.34 ppm (3J = 3.0 Hz, 2H) and he
p o on a he 3-posi ion o he indene ing (H2) p oduces he double a δ = 6.00 ppm (3J
= 3.0 Hz, 2H). The me hoxy p o ons (C11) can be associa ed wi h he single ha
appea s a δ = 3.72 ppm (6H), while he silyl me hyl g oups (H7 and H8) can be
de ec ed as wo single s appea ing u he up ield a δ = 0.60 and δ = 0.53 ppm (each
wi h 6H in ensi y).
Scheme 16: 1H NMR spec um o complex 15.
The 13C NMR spec um o complex 15 (Scheme 17) exhibi s six een esonance signals
in e p e ed as ollowed: he signal a down ield a δ = 160.6 ppm is assigned o he
qua e na y ca bon a om C15 bonded o he me hoxy g oup. The doubly in ensi e signal
appea ing a δ = 135.6 ppm esul s om C14. The emaining qua e na y ca bon a oms
C12, C8 and C9 a o d he signals a δ = 134.5, 129.9 and 128.9 ppm. A δ = 127.0,
126.8, 126.3, 126.1, and 125.5 ppm, he CH- ype ca bon a oms C3, C4, C5, C6, and C7
appea , while he CH- ype ca bon a om C13 a o ds he signal a 113.7 ppm. The signal
associa ed wi h he ca bon a om a he 1-posi ion o he indenyl moie y (C1) a ises a δ
= 113.8 ppm while he ca bon a om a he 2-posi ion o he indene ing (C2) is iden i ied
by he signal a δ = 105.3 ppm. The me hoxy ca bon a om (C16) is cha ac e ized by he
Gene al pa ____________________________________________________________
24
signal a δ = 55.1 ppm, while he wo me hyl g oups a ached o he silicon a om (C10
and C11) appea a δ = -0.5 and -1.1 ppm.
Scheme 17: 13C NMR spec um o complex 15.
The 1H NMR spec um o complex 20 (Scheme 18) shows a mul iple signal a δ = 7.71-
7.69 (4H) and a mul iple signal a δ = 7.20-7.18 (4H) ppm assigned o he p o ons H2
and H3 o he 6-membe ed indene ing. The a oma ic p o ons H5 and H6 gi e ise o
wo double s which appea a δ = 7.10 ppm (d, 3J = 7.2 Hz, 4H) and δ = 7.02 ppm (d, 3J
= 7.2 Hz, 4H). The single a δ = 5.90 ppm (s, 4H) is cha ac e is ic o he p o on H1 a
he indenyl moie y. The olyl CH3 p o ons (H7) p oduce he signal a δ = 2.25 ppm (s,
6H) while he six equi alen p o ons o he silyl me hyl g oups (H4) appea u he
up ield a δ = 0.41 ppm (s, 12H).
Gene al pa ____________________________________________________________
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Scheme 18: 1H NMR spec um o complex 20.
The 13C NMR spec um o complex 20 (Scheme 19) shows h ee signals down ield a δ
= 138.8, 138.1 and 135.4 ppm assigned o he qua e na y ca bon a oms C7, C10, and
C5. The wo signals a δ = 133.8 and 128.4 ppm a e associa ed wi h he CH- ype
ca bon a oms o he phenyl ing o he silyl g oup (C8 and C9) while he CH- ype
ca bons o he indene six-membe ed ing (C3 and C4) display signals a δ = 125.8 and
125.3 ppm. The qua e na y ca bon a om C2 gi es ise o he signal a δ = 128.6 ppm.
The signal a δ = 109.3 ppm is cha ac e is ic o he CH g oup ca bon a om C1 loca ed
a he 1-posi ion o he indenyl moie y. The me hyl g oup a he pa a posi ion o he
silicon a om (C11) p oduces he signal a δ = 21.3 ppm, while he signal a δ = -2.4 ppm
a ises om he me hyl g oups a ached o he silicon a om (C6). Due o he high
symme y o he complex (as well as o he o he 2-indenyl subs i u ed complexes), he
NMR spec a a e easie o e alua e compa ed wi h he spec a o he 1-subs i u ed
bis(indenyl) complexes.
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26
Scheme 19: 13C NMR spec um o complex 20.
The mass spec ome ical cha ac e iza ion o 1- and 2-subs i u ed bis(silylindenyl)
complexes using a di ec inle mass spec ome e (EI, 70 eV) was unsuccess ul. Using
his high ene gy (70 eV) ioniza ion echnique, he molecules p o ed o b eak in o smalle
agmen s. Fo ins ance, complex 17 when analyzed by mass spec oscopy (70 eV)
exhibi ed only peaks co esponding o he agmen om he loss o one ligand (m/z =
425). Acco dingly, ma ix-assis ed lase deso p ion ioniza ion (MALDI-TOF) was used as
a milde ioniza ion echnique o mass spec a measu emen s.
The MALDI-TOF mass spec a o complexes 17 and 19 a e discussed as ep esen a i e
examples. In he mass spec um o he zi conium complex 17 (Scheme 20), he molecula
ion peak is no obse ed. The ion o med by he loss o one chlo ine a om [M+-Cl]
p oduces he peak a m/z = 659 wi h 36% in ensi y. Fu he loss o a second chlo ine
a om [M+-2Cl] gi es he peak a m/z = 624 (in ensi y: 10%). The loss o one indenyl ligand
om he complex molecule gi es a peak a m/z = 429 wi h 16% in ensi y, while u he
loss o a chlo ine a om esul s in he peak a m/z = 391 wi h 18% in ensi y. The base peak
appea s a m/z = 343.
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Scheme 20: Mass spec um o complex 17 ob ained om MALDI-TOF analysis.
In he mass spec um o complex 19 (Scheme 21) he molecula ion peak was again no
obse ed. The peak a m/z = 653.1 wi h 4% in ensi y could be explained by he loss o
one chlo ine a om om he molecule, while he peak a m/z = 616.4 (6% in ensi y) is
gene a ed om he loss o wo chlo ine a oms. The loss o a ligand molecule gi es ise
o he peak a m/z = 425.3 (15% in ensi y), u he loss o a chlo ine a om gene a es he
peak a m/z = 388.3 (25% in ensi y). The 4- olyldime hylsilyl agmen gi es he peak a
m/z = 149.38 wi h 55% in ensi y.

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Scheme 21: Mass spec um o complex 19.
Table 3: 1H and 13C NMRa spec a o complexes 13-24.
No. S uc u e
1
H NMR
13
C NMR
13
Z
Cl Cl
Si
Si
7.52-7.46 m (4H)
7.30-7.28 m (4H)
7.13-7.06 m (8H)
6.3 b (2H, C3-Ind)
6.0 b (2H, C2-Ind)
2.3 s (6H, A -CH3)
0.58 s (6H, Si-CH3)
0.53 s (6H, Si-CH3)
139.3, 134.5, 134.4
(Cq)
134.2 (2C, A -CH)
130.0 (Cq)
128.8, 127.0, 126.8,
126.4, 126.1 (CH),
125.5 (2C, A -CH)
113.5 (Cq, C1-Ind)
105.3 (CH, C2-Ind)
21.5 (A -CH3)
-0.6, -1.3 (Si(CH3)2)
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14
H
Cl Cl
Si
Si
7.49-7.43 m (4H)
7.31-7.29 m (4H)
7.13-7.08 m (8H)
6.3 d (3J =2.8 Hz,
2H, C3-Ind)
5.8 d (3J =2.8 Hz,
2H, C2-Ind)
2.3 s (6H, A -CH3)
0.6 s (6H, Si-CH3)
0.5 s (6H, Si-CH3)
139.3, 134.5 (Cq)
134.2 (2C, A -CH)
133.5, 130.1 (Cq)
128.8, 126.9, 126.4,
126.3, 125.9 (CH),
125.5 (2C, A -CH)
110.1 (Cq, C1-Ind)
102.8 (CH, C2-Ind)
21.5 (A -CH3)
-0.4, -1.2 (Si(CH3)2)
15
Z
Cl Cl
Si
Si
O
O
7.50 d (3J =7.8 Hz,
4H)
7.33 d (3J =7.9 Hz,
4H, A -H)
7.16-7.10 dd (4H)
6.83 d (3J =7.9 Hz,
4H, A -H)
6.33 d (3J =3.0 Hz,
2H, C3-Ind)
6.00 d (3J =3.0 Hz,
2H, C2-Ind)
3.72 s (6H, O-CH3)
0.60 s (6H,Si-CH3)
0.53 s (6H,Si-CH3)
160.6 (Cq)
135.6 (2C, CH)
134.5, 129.9, 128.9
(Cq)
127.0, 126.8, 126.3,
126.1, 125.5 (CH)
113.8 (Cq, C1-Ind)
113.7 (2C, CH)
105.3 (CH, C2-Ind)
55.1 (O-CH3)
-0.5, -1.1 (Si(CH3)2)
16
H
Cl Cl
Si
Si
O
O
7.56-7.47 m (4H)
7.35 m (4H, A -H)
7.21 m (4H)
6.91 m (4H, A -H)
6.38 b (2H, C3-Ind)
6.05 b (2H, C2-Ind)
3.74 s (6H, O-CH3)
0.61 s (6H, Si-CH3)
0.53 s (6H, Si-CH3)
160.9 (Cq)
135.8 (2C, CH)
134.6, 129.7, 129.0
(Cq)
127.2, 126.9, 126.6,
126.3, 125.9 (CH)
111.2 (Cq, C1-Ind)
113.9 (2C, CH)
102.7 (CH, C2-Ind)
55.1 (O-CH3)
-0.5, -1.0 (Si(CH3)2)
Gene al pa ____________________________________________________________
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17b
Z
C
l
C
l
Si
Si
F
F
7.46 b (4H, A -H)
7.30 b (4H, A -H)
7.10 m (2H)
6.89 m (2H)
6.34 m (2H)
6.20 m (2H)
6.03 m (2H, C3-Ind)
5.63 m (2H, C2-Ind)
0.53 s (6H, Si-CH3)
0.49 s (6H, Si-CH3)
163.9 d (Cq, 1JC-F =
247 Hz)
136.0 d (2JC-F = 7.3,
CH-A , 2C)
133.6 d (Cq, 4JC-F =
3.8 Hz, C-F)
130.0, 128.5 (Cq)
127.6, 127.0, 126.3,
125.8, 125.3 (CH)
114.9 d (3JC-F = 19.8
Hz, CH-A , 2C)
113.8 (Cq, C1-Ind)
106.1 (CH, C2-Ind)
-0.5, -0.9 (Si(CH3)2)
18
H
C
l
C
l
Si
Si
F
F
7.50 dd (4H)
7.32 (4H)
7.13 d (4H)
6.95 (4H)
6.25 d (3J = 3.2 Hz,
2H, C3-Ind)
5.94 d (3J =2.8 Hz,
2H, C2-Ind)
0.58 s (6H, Si-CH3)
0.57 s (6H, Si-CH3)
163.8 d (Cq, 1JC-F =
248 Hz, C-F)
136.0 d (2JC-F=7.3,
A -CH, 2C)
133.9 d (Cq, 4JC-F=
3.8 Hz, C-F)
133.4, 128.6 (Cq)
127.2, 126.9, 126.4,
126.0, 125.3 (CH)
115.0 d (3JC-F = 19.5
Hz, A -CH, 2C)
110.7 (Cq, C1-Ind)
102.8 (CH, C2-Ind)
0.6, -1.1 (Si(CH3)2)
19
Si
Si
Z
C
l
C
l
7.65-7.63 m (4H)
7.11-7.09 m (4H)
7.04-6.95 dd (8H,
A -H)
5.96 s (4H, C1-Ind)
2.19 s (6H, A -CH3)
0.35 s (12H, Si-
CH3)
138.7, 138.4, 135.2
(Cq)
133.7 (CH)
129.3 (Cq)
128.4, 125.7, 125.4,
112.3 (CH)
21.3 (A -CH3)
-2.5 (CH3, Si(CH3)2)
20
Si
Si
H
C
l
C
l
7.71-7.69 m (4H)
7.20-7.18 m (4H)
7.10 d (3J =7.2 Hz,
4H, A -H)
7.02 d (3J =7.2 Hz,
4H, A -H)
5.90 s (4H, C1-Ind)
2.25 s (6H, A -CH3)
0.41 s (12H, SiCH3)
138.8, 138.1, 135.4
(Cq)
133.8 (CH)
128.6 (Cq)
128.4, 125.8, 125.3,
109.3 (CH)
21.3 (A -CH3)
-2.4 (Si(CH3)2)
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31
21
Si
Si
Z
Cl Cl
O
O
7.34-7.27 m (8H)
7.00-6.92 m (8H)
6.11 s (4H, C1-Ind)
3.84 s (6H, O-CH3)
0.10 s (12H, SiCH3)
159.7, 144.9, 144.0
(Cq)
129.4 (CH)
129.2 (Cq)
126.3, 126.0, 120.6,
113.9 (CH)
55.1 (O-CH3)
2.1 (Si(CH3)2)
22
Si
Si
H
Cl Cl
O
O
7.40-7.32 m (8H)
7.09-7.01 m (8H)
6.16 s (4H, C1-Ind)
3.84 s (6H, O-CH3)
0.11 s (12H, SiCH3)
160.0, 145.0, 144.1
(Cq)
129.7 (CH)
129.1 (Cq)
126.4, 126.0, 120.8,
114.3 (CH)
55.2 (O-CH3)
2.1 (Si(CH3)2)
23b
Si
Si
Z
Cl Cl
F
F
7.42 m (4H, A -H)
7.29-7.13 m (8H)
7.07 m (4H, A -H)
6.20 s (4H, C1-Ind)
0.08 s (12H, SiCH3)
164.1 d (1JC-F = 253
Hz, Cq)
144.7 d (4JC-F = 3.6
Hz, Cq)
143.4 (Cq)
135.7 d (2JC-F = 7.9
Hz, A -CH)
132.8 (Cq)
129.4, 125.0 (CH)
115.0 d (3JC-F = 19.5
Hz, A -CH)
105.3 (CH, C1-Ind)
-4.0 (Si(CH3)2)
24b
Si
Si
H
Cl Cl
F
F
7.43 m (4H, A -H)
7.28-7.16 m (8H)
7.05 m (4H, A -H)
5.90 s (4H, C1-Ind)
0.45 s (12H, SiCH3)
163.5 d (1JC-F = 254
Hz, Cq)
138.2 d (4JC-F = 3.6
Hz, Cq)
136.0 d (2JC-F = 6.9
Hz, A -CH)
133.5, 128.6 (Cq)
126.0, 125.7 (CH)
115.0 d (3JC-F = 19.5
Hz, CH)
109.1 (CH, C1-Ind)
-2.3 (Si(CH3)2)
a δ (ppm) el. CHCl3 (7.24 ppm, 1H NMR) and el. CDCl3 (77.0 ppm, 13C NMR) a 298 K.
b Two isome s.
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38
This pa e n indica es ha 1-subs i u ed indenyl complexes a e much mo e ac i e in
e hylene polyme iza ion han hei 2-subs i u ed coun e pa s. This beha io may be
explained in he way ha he same silyl subs i uen in posi ion 2 can exe mo e s e ic
hind ance a ound he me al cen e compa ed o he 1-subs i u ed analogues.
2.1.7.5 Polyme analysis
The p oduced polye hylene samples we e analyzed by di e en ial scanning calo ime y
(DSC) and iscosime y. The esul s o he polyme analyses a e summa ized in Table
6.
Table 6: DSC and iscosime y molecula weigh analysis o polye hylenes p oduced
wi h complexes 13-24
Complex ∆Hm [J/g] Tm [°C] C ys allini y [α] Mη [g/mol]
13 162.3 135.4 0.56 292000
14 151.2 136.2 0.52 355000
15 141.9 135.5 0.49 n.d.
16 142.0 136.2 0.49 n.d.
17 152.7 136.9 0.53 270000
18 141.7 135.9 0.49 535000
19 169.2 135.4 0.58 265000
20 144.9 135.2 0.50 445000
21 158.5 137.5 0.55 350000
22 138.9 135.0 0.48 n.d.
23 151.1 135.4 0.52 385000
24 130.8 137.3 0.45 n.d.
F om DSC analyses o he polye hylene samples no signi ican di e ences in he
mel ing poin s we e obse ed. Howe e , molecula weigh measu emen s showed ha
he molecula weigh s o polyme s p oduced wi h ha nium complexes a e signi ican ly
highe han hose o he polyme s p oduced wi h he analogous zi conium complexes.

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This could be a ibu ed o he he modynamically mo e s able bond be ween ha nium
and he polyme chain.[79]
The c ys allini y alues we e ob ained om he ollowing equa ion: α = ΔHm/ΔHm,0 wi h
ΔHm,0 = 290 J/g ex apola ed o 100% c ys alline polye hylene.[81] While he molecula
weigh s o he ha nium ca alyzed polye hylene samples we e highe compa ed wi h he
zi conium ca alyzed polyme s, he opposi e end could be obse ed o he c ys allini y
alues.
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2.2 1,2-Bis(dime hylsilyl)phenylidene-b idged zi conocene and ha nocene
dichlo ide complexes
2.2.1 Gene al ema ks
A wide ange o b idged bis(indenyl) me allocene complexes has been syn hesized and
es ed as ca alys p ecu so s o ole in polyme iza ion. These complexes include
di e en b idging- ype moie ies. Howe e , he mos commonly used b idges a e he
dime hylsilylene, e hylene, isop opylidene, and me hylene uni s.[26,28,82-86]
The s uc u e o he b idging uni in ansa me allocene complexes has a s ong in luence
on he ca alys ac i i y and he molecula weigh o he gene a ed polyme s.[87] The
ac i i y can be imp o ed by enla ging he eac ion space a ound he me al cen e ,
mainly by inc easing he me al-cen oid dis ance and he dihed al angle be ween he
wo indenyl based π-ligands.
In con as o silylene and alkylidene b idged me allocene complexes, ew examples o
ansa-me allocene complexes a e known con aining bulky a oma ic g oups as b idges.
Fo ins ance, o-xylidene- and naph hylidene-b idged ca alys s ha e ecen ly been
syn hesized and e alua ed as ca alys s o e hylene and p opylene polyme iza ion a e
ac i a ion wi h MAO. [88,89]
He ein, a syn hesis o new ansa-complexes o zi conium and ha nium is desc ibed,
which possess wo indenyl ligands ha a e linked h ough a 1,2-
bis(dime hylsilyl)phenylidene b idge (Scheme 25), oge he wi h a s udy o hei ca aly ic
beha io in he homogeneous polyme iza ion o e hylene.
SiSi
M
Cl Cl
M=
Z
,H
Scheme 25: Gene al s uc u al o mula o he me allocene complexes 34 and 35.
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2.2.2 Syn hesis o he ligand p ecu so
1,2-Bis(inden-1-yldime hylsilyl)benzene 27 was p epa ed ia a h ee s eps me hod ha
comp ises a G igna d coupling o 1,2-dib omobenzene wi h chlo odime hylsilane o gi e
1,2-bis(dime hylsilyl)benzene (25), ollowed by chlo ina ion wi h ca bon e achlo ide in
he p esence o a ca aly ic amoun o palladium dichlo ide o ob ain 1,2-
bis(chlo odime hylsilyl)benzene (26).[90] The desi ed compound was eadily p epa ed by
he eac ion o compound 26 wi h wo equi alen s o indenylli hium (p epa ed sepa a ely
ia eac ion o indene and n-bu ylli hium in e he ) (Scheme 26). This eac ion was
necessa ily conduc ed in e he a oom empe a u e. I ano he sol en such as THF is
used, he undesi ed monoindenyl spi o compound is o med as a side p oduc . This
p oceeds by he dep o ona ion a he C1-posi ion in he al eady silyl-bonded indene
ollowed by an in amolecula eac ion wi h he chlo ine a om o he same molecule
leading o he o ma ion o he cyclic mono subs i u ed indenyl de i a i e wi h a sp3-
hyb idized ca bon a om. Compound 27 was ini ially ob ained wi h ace amoun s o he
monoindenyl-subs i u ed de i a i e as side p oduc . Thus, he pu i y was imp o ed ia
p olonged e acua ion a ele a ed empe a u e.
1) Mg
2) ClSiH(CH
3
)
2
PdCl
2
/ CCl
4
25 26
Si Si
Si Si
Cl Cl
SiH HSi
B B -2MgB Cl - CHCl
3
27
Li2
- 2LiCl
Si Si
less han 5% (GC/MS)
+
Scheme 26: Th ee-s ep syn hesis o compound 27.
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2.2.3 Cha ac e iza ion o compound 27
Compound 27 was cha ac e ized by 1H NMR, 13C NMR and GC/MS (Table 7). The 1H
NMR spec um o compound 27 (Scheme 27) shows mul iple signals a δ = 7.76-7.73
(m, 2H), 7.50-7.46 (m, 2H), 7.29-7.26 (m, 4H) and 7.14-7.09 ppm (m, 4H) o he
a oma ic p o ons o bo h he b idge and he indenyl moie y (H10, H11, H4, H5, H6 and
H7). The wo signals appea ing a δ = 6.96 (d, 3J(H,H) =5.2 Hz, 2H) and 6.57 ppm (dd,
2H) can be a ibu ed o he p o ons a he 3- and 2-posi ions o he indenyl moie y (H3
and H2). The p o ons a he 1-posi ions o he indenyl moie ies (H1) p oduce he signal
a δ = 4.00 ppm (s, 2H) while he signal o he silyl p o ons (H8 and H9) appea s a δ =
0.20 ppm (s, 12H).
Scheme 27: 1H NMR spec um o compound 27.
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The 13C NMR spec um o compound 27 (Scheme 28) shows h ee esonance signals a
δ = 145.0, 144.4 and 144.0 ppm a ibu ed o he qua e na y ca bon a oms C8, C9, and
C12. The wo signals a δ =136.2 and 135.7 ppm co espond o C2 and C3 o he
indene i e membe ed ing, while he CH– ype ca bon a oms in he indenyl moie y (C4,
C5, C6 and C7) gi e signals a δ =129.7, 125, 123.6, and 123.0 ppm. The wo signals a
δ =128.3 and 121.0 ppm can be assigned o he ca bon a oms o he phenyl ing (C13
and C14). The ca bon a om a he 1-posi ion o he indenyl ligand (C1) shows a signal a
δ = 45.8 ppm while he silyl me hyl g oups (C10 and C11) show signals a δ = -1.3 and -
1.9 ppm.
Scheme 28: 13C NMR spec um o compound 27.

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The mass spec um o compound 27 (Scheme 29) shows he molecula ion peak a m/z
= 422 wi h 88% in ensi y. The ion o med by he loss o one indenyl uni [M+-indenyl]
gene a es he peak a m/z = 306 (in ensi y 45%) while he loss o wo indenyl uni s om
he molecule gi es ise o he base peak a m/z = 191.
Scheme 29: Mass spec um o compound 27.
2.2.4 Syn hesis and cha ac e iza ion o compounds 29 and 30
Compounds 29 and 30 we e syn hesized by he eac ions o one equi alen o 1,2-
bis(chlo odime hylsilyl)benzene (26) wi h wo equi alen s o 2-me hylindenylli hium and
luo enylli hium, espec i ely (Scheme 31). Bo h eac ions we e conduc ed in e he a
oom empe a u e. Fluo enylli hium was p epa ed by he eac ion o luo ene and n-
bu ylli hium in die hyle he , while 2-me hylindene (28) was p epa ed by he eac ion o 2-
indanone wi h me hyl magnesium b omide in die hyl e he ollowed by a wa e
elimina ion eac ion o he esul ing ca binol in e media e wi h pa a- oluenesul onic acid
in oluene (Scheme 30).[91]
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45
1)
C
H
3
MgB
2) H
2
O/ H
+
28
O
OH p-TosOH
oluene
H
2
O
_
-MgB (OH)
Scheme 30: P epa a ion o 2-me hylindene.
26
Si Si
Cl Cl
2
- 2LiCl
_
Li
+
Si
Si
30
2
- 2LiCl
29
Si
Si
_
Li
+
Scheme 31: P epa a ion o compounds 29 and 30.
Compounds 29 and 30 we e cha ac e ized by 1H NMR and 13C NMR spec oscopy
(Table 7).
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2.2.5 Syn hesis and cha ac e iza ion o he 1,3-bis(dime hylsilyl)phenylidene
b idged bis(indenyl) compound 33
The eac ion o 1,3-dib omobenzene wi h magnesium powde in he p esence o wo
equi alen s o die hoxydime hylsilane in e luxing THF a o ded 1,3-
bis(e hoxydime hylsilyl)benzene 31. E hoxy – chlo ine exchange a compound 31 was
achie ed ia eac ion wi h excess ace yl chlo ide in he p esence o a ca aly ic amoun
o py idine o yield compound 32.[90] A subsequen eac ion o one equi alen o
compound 32 wi h wo equi alen s o indenylli hium in die hyle he a oom empe a u e,
a o ded he desi ed bis(indenyl) compound 33 in 70% o e all yield (Scheme 32).
B B
Si
Cl
Si
Cl
Si
O
Si
O
2
- 2LiCl
SiSi
1) Mg
2) SiMe
2
(OE )
2
- 2 MgB (OE )
THF/ e lux, 3 h
CH
3
COCl / Py idine
e lux, 24 h
31 32
33
_
Li
+
Scheme 32: P epa a ion o compound 33.
Compound 33 was ully cha ac e ized by means o 1H NMR, 13C NMR and GC/MS. The
ull spec al da a a e gi en in Table7.
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Table 7: 1H, 13C NMR and GC/MS da a o compounds 25-33
No.
1
H NMR
13
C NMR MS [m/z] (%)
25a
7.64-7.60 m (2H)
7.44-7.38 m (2H)
4.78-4.72 m (2H)
0.43 s (6H, Si-CH3)
0.41 s (6H, Si-CH3)
144.3 (Cq)
134.3, 128.4 (CH)
-2.6 (Si(CH3)2)
194 [M+] (10)
179 M+-Me (46)
134 (100)
26a
7.90-7.88 m (2H)
7.47-7.45 m (2H)
0.80 s (12H, Si(CH3)2)
141.7 (Cq)
135.5, 129.3 (CH)
5.2 (Si(CH3)2)
247.0 M+-Me (100)
211 M+-HCl (38)
119 (23)
27b
7.76-7.73 m (2H)
7.50-7.46 m (4H)
7.29-7.26 m (2H)
7.14-7.09 m (4H)
6.96 d (3J =5.2 Hz,
2H, C3-Ind)
6.57 dd (2H, C2-Ind)
4.00 s (2H, C1-Ind)
0.22 s (6H, Si-CH3)
0.20 s (6H, Si-CH3)
145.0, 144.4, 144.0 (Cq)
136.2 (CH, C2-Ind)
135.7 (CH, C3-Ind)
129.7, 128.3, 125.0,
123.6 123.0, 121.0 (CH)
45.8 (CH, C1-Ind)
-1.3, -1.9 (Si(CH3)2)
422 M+ (88)
306 M+-Ind (45)
135 (85)
191 M+-2Ind (100)
28a
7.43-7.40 d (1H)
7.31-7.24 m (2H)
7.17-7.12 m (1H)
6.54 s (1H)
3.34 s (2H)
2.21 s (3H)
145.9, 145.8, 143.3 (Cq)
127.1, 126.1, 123.4,
123.2, 119.6 (CH)
42.6 (CH2)
16.7 (CH3)
130 M+ (100)
115 M+ -Me (92)
29a
7.75-7.71 m (2H)
7.46-7.43 m (2H)
7.33 d (2H)
7.20-7.16 m (2H)
7.00-6.89 m (4H)
6.59 s (2H, C3-Ind)
3.83 s (2H, C1-Ind)
1.97 s (J =4.0 Hz,
6H, CH3)
0.26 s (6H, Si-CH3)
0.21 s (6H, Si-CH3)
145.1, 144.8, 144.7,
144.2 (Cq)
136.5, 128.1, 126.3,
125.0, 123.1, 122.4,
119.6, 48.5 (CH)
17.6 (CH3)
-1.2 (Si(CH3)2)
450 M+ (1)
321 (70)
191 (100)
30b
7.72-7.69 m (4H, A -H)
7.24-7.05 m (16H)
4.22 s (2H, C9-Flu)
0.00 s (12H, Si(CH3)2)
145.6, 144.3, 141.3 (Cq)
137.2, 128.4, 126.3,
125.9, 124.7, 120.3,
42.4 (CH)
-1.5 (Si(CH3)2)
n.d.
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2.2.8 C ys al s uc u es o complexes 34 and 35
Single c ys als sui able o he X- ay di ac ion analyses o complexes 34 and 35 we e
ob ained by slow sol en e apo a ion om concen a ed solu ions o pen ane/ oluene
mix u es in an app oxima ely 9:1 a io. The molecula s uc u es o he complexes ha e
been es ablished by single c ys al X- ay di ac ion analyses. The ORTEP diag ams o
34 and 35 a e displayed in Schemes 37 and 38. Table 9 summa izes he c ys al da a
and s uc u al e inemen o complex 34, while he c ys al da a and s uc u al e inemen
o 35 is gi en in Table 10. Selec ed bond leng hs and angles o complexes 34 and 35
a e p esen ed in Tables 11 and 12.
Scheme 37: ORTEP diag am o complex 34, ellipsoids a e d awn in 30% p obabili y
le el. Hyd ogen a oms a e omi ed o cla i y.

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Scheme 38: ORTEP diag am o complex 35, along wi h a om numbe ing scheme,
ellipsoids a e d awn in 30% p obabili y le el. Hyd ogen a oms a e d awn as sphe es
wi h ixed small adius. Hyd ogen a om names a e omi ed o cla i y.
The solid s a e c ys al s uc u e analysis shows ha he me allocene dichlo ide
complexes 34 and 35 a e isos uc u al and adop a pseudo e ahed al coo dina ion
geome y a ound he me al a om o med by wo chlo ine a oms and wo η5-coo dina ed
indenyl ligands. As bo h complexes ha e closely equi alen bond leng hs and angles,
he ollowing desc ip ion o complex 34 is also alid o 35. One o he impo an
ea u es is ha he indenyl ligand planes in he molecule a e wis ed om being
pe ec ly C2-symme ic hus leading o a dis o ed ac o ien a ion. In 34, he angle Cl(1)-
Z -Cl(2) is 96.81° which is compa able o ha o he unb idged zi conocene complex
Ind2Z Cl2 (94.71°)[92] and he Me2Si b idged me allocene complex Me2Si(Ind)2Z Cl2
(98.76°).[93] The angle ha comp ises he zi conium a om and he wo i e membe ed
ing planes, Cen-Z -Cen, is 130.45° which is la ge han ha o Ind2Z Cl2 (128.3°) and
he b idged Me2Si(Ind)2Z Cl2 (127.8°). The Z -C bond dis ances a e di e en ; he
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qua e na y ca bon a oms be ween he i e- and six-membe ed ings, C(2), C(7), C(23),
and C(28), a e appa en ly u he away om he zi conium a om compa ed o he h ee
emaining ca bon a oms. These wo common ca bon a oms a e co alen ly bonded o
h ee o he ca bon a oms, which educes hei bonding abili y o zi conium.[94] The alue
o he dihed al angle be ween he wo planes o he i e ing cen oids is 51.37° which is
smalle han ha o Me2Si(Ind)2Z Cl2 wi h a di e ence o Δ = 10.57°. Fo me allocene
complexes p epa ed o ca aly ic unc ions, he g ea e dihed al angle allows be e
access o he monome molecules o he ca ionic me al cen e . The e o e, ca alys s wi h
wide dihed al angles should show compa a i ely highe ac i i ies. The dis ance
be ween he zi conium and he Cen1 plane is 2.2513 Å being sligh ly longe han he Z -
Cen2 dis ance (2.2114 Å), he dis ance be ween he wo cen oids is 4.05 Å and he
zi conium a om is loca ed 0.935 Å ou o his Cen1-Cen2 ec o .
Table 9: C ys al da a and s uc u e e inemen o 34.
Empi ical o mula C28 H28 Cl2 Si2 Z
Fo mula weigh 582.80
Tempe a u e 293(2) K
Wa eleng h 0.71073 Å
Space g oup P-1; T iclinic
a (Å) 9.1925(18)
b (Å) 10.110(2)
c (Å) 15.726(3)
α(°) 91.63(3)
β(°) 100.26(3)
γ(°) 111.24(3)
Volume 1333.6(5) Å3
Z 2
Densi y (calcula ed) 1.451 Mg/m3
Abso p ion coe icien 2.65 o 26.01°.
F(000) 596
C ys al size 0.28 x 0.18 x 0.16 mm3
The a ange o da a collec ion 0.718 mm-1
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Index anges -10<=h<=9, 9<=k<=12,
-19<=1<=19
Re lec ions collec ed 6271
Independen e lec ions 4372 [R(in ) = 0.0396]
Comple eness o he a =
26.01°
83.0 %
Abso p ion co ec ion None
Re inemen me hod Full-ma ix leas -
squa es on F2
Da a / es ain s / pa ame e s 4372 / 0 / 298
Goodness-o - i on F2 0.938
La ges di . peak and hole R1 = 0.0398,
wR2 = 0.0956
R indices (all da a) 0.534 and -0.314 e.Å-3
Final R indices [I>2sigma(I)] R1 = 0.0547,
wR2 = 0.1022
Table 10: C ys al da a o he ha nium complex 35.
Fo mula C28H28Cl2Si2H
Space g oup P-1, T iclinic
Z 2
a (Å) 10.0503(18)
b (Å) 9.1624(16)
c (Å) 15.643(3)
α(°) 91.567(19)
β(°) 100.285(18)
γ(°) 111.167(8)
Volume (Å3) 1315.0(4)
F(000) 660
Tempe a u e (K) 293
Wa e leng h (Å) 0.71069
C ys al dimensions (mm3) 0.3 × 0.2 × 0.2
Rin 0.056
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[Sin(
θ
)/
λ
]max (Å-1) 0.8709
Densi y (g cm-3) 1.6918
Abso p ion coe icien (mm-1) 4.276
Obse ed C i e ia I > 3σ(I)
No. o obse ed/all e lec ions 8001/ 11018
wRF(obs/all) 0.0395/0.0663
RF(obs/all) 0.0422/0.0446
Δ
ρ
max/ Δ
ρ
min (eÅ-3) 1.61/1.79
GoF(obs/all) 1.01/-0.87
Table 11: Selec ed Bond leng hs and angles o 34.
Selec ed bond leng hs [Å] Si(1)-C(1) 1.867(4)
Z -Cl(1) 2.4230(14) Si(2)-C(20) 1.872(4)
Z -Cl(2) 2.4398(11) Cen1-Z 2.2513
Z -C(1) 2.499(3) Cen2-Z 2.2114
Z -C(2) 2.634(3) Cen1-Cen2 4.0520
Z -C(7) 2.654(3 Selec ed bonds angles[°]
Z -C(8) 2.506(4) Cl(1)-Z -Cl(2) 96.81(5)
Z -C(9) 2.490(3) C(1)-Si(1)-C(12) 111.68(18)
Z -C(20) 2.491(3) C(20)-Si(2)-C(17) 114.49(16)
Z -C(21) 2.465(3) C(2)-C(1)-Si(1) 126.2(3)
Z -C(22) 2.479(3) C(28)-C(20)-Si(2) 129.1(3)
Z -C(23) 2.565(4) Dihed al angle 51.368
Z -C(28) 2.617(4) Cen1-Z -Cen2 130.453
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Table 12: Selec ed Bond leng hs and angles o 35.
Selec ed bond leng hs [Å] Si(1)-C(1) 1.868(4)
H -Cl(1) 2.4095(14) Si(2)-C(10) 1.855(4)
H -Cl(2) 2.3921(14) Cen1-H 2.194(4)
H -C(1) 2.469(4) Cen2-H 2.231(5)
H -C(2) 2.449(4) Cen1-Cen2 4.024(8)
H -C(3) 2.464(4) Selec ed bonds angles[°]
H -C(4) 2.549(4) Cl(1)-H -Cl(2) 95.91(4)
H -C(9) 2.596(4) C(1)-Si(1)-C(23) 113.77(15)
H -C(10) 2.473(4) C(10)-Si(2)-C(24) 111.32(19)
H -C(11) 2.452(4) C(9)-C(1)-Si(1) 129.7(3)
H -C(12) 2.485(4) C(18)-C(10)-Si(2) 125.8(3)
H -C(13) 2.644(4) Dihed al angle 51.478(150)
H -C(18) 2.625(4) Cen1-H -Cen2 130.813(10)
2.2.9 Reac ions o compounds 29, 30 and 33 wi h zi conium e achlo ide
Many u ile a emp s we e made o p epa e he zi conium complexes de i ed om
compounds 29, 30 and 33. The i led compounds we e eac ed wi h Z Cl4 by a simila
me hod used in Scheme 29. The a emp s o cha ac e ize he ob ained powde s wi h
NMR spec oscopy we e unsuccess ul due o hei insolubili y in common o ganic
sol en s. In he mass spec a, he molecula ion peak o any o he c acking pa e ns
ele an o he a ge ed complexes we e no de ec ed. Ins ead, a peak o he dili hium
sal appea ed [m/z = 435 co esponding o he compound 33 dili hium sal ]. The use o
di e en sol en s such as oluene o die hyl e he , besides THF, and p olonged hea ing
ailed o d i e hese eac ions owa ds comple ion.

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2.2.10 E hylene polyme iza ion expe imen s wi h complexes 34 and 35
Complexes 34 and 35 a e ansa bis(1-indenyl) me allocene dichlo ide complexes, he
wo indenyl ligands a e e he ed ia a 1,2-bis(dime hylsilyl) phenylene b idge. (Scheme
39).
SiSi
M
Cl Cl
34 (M = Z )
35 (M = H )
Scheme 39: S uc u al o mula o complexes 34 and 35.
The ca aly ic ac i i ies o complexes 34 and 35 in he homogeneous polyme iza ion o
e hylene along wi h he esul s o he polyme analyses a e summa ized in Table 13.
Me hylaluminoxane (MAO) was used as a coca alys (M:Al = 1:2000), he expe imen s
we e conduc ed a a polyme iza ion empe a u e o 60°C, 10 ba e hylene p essu e, and
in 250 ml o pen ane o one hou . The p oduced polye hylene samples we e analyzed
by DSC and iscosime y.
Table 13: E hylene polyme iza ion ac i i ies and analyses o he polyme s p oduced
wi h complexes 34/MAO and 35/MAO.
Complex
No. M
Ac i i ya
DSC Mη [g/mol]
∆Hm
[J/g]
Tm
[°C] [α]
34 Z 7610 124.5 135.5 0.43 366000
35 H 3590 124.6 135.5 0.43 375000
a (kg PE/mol ca . h)
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Bo h MAO-ac i a ed zi conium and ha nium ca alys s we e ac i e in e hylene
polyme iza ion. The zi conium ca alys 34/MAO ga e a highe ac i i y compa ed o he
ha nium complex de i ed om he same ligand while he ha nium ca alys 35/MAO
p oduced polye hylene wi h appa en ly highe molecula weigh . This esul is consis en
wi h he ac epo ed p e iously ha zi conocene ca alys s p o ide highe ac i i ies
while he ha nocene analogues p oduce polyole ins wi h g ea e molecula weigh s.[95]
The di e ence in he polyme iza ion beha io be ween Z - and H -based ca alys s could
be a ibu ed o he modynamically s onge σ-bonds be ween ha nium and he polyme
chain (H -C), hinde ing no only he chain p opaga ion bu also he elease o he chain,
gi ing ise o less ac i i ies and highe molecula weigh polye hylenes.[79] In line wi h
his assump ion, a ecen s udy o ha nocene ca alys s demons a ed ha he ac i a ion
ene gies o chain p opaga ion and e mina ion a e signi ican ly highe compa ed wi h
zi conium ca alys s.[96]
The ca aly ic ac i i y o 34/MAO in he homogeneous polyme iza ion o e hylene is, as
expec ed, lowe , han he ac i i ies obse ed o he unb idged bis-indenyl me allocene
complex[77] and ha o he single a om b idged me allocene complexes such as -CH2-
[97,98], -Me2C-[97,99], and -Me2Si-[29,85] b idged species. Simila esul s a e obse ed when
compa ing he ac i i y o 34/MAO wi h he widely known e hylidene b idged ca alys
p ecu so ,[100,101] ac-[E (Ind)2)]Z Cl2 ("B in zinge ca alys "). Howe e , in e ms o
molecula weigh , ca alys 34/MAO p oduces he polye hylene wi h he highes
molecula weigh compa ed wi h he abo e men ioned ca alys s (excep he Me2Si-
b idged one). The compa a i ely lowe ac i i y o 34/MAO can be a ionalized by he
exis ence o he 4 a oms-b idge, 1,2-bis(dime hylsilyl)phenylene, inco po a ing 2 C and
2 Si a oms. This igid and long b idge esul ed in a smalle dihed al angle and hus he
zi conium cen e becomes mo e shielded.
F om he c ys al s uc u e da a o complex 34/MAO (Scheme 37, Table 9), he alue o
he dihed al angle was de e mined o 51.4°, whe eas he dihed al angle epo ed o
CH2-, Me2C-, Me2Si-, and C2H4-b idged me allocene complexes a e 72.4°, 70.9°, 61.6°
and 62.1°. A g ea e alue o he dihed al angle be ween he ligand planes enhances
he ac i i y in ole in polyme iza ion by inc easing he eac ion space o he me al
cen e .[87]
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Ca alys 34 exhibi ed a a be e ca aly ic pe o mance in e ms o bo h ac i i y and
molecula weigh compa ed wi h he known me allocene ca alys s comp ising 4-a om-
b idges such as o-xylidene-b idged[88] and (-Me2Si-CH2-CH2-Me2Si-)-b idged[102]
ca alys s. This dis inc ion could be explained by he a ou able eplacemen o he wo
me hylene g oups wi h wo dime hylsilyl g oups in 34.
Changing he me al cen e in his ca alys sys em seems o ha e no in luence on he
mel ing poin s and c ys allini y alues o he polye hylenes.
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2.3 2,2’-Bis(me hylene)biphenylidene-b idged 1-indenyl complexes o g oup (IV)
me als
2.3.1 Gene al ema ks
The ac i i y and s e eoselec i i y o a me allocene-based ca alys in ole in
polyme iza ion can be signi ican ly in luenced by sligh s uc u al a ia ions in he
b idging uni (s uc u e p ope y ela ionship).[25] In his s udy, he syn hesis o new
ansa- i anocene, zi conocene, and ha nocene dichlo ide complexes is epo ed. The
i led complexes comp ise wo indenyl o 3-me hylindenyl ligands e he ed, a he 1-
posi ion, ia a 2,2’-bis(me hylene)-1,1’-biphenylidene b idge. Mo eo e , he ca aly ic
beha io o he p epa ed ansa-me allocene ca alys s in he homopolyme iza ion o
e hylene was in es iga ed a e ac i a ion wi h MAO.
2.3.2 P epa a ion o he ligand p ecu so s 38 and 39
Diphenic acid was con e ed o he co esponding 2,2-bis(hyd oxyme hyl) biphenyl 36
acco ding o a epo ed me hod.[103] Reduc ion o diphenic acid wi h li hium aluminium
hyd ide in THF and pu i ica ion by c ys alliza ion om a chilled me hanol solu ion ga e
36 in good yield. T ea men o he diol compound 36 wi h phospho us ib omide in
me hylene chlo ide a o ded 2,2'-bis(b omome hyl) biphenyl 37.[104]
Compounds 38 and 39 we e hen ob ained ia eac ions o 2,2'-bis(b omome hyl)
biphenyl 37 wi h wo equi alen s o indenylli hium o 2-me hylindenylli hium. Bo h
eac ions we e ca ied ou in THF a -78°C Thus he indenyl moie ies we e coupled
h ough he 3-posi ion (Scheme 40).
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display ou signals a δ = 7.50 (d, 2H), 7.35-7.31 (m, 6H) 7.27-7.24 ( , 2H) and 7.22-
7.17 (m, 6H) ppm. The p o ons loca ed a he 2-posi ions o he indenyl ings (H2)
gene a e he double a δ = 6.08 (d, 3J = 3.3 Hz, 2H) ppm while he p o ons a he 1-
posi ions o he indenyl ings (H1) p oduce he double a δ = 5.11 (d, 3J = 3.3 Hz, 2H)
ppm. The p o ons o he me hylene g oup (H7, H8) gi e he wo signals a δ = 4.23 (d, J
= 15.9 Hz, 2H) and 4.00 (d, J =16.2 Hz, 2H) ppm.
Scheme 45: 1H NMR spec um o complex 41.

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The 13C NMR spec um o complex 41 (Scheme 46) shows wo esonances a δ = 141.4
and 136.2 ppm a ibu ed o he qua e na y ca bon a oms in he biphenyl b idging uni
(C11 and C16). The wo signals appea ing a δ = 131.1 and 130.7 ppm a e assigned o
C5 and C6 o he indenyl ings. The emaining qua e na y ca bon a oms C8, C9 and C3
a e iden i ied wi h he signals appea ing a δ = 127.9, 126.0, and 118.4 ppm. The signal
a δ = 127.8 ppm can be assigned o he CH ca bon a om C7 while he ca bon a om C4
co esponds o he chemical shi a δ = 122.8 ppm. The a oma ic CH- ype ca bon
a oms in he biphenyl moie y (C12, C13, C14, and C15) a e associa ed wi h he signals
a δ =126.6, 126.2, 125.9, and 124.9 ppm. The signal a δ = 122.1 ppm is assigned o
he ca bon a om a he 2-posi ions o he indenyl g oups (C2) while he signal a δ =
104.7 ppm is cha ac e is ic o he ca bon a om a he 1-posi ion o he indenyl moie ies
(C1). The benzylic CH2 ca bon a oms (C10) appea a δ = 30.8 ppm.
Scheme 46: 13C NMR spec um o complex 41.
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The mass spec um o complex 42 is also discussed as an example. In he mass
spec um o complex 42 (Scheme 47), he molecula ion peak appea s a m/z = 658 wi h
14% in ensi y. The ion wi h m/z = 530 and 14% in ensi y can be explained by he loss o
one me hylene-indenyl agmen om he molecule, while he peak appea ing a m/z =
410 wi h 78% ela i e in ensi y a ises om he ee bis(indenyl) ligand. Fu he loss o
one indenyl agmen om he ligand gi es ise o he peak a m/z = 293 wi h 47%
in ensi y ela i e o he base peak. The base peak a m/z = 117 is gene a ed by indanyl
agmen s.
Scheme 47: Mass spec um o complex 42.
Table 15: 1H, 13C NMR and MS da a o complexes 40-44.
No.
1
H-NMR
13
C-NMR MS [m/z] (%)
40a)
7.64-7.61 m (2H)
7.40-7.36 m (2H)
7.26-7.19 m (8H)
7.18-7.12 m (4H)
5.99 b (2H)
5.12 b (2H)
4.30 d (J =15.4 Hz, 2H)
4.14 d (J =15.4 Hz, 2H)
142.4, 141.3, 132.8 (Cq)
131.5, 131.0, 129.6 (CH)
129.4 (Cq)
128.8, 128.4, 128.3,
127.1, 125.8, 123.3 (CH)
120.9 (Cq)
108.1 (CH)
32.6 (CH2)
526 M+ (12)
491 M+-Cl (52)
455 M+-Cl-HCl
(15)
409 ligand-H
(100)
293 (90)
41b) 7.50 d (3J =8.6 Hz, 2H)
7.35-7.31 m (6H)
7.27-7.24 (2H)
141.4, 136.2 (Cq)
131.1,130.7 (CH)
127.9 (C
q
)
570 M+ (45)
410 ligand (100)
293 (67)
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7.22-7.17 m (6H)
6.08 d (3J =3.3 Hz, 2H,
C2-Ind)
5.11 d (3J =3.3 Hz, 2H,
C1-Ind)
4.23 d (J =15.9 Hz, 2H)
4.00 d (J =16.2 Hz, 2H)
127.8, 126.6, 126.5,
126.2 (CH)
126.0 (Cq)
125.9, 122.8, 122.1 (CH)
118.4 (Cq)
104.7 (CH)
30.8 (CH2)
117 (96)
42a)
7.52-7.49 m (2H)
7.40-7.38 m (2H)
7.28-7.21 m (8H)
7.17-7.12 m (4H)
6.10 d (3J =3.4 Hz, 2H)
5.02 b (2H)
4.29 d (J =16 Hz, 2H)
4.15 d (J =16 Hz, 2H)
142.1, 137.0 (Cq)
131.7, 131.2, 128.3,
127.0, 126.9, 126.5,
126.3 (CH)
126.2 (Cq)
123.3, 122.2 (CH)
118.6, 116.5 (Cq)
101.8 (CH)
31.1 (CH2)
658 M+ (14)
529 (14)
410 ligand (78)
293 (47)
117 (100)
43a)c)
7.85-6.76 m (16H, A -H)
6.35 s (2H)
4.54 d (J =15.8 Hz, 2H, CH2)
4.03 d (J =15.8 Hz, 2H, CH2)
2.21 b (6H, CH3)
141.5, 138.3, 136.7 (Cq)
133.0, 131.1, 129.5 (CH)
129.1 (Cq)
127.7, 126.1, 125.8,
124.3, 123.0, 119.8 (CH)
117.0, 114.5 (Cq)
34.3 (CH2)
21.8 (CH3)
599 M+ (5)
527 M+-2Cl (13)
437 M+-Z Cl2-H
(22)
307 (33)
131 (100)
44a)c)
7.95-7.08 m (8H, A -H)
6.85 s (1H)
4.58 d (J =16.3 Hz, 1H, CH2)
4.07 d,(J =16.3 Hz, 1H, CH2)
2.32 b (3H, CH3)
144.0, 140.1, 137.7 (Cq)
134.8, 132.1, 130.1 (CH)
129.0 (Cq)
128.8, 126.9, 126.4,
124.9, 123.5, 121.0 (CH)
117.3, 115.9 (Cq)
34.7 (CH2)
22.0 (CH3)
n.d.
a) δ (ppm) el. CD2Cl2 (5.30 ppm, 1H NMR and 54.0 ppm, 13C NMR) a 298 K.
b) δ (ppm) el. CDCl3 (7.24 ppm, 1H NMR and 77.0 ppm, 13C NMR) a 298 K.
c) Two isome s, da a gi en o he mos in ensi e signals.
2.3.6 C ys al s uc u e o complex 41
The solid s a e molecula s uc u e o he zi conocene complex 41 was de e mined by
single c ys al X- ays di ac ion analysis. C ys als sui able o X- ay measu emen s we e
g own om a concen a ed solu ion o a pen ane/ oluene mix u e. The ORTEP iew o
he molecula s uc u e o complex 41 is displayed in Scheme 48. The c ys allog aphic
Gene al pa ____________________________________________________________
74
da a and s uc u al e inemen a e p esen ed in Table 16 while he selec ed bond
leng hs and angles a e collec ed in Table 17. The a angemen o he wo i e-
membe ed ing cen oids and he wo chlo ine a oms a ound he zi conium can be
desc ibed as a pseudo e ahed al geome y. The wo indenyl ligands a e aligned in a
s agge ed con o ma ion leading o an asymme ic ac o ien a ion. In consis ence wi h
his, he alues o he angles Cl1-Z -Cl2 and Cen-Z -Cen a e 97.23° and 128.73°. These
alues co espond o hose o p e iously cha ac e ized b idged me allocene
complexes.[87] The bond leng hs o he zi conium a om wi h he ca bon a oms a y
be ween 2.46-2.61 and 2.43-2.65 Å. o he wo i e-membe ed ings. The wo phenyl
ings o he biphenyl b idge a e aligned in di e en planes wi h a dihed al angle o 79.8°.
The alue o he dihed al angle be ween he wo planes o he i e ings cen oids is
53.72° which is smalle compa ed o he alue known o Me2Si(Ind)2Z Cl2 (61.9°).[93]
Scheme 48: The ORTEP diag am o he complex 41, ellipsoids a e d awn in a 30%
p obabili y le el. Hyd ogen a oms a e omi ed o cla i y.
Gene al pa ____________________________________________________________
75
Table 16: C ys al da a o complex 41.
Fo mula C32H24Cl2Z 1
Space g oup I 41/a, Te agonal
Z 16
a (Å) 26.045(2)
b (Å) 26.045(2)
c (Å) 14.9997(10)
α(°) 90
β(°) 90
γ(°) 90
Volume (Å3) 10175.1(13)
F(000) 4640.0
Tempe a u e (K) 293
Wa e leng h (Å) 0.71069
C ys al dimensions (mm3) 0.30 × 0.28 × 0.20
Rin 0.125
[Sin(
θ
)/
λ
]max (Å-1) 0.600
Densi y (g cm-3) 1.4896
Abso p ion coe icien (mm-1) 0.662
Obse ed C i e ia I > 3σ(I)
No. o obse ed/all e lec ions 2054/4589
wRF(obs/all) 0.0435/0.0544
RF(obs/all) 0.0522/0.1801
Δ
ρ
max/ Δ
ρ
min (eÅ-3) 1.22/-1.46
GoF(obs/all) 1.59/2.00

Gene al pa ____________________________________________________________
76
Table 17: Selec ed bond leng hs and angles
Selec ed bond leng hs[Å] C(23)-C(24) 1.5075(1)
Z -Cl(1) 2.4245(1) Z -Cen1 2.2230(5)
Z -Cl(2) 2.4279(1) Z -Cen2 2.2486(5)
Z -C(1) 2.6147(2) Cen1-Cen2 4.0317(2)
Z -C(6) 2.5122(1) Selec ed bonds angles[°]
Z -C(7) 2.4627(1) Cl(1)-Z -Cl(2) 97.233(2)
Z -C(8) 2.4989(1) C(1)-C(9)-C(10) 124.566(4)
Z -C(9) 2.5434(1) C(9)-C(10)-C(11) 115.183(4)
Z -C(24) 2.5775(2) C(23)-C(24)-C(25) 123.387(4)
Z -C(25) 2.6504(1) C(22)-C(23)-C(24) 113.375(4)
Z -C(30) 2.6049(2) Cen1-Z -Cen2 128.734(3)
Z -C(31) 2.4291(1) Cen (1) ^ Cen(2) 53.723(4)
Z -C(32) 2.4723(1) Ph(1) ^ Ph(2) 79.829(5)
C(9)-C(10) 1.5092(1)
2.3.7 E hylene polyme iza ion s udies o complexes 40-44
Complexes 40-44 a e ansa-me allocene dichlo ide complexes o g oup IV me als (Ti, Z ,
and H ). The wo indenyl ligands a e e he ed h ough he 3-posi ions ia a 2,2’-
bis(me hylene)-1,1’-biphenylidene b idge. The gene al s uc u e o mula o he
complexes is illus a ed in Scheme 49.
M
C
l
C
l
R
R
Scheme 49: S uc u al o mula o complexes 40-44.
Gene al pa ____________________________________________________________
77
The ca aly ic ac i i ies o complexes 40-44 in he homogeneous polyme iza ion o
e hylene we e in es iga ed a e ac i a ion wi h me hylaluminoxane (M:Al = 1:2000). The
expe imen s we e conduc ed a a polyme iza ion empe a u e o 60°C, 10 ba e hylene
p essu e, and in 250 ml o pen ane o one hou . The p oduced polye hylene samples
we e analyzed by DSC and iscosime y. The esul s a e illus a ed in Table 18.
Table 18: Ac i i ies and polyme analysis esul s o ca alys s 40-44
Complex No.
Ac i i y
[kg PE/mol ca . h]
DSC
∆Hm [J/g]
Tm [°C]
[α]
Mη [g/mol]
Ti
C
l
C
l
40 Inac i e - -
Z
C
l
C
l
41 12460
148.1
135.0
0.51
355000
H
C
l
C
l
42 3810
144.9
135.2
0.5
310000
Gene al pa ____________________________________________________________
78
Z
C
l
C
l
43 3010
145.1
135.4
0.5
485000
H
C
l
C
l
44 1020 n.d. n.d.
In he se ies o complexes 40-44, he zi conium ca alys 41/MAO was he mos ac i e
ca alys [12460 kg PE/mol ca . h] whe eas he ha nium ca alys 42/MAO bea ing he
same ligand showed lowe ac i i y [3810 kg PE/mol ca . h]. The i anium complex 40
was inac i e in e hylene polyme iza ion unde he p esc ibed condi ions. This inac i i y
can be a ibu ed o he ins abili y o Ti(IV) complexes and hei endency o educ ion o
gi e inac i e Ti(III) species a con en ional polyme iza ion empe a u es.[105] On going
om 41/MAO o he 3-me hyl subs i u ed zi conium ca alys 43/MAO, a ma ked
dec ease in ac i i y is obse ed ( om 12460 o 3010 kg PE/mol ca . h). A simila
dec ease in ac i i y has been obse ed when using he 3-alkyl subs i u ed Me2Si-
b idged ca alys s [Me2Si(3-R-Ind)2]Z Cl2[85]. In his ega d, he d op in ac i i y can be
a ibu ed o he inc ease o s e ic conges ion a ound he me al cen e caused by he
wo me hyl g oups a he indenyl ligands.
Ac oss he se ies, changing he me al and in oduc ion o me hyl g oups p o ed o ha e
no in luence on he he mal p ope ies and he c ys allini ies o he p oduced polyme s.
By compa ing he ca aly ic pe o mance o 41/MAO wi h he p e iously epo ed ele an
ansa-ca alys s, he e is a good co ela ion be ween he ca aly ic ac i i y o he ansa-
ca alys s and hei dihed al angles. The dihed al angle o complex 41 is 53.7° (Table 17)
which is smalle han ha o he CH2-b idged (72.4°) and he Me2C-b idged me allocene
Gene al pa ____________________________________________________________
79
complexes (70.9°). Howe e , ca alys 41/MAO exhibi ed highe ca aly ic ac i i y (12460
kg PE/mol ca . h) han he CH2-b idged ca alys (6900 kg PE/mol ca . h)[97] and he
Me2C-b idged ca alys (10000 kg PE/mol ca . h)[97]. This could be o igina ed o he
he mal ins abili y o he single ca bon a om b idged me allocene complex. Mo eo e ,
ca alys 41/MAO p oduces a polye hylene wi h highe molecula weigh compa ed wi h
he abo e men ioned single ca bon a om b idged me allocene complexes. Addi ionally,
ca alys 41/MAO showed a be e ca aly ic pe o mance in e ms o bo h ac i i y and
molecula weigh o he p oduced polyme s compa ed wi h he o-xylylene-[88] and he
1,2-bis(dime hylsilyl)e hylene-b idged[102] me allocene ca alys s.
The ca aly ic ac i i y pe o med by 41/MAO is signi ican ly lowe han he ac i i y
epo ed o he unb idged ca alys (29300 kg PE/mol ca . h)[77], he Me2Si-b idged
ca alys (19870 kg PE/mol ca . h)[85], and he e hylidene-b idged ca alys [101] (16500 kg
PE/mol ca . h) due o he ema kable di e ence in he dihed al angle alues and hus
he accessibili y o he me al cen e .
Gene al pa ___________________________________________________________
86
Table 19: 1H and 13C NMRa spec a o complexes 46 and 47.
No. 1H NMR 13C NMR
46
7.78 d (3J = 8.2 Hz, 4H, A -H)
7.33 d (3J = 8.2 Hz, 4H, A -H)
7.20-7.17 (4H)
7.00-6.94 m (8H)
6.87 d (3J = 7.3 Hz, 4H)
2.15 s (6H, A -CH3)
0.70 s (12H, Si(CH3)2)
138.3, 137.4, 136.3 (Cq)
134.0, 128.3 127.5, 126.2,
124.0, 123.3 (CH)
120.4, 102.0 (Cq)
21.3, (CH3)
0.5 (Si(CH3)2)
47
7.81 d (3J = 9.1 Hz, 4H, A -H)
7.39 d (3J = 9.1 Hz, 4H, A -H)
7.21-7.12 (4H)
7.05-6.89 m (8H)
6.85 d (3J = 7.3 Hz, 4H)
2.15 s (6H, A -CH3)
0.70 s (12H, Si(CH3)2)
139.7, 137.9, 136.1 (Cq)
134.6, 128.4 127.7, 126.5,
124.2, 123.1 (CH)
120.9, 103.1 (Cq)
21.4, 0.5 (CH3)
0.5 (Si(CH3)2)
a δ (ppm) el. CDCl3 (7.24 ppm, 1H NMR and 77.0 ppm, 13C NMR) a 298 K.
2.4.6 E hylene polyme iza ion expe imen s wi h complexes 45 and 46
Complexes 46 and 47 we e es ed o e hylene polyme iza ion a e ac i a ion wi h
me hylaluminoxane (MAO) wi h a M:Al a io o 1:2000. The expe imen s we e
conduc ed a 60°C and 10 ba e hylene p essu e in 250 ml o pen ane. These
complexes we e ound o be inac i e in polyme iza ion eac ions. The same esul was
epo ed by Al e al.[107] using unb idged 9-subs i u ed phenyl luo enyl complexes o
he polyme iza ion o e hylene and p opene. The ine ness o he luo enyl complexes
46 and 47 could be a ibu ed o he he mal ins abili y esul ing om ing-slippage
eac ions changing he hap ici y o he luo enyl ings om η5→ η3→ η1[106] The
bulkiness o he subs i uen s may also be a eason o he inac i i y o 46 and 47.

Expe imen al pa ________________________________________________________
87
3. Expe imen al Pa
3.1 Gene al
All eac ions we e ca ied ou unde an ine gas a mosphe e o pu e oxygen- ee a gon
using s anda d Schlenk echniques. n-Pen ane, n-hexane, die hyl e he , oluene, and
e ahyd o u an we e pu i ied by dis illa ion o e Na/K alloy. Die hyl e he was
addi ionally dis illed o e li hium aluminum hyd ide. Toluene was addi ionally dis illed
o e phospho us pen oxide. Me hylene chlo ide and ca bon e achlo ide we e d ied
o e phospho us pen oxide. Deu e a ed o ganic sol en s (CDCl3, CD2Cl2, and C6D6) o
NMR spec oscopy we e pu chased om Eu iso-Top and s o ed o e molecula sie es
(3 Å). A gon (5.0) and e hylene (3.5) we e pu chased om Rieβne Company.
Me hylaluminoxane (10% in oluene) was pu chased om Chem u a Eu ope Limi ed
(Be gkamen). All o he s a ing ma e ials we e comme cially a ailable and used wi hou
u he pu i ica ion.
3.2 NMR spec oscopy
NMR spec a we e eco ded wi h B uke ARX (250 MHz), Va ian Ino a (300 MHz) o
Va ian Ino a (400 MHz) spec ome e s. All spec a we e eco ded a 298 K. In he 1H-
NMR spec a, he chemical shi o he esidual p o on signal o he sol en was used as
a e e ence (δ = 7.24 ppm o chlo o o m, δ = 5.32 ppm o me hylene chlo ide, δ = 7.16
ppm o benzene). In he 13C-NMR spec a, he chemical shi o he sol en was used
as a e e ence (δ = 77.0 ppm o chlo o o m-d1, δ = 54.0 ppm o me hylene chlo ide-d2,
δ = 128.0 ppm o benzene-d6).
3.3 GC/MS
GC/MS spec a we e eco ded wi h a The mo FOCUS gas ch oma og aph combined
wi h a DSQ mass de ec o . A 30 m HP-5 used silica column (in e nal diame e 0.32
mm, ilm 0.25 µm and low 1 ml/min) was used and helium (4.6) was applied as ca ie
gas. The measu emen s we e eco ded using he ollowing empe a u e p og am:
S a ing empe a u e: 50 °C, du a ion: 2 minu es;
Hea ing a e: 20 °K/minu e, du a ion: 12 minu es;
Expe imen al pa ________________________________________________________
88
Final empe a u e: 290 °C, du a ion: 27 minu es.
3.4 Mass spec ome y
Mass spec a we e eco ded wi h a VARIAN MAT CH-7 ins umen (di ec inle , EI, E =
70 EV) and a VARIAN MAT 8500 spec ome e a he Zen ale Analy ik o he Uni e si y
o Bay eu h. Ma ix Assis ed Lase Deso p ion Ioniza ion Time-o -Fligh Mass
Spec ome y (MALDI-TOF-MS) measu emen s we e pe o med on a B uke Dal onic
Re lex TOF using g aphi e as he ma ix. The lase in ensi y was se o 60-65 %. The
sample solu ions we e p epa ed in oluene o me hylene chlo ide a a concen a ion o 1
mg/ml.
3.5 Elemen al analysis
Elemen al analyses we e pe o med wi h a Va io EL ІІІ CHN ins umen . The e o e, 4-6
mg o he complex we e weighed in o a s anda d in pan. The in pan was ca e ully
closed and in oduced in o he au o sample o he ins umen . The alues o C, H and N
we e calib a ed using ace amide as a s anda d.
3.6 DSC analysis
DSC analyses we e pe o med on a Me le Toledo DSC/SDTA 821e ins umen . The
polyme samples we e p epa ed by enclosing 4-6 mg o he polyme s in s anda d
aluminum pans. The samples we e in oduced in o he au o sample o he ins umen
and he measu emen s we e eco ded using he ollowing empe a u e p og am:
Fi s hea ing phase: om 50 °C o 160 °C (10 °C/minu e);
Cooling phase: 160 °C o 50 °C (10 °C/minu e);
Second hea ing phase: om 50 °C o 160 °C (10 °C/minu e).
Liquid ni ogen was used as a cooling medium. Mel ing en halpies and mel ing poin s
we e aken om he second hea ing phase. The alues we e calib a ed using indium as
a s anda d (m.p. 429.78 K, Hm = 28.45 J/g).
Expe imen al pa ________________________________________________________
89
3.7 Viscosime y analysis
Viscosime y analyses o he de e mina ion o he iscosi y a e age molecula weigh s
[Mη] o he polye hylene samples we e pe o med on an Ubbelohde p ecision capilla y
iscome e in cis/ ans-decalin a 135 ± 0.1 °C. Fo he p epa a ion o he sample
solu ions, an amoun o 50 mg o he polyme was dissol ed in decalin (45 ml) by
hea ing o 3 hou s a 135 °C. Mη alues we e de e mined by compa ing he ob ained
alues wi h calib a ion cu es a ailable o di e en polyme concen a ions.
3.8 Single c ys al X- ays di ac ion
The c ys al s uc u e analysis o complex 34 was pe o med wi h a STOE-IPDS II
di ac ome e equipped wi h an Ox o d C yos eam low- empe a u e uni . The c ys al
s uc u e analysis o complexes 35 and 41 was pe o med wi h a Ma IP MAR345DTB
de ise (Mo-Kα adia ion, γ = 0.71073 Å).
C ys al da a:
Complex 34: Yellow cubic c ys als, c ys al sys em is iclinic; space g oup is P-1; a =
9.1925 (18) Å, b = 10.110(2) Å, c = 15.726(3) Å; α = 91.36(3)°, β = 100.26(3)°, γ =
111.24(3)°; olume is 1333.6(5) Å3; d (calc) = 1.451 g/cm3; wa eleng h = 0.71073 Å;
abso p ion coe icien = 0.718 mm-1 ; F(000) = 596; e lec ions collec ed 6271;
independen e lec ions 4372 [R(in ) = 0.0396]; Goodness-o - i = 0.938; R indices (R1 =
0.0547, wR2 = 0.1022).
Complex 35: Yellow cubic c ys als, c ys al sys em is iclinic; space g oup is P-1; a =
10.0503(18) Å, b = 9.1624 (16) Å, c = 15.643(3) Å; α = 91.567(19)°, β =100.285(18)°, γ
= 111.167(8)°; olume is 1315.0(4) Å3; d = 1.6918 g/cm3; wa eleng h = 0.71069 Å;
abso p ion coe icien = 4.276 mm-1 ; F(000) = 660; no. o all e lec ions 11018; no. o
obse ed e lec ions 8001 [R(in ) = 0.056]; GOF (obs/all) = 1.01/-0.87; R(F) = 0.0422
(wR(F) = 0.0395).
Expe imen al pa ________________________________________________________
90
Complex 41: Yellow cubic c ys als, c ys al sys em is e agonal; space g oup is I 41/a; Z
= 16; a = b = 26.045 (2) Å, c = 14.9997(10) Å,; α = β = γ = 90°; olume is 10175(13) Å3;
d = 1.4896 g/cm3; wa eleng h = 0.71069 Å; abso p ion coe icien = 0.662 mm-1 ;
F(000) = 4640; no. o all e lec ions 4589; no. o obse ed e lec ions 2054 [R(in ) =
0.125]; GOF (obs/all) = 1.59/2.00; R(F) = 0.0522 (wR(F) = 0.0435).
3.9 Polyme iza ion o e hylene
Few millig ams o he complexes we e dissol ed o suspended in oluene (5-10 ml) and
mixed wi h he app op ia e amoun o me hylaluminoxane (MAO). The ac i a ed
complexes we e suspended in pen ane (250 ml) in a 1l Schlenk lask and hen
ans e ed unde a gon o a 1l Büchi au ocla e. The empe a u e o he he mos a was
adjus ed o he desi ed alue and an e hylene p essu e o 10 ba was applied o one
hou . A e eleasing he p essu e, he ob ained polyme was il e ed o e a i , washed
wi h dilu e hyd ochlo ic acid, wa e , and inally wi h ace one and d ied unde acuum.
3.10 Syn hesis p ocedu es
3.10.1 Gene al syn hesis o he a ylchlo odime hylsilane compounds 1-4
A solu ion o a 4-subs i u ed 1-b omobenzene (15.0 mmol) in THF (40 ml) was added
d opwise a oom empe a u e o a mix u e o magnesium powde (20.0 mmol) and
dichlo odime hylsilane (52.0 mmol) in THF (100 ml). A e he addi ion was comple e,
he lask con en was hea ed a e lux o app oxima ely 4 hou s and subsequen ly
s i ed a oom empe a u e o e nigh . The sol en and he excess
dichlo odime hylsilane we e emo ed in acuo (25 mba ). The esidue was ex ac ed
h ee imes wi h n-pen ane (300 ml) and he excess magnesium and magnesium sal s
we e il e ed o . The combined pen ane solu ions we e concen a ed unde acuum and
he esidue was dis illed unde educed p essu e. The compounds 1-4 we e ob ained as
colo less liquids in 60-75% yields.
Expe imen al pa ________________________________________________________
91
3.10.2 Gene al syn hesis o he 1-(a yldime hylsilyl)indenyl compounds 5-8
An amoun o 10 mmol o n-bu ylli hium (1.6 M in hexanes) was added o 10 mmol o
indene dissol ed in 100 ml o die hyl e he a 0°C. The solu ion was s i ed o 2 hou s a
oom empe a u e. The solu ion was again cooled o 0 °C and hen an equi alen
amoun o he app op ia e a ylchlo odime hylsilane (1-4) in die hyl e he was added
slowly. The esul ing solu ion was s i ed o e nigh a oom empe a u e. The sol en
was emo ed in acuo and he esidue was ex ac ed wice wi h pen ane. The
suspension was il e ed and passed h ough silica gel. A e emo ing he sol en ,
compounds 5-8 we e ob ained as yellow oily liquids in 70-80% yields.
3.10.3 Syn hesis o 2-b omoindene
To a mix u e o indene (200 mmol), dis illed wa e (15 ml) and dime hyl sul oxide (70 ml)
was added po ion wise an amoun o 210 mmol o N-b omosuccinimide. The esul ing
o ange solu ion was s i ed o 10 hou s a oom empe a u e, hyd olyzed wi h chilled
wa e (100 ml), and ex ac ed wi h die hyl e he (3 x 100 ml). The combined ex ac s
we e d ied wi h magnesium sulpha e and concen a ed o gi e c ys als o 2-
b omoindan-1-ol upon s anding o e nigh a -24 °C. The ob ained 2-b omoindan-1-ol
(120 mmol) was suspended in 100 ml o oluene and mixed wi h a ca aly ic amoun o
pa a- oluenesul onic acid monohyd a e. The mix u e was hea ed a e lux o 12 hou s,
and wa e was emo ed by a Dean-S a k appa a us. The esul ing da k b own
suspension was il e ed and he ola iles we e emo ed unde acuum. The esidue
was passed h ough silica gel using pen ane as eluen , hen he sol en was
e apo a ed, and he c ude p oduc was dis illed in acuo. 2-B omoindene was inally
ob ained as yellow c ys als in 55% yield.
3.10.4 Gene al syn hesis o he 2-(a yldime hylsilyl)indenyl compounds 9-12
Magnesium powde (18.0 mmol) and 15 ml o THF we e placed in a 250 ml lask. A
solu ion o 2-b omoindene (15.0 mmol) in 40 ml o THF was added o e a pe iod o 40
minu es using a p essu e equalizing-addi ion unnel. A e he addi ion was comple ed,
he eac ion mix u e was hea ed a e lux o 4 hou s. The un eac ed magnesium was
il e ed o and he iole - ed colou ed G igna d solu ion was added d opwise o a s i ed

Expe imen al pa ________________________________________________________
92
solu ion o he app op ia e a ylchlo odime hylsilane 1-4 (15.0 mmol) and 50 ml o THF a
oom empe a u e. The esul ing mix u e was s i ed o ano he 12 hou s. The sol en
was emo ed unde acuum and he esidue was ex ac ed wice wi h n-pen ane. The
suspension was il e ed and passed h ough silica gel. A e emo ing he sol en ,
compounds 9-12 we e ob ained as ed o yellow oily liquids in 65-80% yields.
3.10.5 Gene al syn hesis o he ansi ion me al complexes 13-24
An amoun o 2 mmol o he app op ia e 1- o 2-subs i u ed indenyl compound was
dissol ed in 50 ml o die hyl e he . To his solu ion, n-bu ylli hium (2 mmol 1.6 M in
hexanes) was added a -78 °C. This solu ion was allowed o wa m o oom empe a u e
and s i ed o u he 3 hou s. Subsequen ly, his mix u e was ans e ed o a
suspension o zi conium e achlo ide (1 mmol) o ha nium e achlo ide (1 mmol) in 20
ml o die hyl e he a -78 °C. The mix u e was slowly allowed o come o oom
empe a u e and s i ed o u he 24 hou s. Die hyl e he was emo ed and oluene
(100 ml) was added. The oluene suspension was il e ed, he olume o he il a e was
educed, and he complexes we e p ecipi a ed by addi ion o n-pen ane. A e il a ion,
he p ecipi a e was washed se e al imes wi h n-pen ane and d ied in acuo o ob ain
he desi ed complexes as colou ed powde s in 60-70% yields.
Table 20: Elemen al analysis da a o complexes 13-24.
No. Cex
p
% C heo % Hex
p
% H heo %
13 62.21 62.76 5.41 5.56
14 54.93 55.70 4.52 4.93
15 59.10 59.97 4.88 5.31
16 52.75 53.50 4.35 4.74
17 58.15 58.60 4.82 4.63
18 51.20 52.08 4.25 4.11
19 62.05 62.76 5.22 5.56
20 54.01 55.70 5.30 4.93
21 58.99 59.97 5.04 5.31
22 52.66 53.50 4.37 4.74
23 58.03 58.60 4.99 4.63
24 51.66 52.08 4.55 4.11
Expe imen al pa ________________________________________________________
93
3.10.6 P epa a ion o 1,2-bis(chlo odime hylsilyl)benzene (26)
A solu ion o 1,2-dib omobenzene (16.5 g, 70 mmol) in 70 ml o THF was added slowly
o a s i ed mix u e o magnesium powde (3.7 g, 147 mmol) and chlo odime hylsilane
(14.0 g, 147 mmol) in 15 ml o THF. The mix u e was e luxed o 3 hou s. A e cooling,
he solu ion was decan ed om solid magnesium sal s and he sol en was emo ed
unde acuum. The esidual oil was ex ac ed and washed wi h a la ge amoun o n-
hexane. A e emo al o he sol en , he esidue was pu i ied by dis illa ion unde
educed p essu e o a o d 1,2-bis(dime hylsilyl)benzene (25) in 60% yield. Compound
25 (20 mmol) was mixed wi h 40 ml o d y ca bon e achlo ide and 0.2 g o palladium
dichlo ide in a 100 ml wo necked lask equipped wi h a e lux condense . The mix u e
was e luxed o 3 hou s and excess ca bon e achlo ide and chlo o o m we e emo ed
by e acua ion. The esidual oil was dis illed a 85 °C (1 mba ) o ob ain compound 26 in
90% yield.
3.10.7 P epa a ion o 2-me hylindene (28)
A quan i y o 48 mmol o me hyl magnesium b omide (3M in e he ) was added d opwise
o a solu ion o 2-indanone (6.0 g, 48 mmol) in 100 ml o die hyl e he . A e wa ds, he
esul ing mix u e was s i ed o 2 hou s a oom empe a u e and hen hyd olyzed wi h
150 ml o dilu ed hyd ochlo ic acid (1.0 M). The e he con aining laye was sepa a ed
and he aqueous laye was ex ac ed ou imes wi h e he (each 100 ml). The o ganic
ex ac s we e combined, d ied o e sodium sulpha e, and he sol en was emo ed wi h
a o a y e apo a o . The esidue was mixed wi h 100 ml o oluene and a ca aly ic
amoun o pa a- oluenesul onic acid monohyd a e (PTSA). The suspension was
e luxed o 3 hou s in a Dean-S a k appa a us. The esul ing da k b own suspension
was il e ed and he ola iles we e emo ed unde acuum. The esidue was passed
h ough silica gel using pen ane as eluen . The sol en was emo ed by dis illa ion a
a mosphe ic p essu e o a o d 2-me hylindene as a ligh yellow oil in 40% yield.
3.10.8 Gene al syn hesis o he ligand p ecu so s 27, 29, and 30
An amoun o 16 mmol o indene, 2-me hylindene, o luo ene was dissol ed in 70 ml o
die hyl e he and cooled o -5 °C. Subsequen ly, n-bu ylli hium (16 mmol) was added
Expe imen al pa ________________________________________________________
94
d opwise o e 30 minu es ollowed by s i ing a oom empe a u e o 2 hou s. To his
mix u e, ano he solu ion o 1,2-bis(chlo odime hylsilyl)benzene (8 mmol) in 50 ml o
die hyl e he was added d opwise om a d opping unnel equipped wi h a p essu e
equalize . A e he addi ion was comple ed, he solu ion was s i ed o one hou and
il e ed om he solid li hium chlo ide. The solu ion was e apo a ed and me hylene
chlo ide (200ml) was added. A e il a ion, he sol en was emo ed unde high
acuum. Compounds 27 and 29 we e ob ained as hea y b ownish waxy ma e ials in 80-
90% yields, while compound 30 was ob ained as a solid which was u he pu i ied by
c ys alliza ion om me hylene chlo ide a -24 °C.
3.10.9 P epa a ion o 1,3-bis(chlo odime hylsilyl)benzene (32)
A mix u e o 1,3-dib omobenzene (19.0 g, 80 mmol) and die hoxydime hylsilane (166
mmol) in THF (40 ml) was added o e a pe iod o 1 hou o magnesium powde (170
mmol) suspended in 20 ml o THF. A e he mix u e was hea ed o e lux o 3 hou s
and hen cooled, he esul ing magnesium sal s we e il e ed o . The sol en was
e apo a ed and he esidue was dis illed unde educed p essu e o gi e pu e 1,3-
bis(e hoxydime hylsilyl)benzene (31) in 70% yield. An amoun o 50 mmol o compound
31 was placed in a 100 ml wo-necked lask and mixed wi h 0.2 ml o py idine and 30 ml
o ace yl chlo ide. A e he mix u e was hea ed o e lux o 72 hou s, excess ace yl
chlo ide and he esul ing e hyl ace a e we e e apo a ed, and he esidue was dis illed
unde educed p essu e o gi e he desi ed compound as a colou less liquid in 95%
yield.
3.10.10 P epa a ion o 1,3-bis(inden-1-yldime hylsilyl)benzene (33)
To a solu ion o indene (23 mmol) in die hyl e he (100 ml) a 0 °C, n-bu ylli hium (23
mmol) was added d opwise. The esul ing solu ion was s i ed o 2 hou s a oom
empe a u e ill gas e olu ion had ceased. A solu ion o 1,3-
bis(chlo odime hylsilyl)benzene (32) (11.5 mmol) in die hyl e he (40 ml) was added
o e 1 hou a oom empe a u e. A e he addi ion was comple ed, he mix u e was
s i ed o u he 4 hou s and dis illed wa e (100 ml) was added. The o ganic laye was
sepa a ed and he aqueous laye was ex ac ed wi h e he (2×100 ml). The o ganic
Expe imen al pa ________________________________________________________
95
po ion was d ied o e sodium sulpha e, and he ola iles we e emo ed unde high
acuum o ob ain he desi ed compound as a b own colou ed oil in 70% yield.
3.10.11 Gene al syn hesis o he ansi ion me al complexes 34 and 35
A quan i y o 2 mmol o 1,2-bis(1-indenyldime hylsilyl)benzene (27) was dissol ed in 50
ml o THF and cooled o -78 °C. To his solu ion, n-bu ylli hium (4 mmol, 1.6 M in
hexanes) was slowly sy inged. This solu ion was allowed o wa m o oom empe a u e
and s i ed o u he 3 hou s ill no mo e gas e olu ion was obse ed. The esul ing
solu ion was ans e ed ia cannula o a solu ion o zi conium e achlo ide (2 mmol) o
ha nium e achlo ide (2 mmol) in 20 ml o THF a -78 °C. A e wa ming o oom
empe a u e, he mix u e was subsequen ly s i ed o 48 hou s a 60-65 °C. The sol en
was emo ed in acuo and oluene (100) ml was added. The oluene suspension was
il e ed, he clea solu ion was concen a ed o app oxima ely 5 ml and he complexes
we e p ecipi a ed by he addi ion o n-pen ane. A e il a ion, he p ecipi a e was
washed se e al imes wi h n-pen ane and d ied in acuo o ob ain he desi ed
complexes as yellow powde s in 70-75% yields. Bo h complexes we e c ys allized om
concen a ed pen ane/ oluene mix u es o ob ain yellow cubic c ys als sui able o X- ay
c ys allog aphy analysis.
Table 21: Elemen al analysis da a o complexes 34 and 35.
No. Cex
p
% C heo % Hex
p
% H heo %
34 57.65 57.70 4.79 4.84
35 49.75 50.19 4.25 4.21
3.10.12 P epa a ion o 2,2’-bis(b omome hyl) biphenyl (37)
A solu ion o diphenic acid (7.74 g, 32 mmol) in 40 ml o THF was added o e 40
minu es o a suspension o li hium aluminum hyd ide (2.508 g, 66.0 mmol) and 50 ml
THF a 0 C°. A e he addi ion, he lask con en s we e hea ed unde e lux o e nigh .
Then, he eac ion was ca e ully hyd olyzed wi h wa e (75 ml) and a 15% sodium
hyd oxide solu ion (75 ml). Die hyl e he (100 ml) was added and he o ganic phase was
sepa a ed, d ied o e sodium sulpha e, and e apo a ed o d yness. The esidue was
Summa y______________________________________________________________
102
dep o ona ion o he ligand p ecu so s using n-BuLi ollowed by eac ions o he
co esponding me al e achlo ide.
M
Cl Cl
RR
R = H, Me; M = Ti, Z , H
The se ies o he unsubs i u ed ansa-complexes (R = H) showed highe ac i i ies
compa ed o he me hyl subs i u ed coun e pa s. The zi conium complex 42 showed
he highes ac i i y (12460 kg PE/mol ca . h) ollowed by he ha nium complex 43 (3820
kg PE/mol ca . h) while he i anium complex 40 was inac i e which could be a ibu ed
o he mal ins abili y and a endency o decomposi ion. The in oduc ion o me hyl
g oups a he 1-posi ion o he indenyl moie ies leads o a ema kable dec ease in he
ac i i y p obably due o s e ic hind ance esul ing om he wo me hyl g oups. The
ob ained polye hylenes we e analyzed by di e en ial scanning calo ime y (DSC) and
iscosime y.
A se ies o symme ic unb idged 9-subs i u ed dime hyl( olyl)silyl- luo enyl complexes o
zi conium and ha nium was syn hesized, cha ac e ized and es ed in ca aly ic e hylene
polyme iza ion eac ions. These complexes we e inac i e in he MAO assis ed
polyme iza ion o e hylene. This could be e e ed o hei ins abili y owa ds ing-
slippage eac ions changing he hap ici y (η5→ η3→ η1) o he luo enyl ings.

Zusammen assung______________________________________________________
103
5. Zusammen assung
Die Ziel de o liegenden A bei wa en die Syn hese und Cha ak e isie ung neua ige
e b ück e und un e b ück e Bis(indenyl)-Komplexe on Me allen de IV.
Nebeng uppe und die Un e suchung ih e ka aly ischen Eigenscha en bei de
homogenen E henpolyme isa ion. Zu diesem Zweck wu den e schiedene
Liganden o s u en syn he isie , wie z.B. Silylindenyl-Ve bindungen mi Subs i uen en in
1- und 2-Posi ion, 1,2-Bis(inden-1-yldime hylsilyl)benzol, 2,2’-Bis(inden-1-ylme hyl)-1,1’-
biphenyl und Fluo enylde i a e mi Silylsubs i uen en in 9-Posi ion. Die en sp echenden
Dichlo id-Komplexe de G uppe-IV-Me alle wu den syn he isie und als
Ka alysa o o s u en ü die E henpolyme isa ion eingese z .
De e s e Teil diese A bei besch eib die Syn hese symme ische , un e b ück e
Zi konium- und Ha niumkomplexe mi Silylindenyl-Liganden, die Subs i uen en in 1- und
2-Posi ion agen, und die Un e suchung ih es Po en ials ü die E henpolyme isa ion.
Silylindenyl-Ve bindungen mi Subs i uen en in Posi ion 1 esul ie en aus de Reak ion
de en sp echenden Monochlo silane mi Indenylli hium.
Silylindenyl-Ligand o s u en mi Subs i uen en in Posi ion 2 wu den du ch die G igna d-
Reak ion on A yldime hylchlo silanen mi 2-B ominden e hal en.
Zusammen assung______________________________________________________
104
Um die en sp echenden Dichlo id-Komplexe zu e hal en wu den zunächs die
subs i uie en Indenyl e bindungen mi n-Bu ylli hium dep o onie und anschließend mi
Zi konium- ode Ha nium e achlo id in Die hyle he umgese z .
RSi
R
Si
R
Si
M
Cl Cl
2
1) 2 n-BuLi, E 2O, -78°C -
- 2 BuH
2) MCl4, E 2O, -78°C -
- 2 LiCl
R = Me, OMe, F
M=
Z
, H
Si
RSi
R
Si
R
M
Cl Cl
2
1) 2 n-BuLi, E
2
O, -78 °C-
-2 BuH
2) MCl
4
, E
2
O, -78 °C-
-2 LiCl
R = Me, OMe, F
M= Z
, H
Die so he ges ell en Komplexe wu den mi MAO als Coka alysa o ü die
E henpolyme isa ion eingese z , um den Ein luss des Subs i u ionsmus e s au die
Ak i i ä zu un e suchen.
Komplex 17 mi einem Fluo a om in pa a-Posi ion de Silylphenyl-G uppe zeig e dabei
die höchs e Ak i i ä (7740 kg PE/mol Ka . h) un e den Me allocenkomplexen 13-18 mi
Subs i uen en in Posi ion 1.
Zusammen assung______________________________________________________
105
Im Gegensa z dazu wies Komplex 16 mi eine Me hoxyg uppe an de selben Posi ion
die ge ings e Ak i i ä (50 kg PE/mol Ka . h) au . Ein ähnliches Ve hal en wa bei den
Komplexen mi Subs i uen en in Posi ion 2 (19-24) zu beobach en. G undsä zlich wa en
jedoch die Komplexe mi Subs i uen en in Posi ion 1 seh iel ak i e als de en Analoga
mi Subs i uen en in Posi ion 2.
Die e hal enen Polyme e wu den mi Hil e on „di e en ial scanning calo ime y“ (DSC)
und Viskosime ie-Messungen cha ak e isie .
De zwei e Teil de A bei beschä ig sich mi de Syn hese und Cha ak e isie ung eine
neuen Klasse on Zi konium- und Ha niumkomplexen mi ansa-Bis(indenyl)-Liganden,
in welchen die beiden Indenyl es e du ch eine 1,2-Bis(dime hylsilyl)benzol-B ücke in
den Posi ionen 1 und 1’ e bunden sind.
Die Liganden o s u en wu de in d ei Sch i en he ges ell . Nach de G igna d-Reak ion
on Chlo dime hylsilan mi 1,2-Dib ombenzol und de PdCl2-ka alysie en Chlo ie ung
wu de die Liganden o s u e du ch die Umse zung mi Indenylli hium e hal en.
Si Si
B B
1) Mg, 2 Me2SiHCl
-2 MgB Cl
2) PdCl2, CCl4
-CHCl3
3) [Ind]-Li+
-2 LiCl
Die en sp echenden Zi konium- und Ha niumkomplexe esul ie en aus de
Dep o onie ung de Bis(indenyl)-Ve bindung mi n-BuLi ge olg on eine Umse zung mi
dem en sp echenden Me all e achlo id in THF.
Zusammen assung______________________________________________________
106
SiSi
M
Cl Cl
Si Si
1) 2 n-BuLi / THF, -78 °C
2) MCl4 / THF, 60 °C, 72 h
-2 LiCl
-2 BuH
M = Z , H
Die Fes kö pe s uk u en beide Komplexe wu den mi Hil e on K is all-
S uk u analysen au geklä . Beide Komplexe e wiesen sich als seh ak i bei de
E henpolyme isa ion. De Zi konium-Komplex 34 wa dabei noch ak i e (7610 kg
PE/mol Ka . h) als sein Ha nium-Analogon 35 (3590 kg PE/mol Ka . h).
Wei e hin wu de ein zwei e S uk u yp on ansa-Me allocenekomplexen syn he isie
und dessen Eigenscha en bei de homogenen E henpolyme isa ion un e such . Das
Ligandsys em bes eh aus zwei Indenylg uppen, die übe eine 2,2’-Dime hylbiphenyl-
B ücke an den Posi ionen 3 und 3’ e bunden sind.
Die Reduk ion on Diphensäu e mi Li hiumaluminiumhyd id (LiAlH4) ge olg on den
Reak ionen mi Phospho ib omid und Indenylli hium lie e e die Ligand o s u e.
Um die en sp echenden Komplexe de G uppe-IV-Me alle zu e hal en, wu den zunächs
die subs i uie en Indenyl e bindungen mi n-Bu ylli hium dep o onie und anschließend
mi den en sp echenden Me all e achlo iden umgese z .
M
Cl Cl
RR
R = H, Me; M = Ti, Z , H
Zusammen assung______________________________________________________
107
Im Ve gleich zu den me hylsubs i uie en De i a en (R = Me) zeig en die
unsubs i uie en ansa-Komplexe (R = H) höhe e Ak i i ä en. Die höchs e Ak i i ä wu de
dabei om Zi koniumkomplex 42 e ziel (12460 kg PE/mol Ka . h) ge olg om
Ha niumkomplex 43 (3816 kg PE/mol Ka . h). De Ti an-Komplex 40 hingegen wa
inak i , was du ch dessen he mische Ins abili ä und Tendenz zu Ze se zung
beg ünde we den könn e.
Die Ein üh ung on Me hylsubs i uen en in Posi ion 1 de Indenylg uppen üh zu einem
beach lichen Rückgang de Ak i i ä . De G und da ü lieg wah scheinlich in de
s e ischen Hinde ung du ch die beiden Me hylg uppen.
Die e hal enen Polye hylene wu den mi Hil e on „di e en ial scanning calo ime y“
(DSC) und Viskosime ie-Messungen cha ak e isie .
Wei e hin wu den eine Reihe symme isch un e b ück e (Tolyl) luo enyl-Zi konium- und
Ha niumkomplexe syn he isie , cha ak e isie und ü die E henpolyme isa ion
un e such . Diese Komplexe e wiesen sich dabei als inak i in Kombina ion mi MAO.
De G und ü de en Inak i i ä is seh wah scheinlich in “ ing-slippage“-Reak ionen zu
suchen, die mi wechselnden Hap izi ä en (η5→ η3→ η1) de Fluo enylliganden
einhe gehen. Diese Reak ionen sind allgemein bekann ü un e b ück e
Fluo enylkomplexe.

Re e ences____________________________________________________________
108
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