New alkenyl-substituted group 4 C-ansa-metallocene complexes. Reactivity of the substituent at the carbon ansa bridge

Article abstract of DOI:10.1016/j.jorganchem.2009.01.038

The allyl-substituted group 4 metal complexes [M{(R)CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] [M = Ti, R = CH₂CH{double bond, long}CH₂, (2); R = CH₂C(CH₃

Full text of DOI:10.1016/j.jorganchem.2009.01.038

Journal of Organometallic Chemistry 694 (2009) 1959–1970
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
New alkenyl-substituted group 4 C-ansa-metallocene complexes. Reactivity of the
substituent at the carbon ansa bridge
a
a
a
a
Antonio Antiñolo a, , Rafael Fernández-Galán , Noelia Molina , Antonio Otero , Iván Rivilla ,
*
Ana M. Rodríguez b
a Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, Facultad de Químicas, Campus Universitario, 13071 Ciudad Real, Spain
b ETS Ingenieros Industriales, Avenida Camilo José Cela, 3, 13071 Ciudad Real, Spain
a r t i c l e i n f o
a b s t r a c t
The allyl-substituted group 4 metal complexes [M{(R)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti, R = CH2CH@CH2,
(2); R = CH2C(CH3)@CH2 (3); M = Zr, R = CH2CH@CH2 (4), R = CH2C(CH3)@CH2 (5)] have been synthesized by
the reaction of allyl ansa-magnesocene derivatives and the tetrachloride salts of the corresponding tran-
Article history:
Received 17 December 2008
Received in revised form 20 January 2009
Accepted 21 January 2009
Available online 30 January 2009
sition metal. The dialkyl complexes ½MðRÞCHð
g
5-C5Me4Þð
g
5-C5H4ÞR02] [M = Ti, R = CH2=CHCH2, R0 = Me
(6), R0 = CH2Ph (7); R = CH2C(CH3)@CH2, R0 = Me (8), R0 = CH2Ph (9); M = Zr, R = CH2CH@CH2, R0 = Me
(10), R0 = CH2Ph (11); R = CH2C(CH3)@CH2, R0 = Me (12), R0 = CH2Ph (13)] have been synthesized by the
reaction of the corresponding ansa-metallocene dichloride complexes 2–5 and two molar equivalents
of the alkyl Grignard reagent. Compounds 2–5 reacted with H2 under catalytic conditions (Wilkinson’s
Keywords:
Metallocenes
Zirconium
catalyst or Pd/C) to give the hydrogenation products [M{(R)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti and
Titanium
R = CH2CH2CH3 (14) or R = CH2CH(CH3)2 (15); M = Zr and R = CH2CH2CH3 (16) or R = CH2CH(CH3)2 (17)].
The reactivity of 2–5 has also been tested in hydroboration and hydrosilylation reactions. The hydrobo-
ration reactions of 3, 4 and 5 with 9-borabicyclo[3.3.1]nonane (9-BBN) yielded the complexes [M{(9-
Hydrosilylation
Hydrogenation
Hydroboration
BBN)CH2CH(R)CH2CH(
(20)]. The reaction with the silane reagents HSiMe2Cl gave the corresponding [M{ClMe2-
SiCH2CHRCH2CH(
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti and R = H (21); M = Zr and R = H (22) or R = CH3
(23)]. The reaction of 22 with t-BuMe2SiOH produced new complex [Zr{t-BuMe2SiOSi-
(Me2)CH2CH2CH2CH(
5-C5Me4)( 5-C5H4)}Cl2] (24) through the formation of Si–O–Si bonds. On the other
hand, reactivity studies of some zirconocene complexes were carried out, with the insertion reaction of
phenyl isocyanate (PhNCO) into the zirconium–carbon -bond of [Zr{(n-Bu)CH(
5-C5Me4)(g5
C5H4)}2Me2] (25) giving [{(n-Bu)CH(
5-C5Me4)( 5-C5H4)]}Zr{Me{ 2-O,N-OC(Me)NPh}] as a mixture of
two isomers 26a–b. The reaction of [Zr{(n-Bu)(H)C(
5-C5Me4)( 5-C5H4)}(CH2Ph)2] (27) with CO also pro-
vided a mixture of two isomers [{(n-Bu)CH(
5-C5Me4)( 5-C5H4)]}Zr(CH2Ph){ 2-O,C-COCH2Ph}] 28a–b.
g g
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti and R = H (18); M = Zr and R = H (19) or R = CH3
g
g
a
g
g
r
g
-
g
g
j
g
g
g
g
j
The molecular structures of 4, 11, 16 and 17 have been determined by single-crystal X-ray diffraction
studies.
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
a heterogeneous medium [5]. One route for the immobilisation of
metallocene complexes is the reactivity of a C@C bond of an alke-
Group 4 metallocene complexes have been extensively investi-
gated as catalysts for the polymerisation of -olefin over the last
nyl substituent on the cyclopentadienido ring or at the ansa-
bridged atom [6]. Several studies have been carried out in which
hydrosilylation of the ansa-zirconocene complexes with vinyl or al-
lyl groups in the silicon bridge is followed by supporting the sys-
tem on silica [7], modified silica surfaces [3a] or organosilicon
dendrimers [8]. In other cases, the initial modification by hydrosi-
lylation of ansa-cyclopentadienyl ligands is followed by their
incorporation in group 4 metallocene systems [9].
Most of the ansa-metallocene complexes published contain sili-
con as the bridging atom, and there are very few examples in which
functional groups are attached to the bridgehead atom [3a,10].
Moreover, we have reported the synthesis and catalytic reactivity
of group 4 metallocene complexes [11] and more recently the
a
few decades [1] and the ansa-cyclopentadienyl systems have also
been at the forefront of metallocene catalysis chemistry [2]. The
introduction of functional groups in the metallocene ligand system
can be exploited by immobilizing the catalyst on different sub-
strates without greatly altering the general structure of the com-
plex [3]. Moreover, due to industrial applications [4], the current
trend in the field of metallocene catalysis is moving toward sup-
ported catalysts that allow homogeneous single-site selectivity in
* Corresponding author. Tel.: +34 26 295300; fax: +34 26 295318.
E-mail address: antonio.antinolo@uclm.es (A. Antiñolo).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.01.038

1960
A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
a
b
Scheme 1. Different isomers for the insertion reactions of PhNCO into the chiral carbon atom-bridged dialkyl ansa-zirconocene complexes.
precursor K[(C5Me4)@CH(C5H4)] for the facile synthesis of ansa-
metallocene with variable substitution at the bridging carbon atom
[12]. We also described the development of new ansa-metallocene
complexes of group 4 that have vinyl or allyl substituents at the sil-
icon ansa bridge or at the cyclopentadinyl rings [13].
enyl moiety and to the four methyl groups of the tetramethylcyclo-
pentadienyl fragment (see Section 4). The proton at the ansa bridge
gave a triplet due to coupling to the two allyl protons in the
a-po-
sition. The allyl-substituted groups, C H2CbR)@C H2 (R = H, CH3),
a
c
exhibited three sets of signals corresponding to the C H2 protons
a
We report here the synthesis of new ansa-metallocene group 4
complexeswithanallylgrouponthemethylene-bridge anddescribe
its hydrogenation, hydroboration and hydrosilylation reactions. The
latter reaction was performed with the aim of obtaining methylene-
bridged metallocene complexes that have a chlorosilane (Si–Cl)
functionality that is a suitable anchoring moiety for immobilization
onto silica surfaces. The insertion reactionsof PhNCO and CO into the
Zr–C bond of some chiral carbon atom-bridged dialkyl ansa-zircono-
cene complexes are also described, and these generate – in addition
to the different O-inside(a) and N-inside(b) configuration modes –
the trans (1) and cis (2) isomers with respect to the substituent on
the bridge (see Scheme 1). These results can be extrapolated to other
dimethyl or dibenzyl ansa-zirconocene complexes with different
substituents.
bonded to the carbon bridge atom, the central group protons CbR,
and the olefinic protons for the terminal C H2. The 13C{1H} NMR
c
spectra showed the expected signals for the different ligand sys-
tems corresponding to the allyl-functionalized ansa-carbon bridge-
head complexes.
The molecular structure of 4 was established by single-crystal
X-ray diffraction studies. The molecular structure and atomic num-
bering scheme are shown in Fig. 1.
The poor quality of the crystals obtained for compound 4 pre-
clude a detailed discussion of distances and angles for this
compound.
We previously showed that some dialkylation processes of
silicon-bridged ansa-zirconocene complexes are controlled by ste-
ric factors and that this may be due to the alkyl ligand or the sub-
stituents in the b-position of the cyclopentadienyl ring [11b,c].
The dialkyl derivatives ½MðRÞHCð
g
5-C5Me4Þð
g
5-C5H4ÞR02] [M = Ti,
2. Results and discussion
R = CH2CH@CH2, R0 = Me (6), R0 = CH2Ph (7); R = CH2C(CH3)@CH2,
Solutions of ansa-biscyclopentadienyl Mg{(R)CH(C5H4)(C5Me4)}-
(thf)2 [R = CH2CH@CH2 (1a), CH2C(CH3)@CH2 (1b)] in thf were pre-
pared by treatment of the appropriate allyl Grignard reagent
MgClR [R = CH2CH@CH2, CH2C(CH3)@CH2] in thf solution with
K[(C5Me4)@CH(C5H4)] [12a] in equimolar amounts through a
nucleophilic addition reaction at the exocyclic double bond. The
solutions of 1a and 1b were used without further manipulation
to prepare new ansa-metallocene complexes. Indeed, the sub-
sequent addition of MCl4(thf)2 (M = Ti or Zr) to these solutions
yielded the corresponding ansa-metallocene dichloride complexes
[M{(R)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti and R = CH2CH@CH2
(2), CH2C(CH3)@CH2, (3); M = Zr and R = CH2CH@CH2, (4), CH2C-
(CH3)@CH2, (5)] (Scheme 2).
The new chiral ansa-metallocene dichloride complexes 2–5
were isolated as crystalline solids and characterized spectroscopi-
cally by mono- (1H and 13C {1H}) and bidimensional NMR experi-
ments (g-COSY and g-HSQC) (see Section 4). Only signals for one
compound were observed in all the spectra. The 1H NMR spectra
of the C1 symmetric complexes 2–5 display eight signals, which
are assigned to the four protons of the unsubstituted cyclopentadi-
Fig. 1. View of the molecular structure and atom labelling scheme for
[Zr{(CH2@CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (4).
Scheme 2.

A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
1961
Scheme 3. Synthesis of the dialkyl ansa-metallocene complexes 6–13.
R0 = Me (8), R0 = CH2Ph (9); M = Zr, R = CH2CH@CH2, R0 = Me (10),
R0 = CH2Ph (11); R = CH2C(CH3)@CH2, R0 = Me (12), R0 = CH2Ph
(13)] were prepared by the reaction of two equivalents of the cor-
responding alkyl Grignard reagent and the ansa-zirconocene
dichloride complexes 2–5 (Scheme 3). Compounds 6–13 were iso-
lated as crystalline solids and characterized by spectroscopic
methods. The alkylation reactions of the ansa-carbon bridged
complexes were carried out as previously described for the sili-
con-bridged compounds [11c] since the reduction of the ‘‘bite an-
gle” from the silicon to the carbon ansa-bridge atom does not
increase the steric hindrance around the metal atom and there-
fore it does not disfavour the dialkylation process.
5, where the 2-methylallyl group is present as the substituent on
the carbon bridge, with a Pd/C catalyst were carried out under the
same conditions, the final product was a 50:50 mixture of the start-
ing material and the corresponding n-propyl hydrogenated product
in the case of 5 and unreacted starting materials in the case of 3.
VaryingtheH2 pressure orincreasingthetemperaturegavethesame
results. The latter observation apparently results from a steric hin-
drance due to methyl group in the 2-methylallyl substituent.
The 1H and 13C{1H} NMR spectra of 14 and 16 showed, in addi-
tion to the expected resonance for the ansa-ligand, signals associ-
The dialkyl ansa-zirconocene complexes 6–13 were character-
ized by 1H and 13C{1H} NMR spectroscopy. The 1H and 13C{1H}
NMR spectra of 10, as well as those of 6, 8 and 12, gave two unique
signals for the metal-bonded methyl groups, thus confirming the
dialkylation and the chirality of these ansa-metallocene complexes
(see Section 4).
On the other hand, due to the chirality around the C bridge atom
and the C1 symmetry of 11, as well as 7, 9 and 13, the methylene
protons of the two non-equivalent benzyl ligands are diastereotop-
ic and an AA0BB0 system was observed in the 1H NMR spectra. This
system consists of four signals, two doublets at 0.98 and 1.01 ppm
(2JH–H = 7.3 Hz) and another two doublets at 1.82 and 1.85 ppm
(2JH–H = 11.7 Hz) for Hendo or Hexo of the methylene group of the
two benzyl ligands in the particular case of 11. The 13C{1H} NMR
spectra showed two resonances at 59.6 and 59.9 ppm for the two
benzyl carbon atoms (CH2) and this confirmed the non-equivalence
of these groups.
Fig. 2. Molecular structure and atom labelling scheme for [Zr{(CH2@CHCH2)CH(g5
C5Me4)(
-
g
5-C5H4)}(CH2Ph)2] (11) with thermal ellipsoids at the 30% probability.
The molecular structure of 11 was established by single-crystal
X-ray diffraction studies, which allowed us to confirm the spectro-
scopic data and to compare the data with the structure obtained
for complex 4. The molecular structure and atomic numbering
scheme for 11 are shown in Fig. 2 and selected bond lengths and
angles are given in Table 1.
The structure of 11 is similar to that of 4, bound by a chelating
ansa-ligand with a bent metallocene conformation and a pseudo-
tetrahedral geometry around the zirconium atom. In complex 11
the pseudo-tetrahedral environment of the zirconium atom is
completed by the two benzyl groups. The two benzyl groups,
which replace the two chlorine atoms, are arranged in space with
the phenyl ring inclined toward the non-substituted cyclopentadi-
enyl ring.
Table 1
Bond lengths (Å) and angles (°) for 11.
11
Zr(1)–C(19)
Zr(1)–C(26)
Zr(1)–Ct(1)
Zr(1)–Ct(2)
C(1)–C(6)
2.326(3)
2.297(3)
2.507(3)
2.523(3)
1.529(4)
1.531(4)
1.509(4)
1.497(4)
1.300(4)
C(6)–C(7)
C(6)–C(16)
C(16)–C(17)
C(17)–C(18)
C(26)–Zr(1)–C(19)
Ct(1)–Zr(1)–Ct(2)
C(1)–C(6)–C(16)
C(7)–C(6)–C(16)
C(1)–C(6)–C(7)
C(6)–C(16)–C(17)
C(16)–C(17)–C(18)
C(20)–C(19)–Zr(1)
C(27)–C(26)–Zr(1)
103.6(1)
116.7(3)
115.6(2)
117.3(2)
101.1(2)
113.2(2)
125.7(3)
121.8(2)
119.7(2)
The reactivity of complexes 2–5 was tested in the hydrogenation
reaction of the unsaturated bond of allyl groups. All of the complexes
react under H2 pressure in the presence of Wilkinson’s catalyst
RhCl(PPh3)3 at room temperature to give a single saturated ansa-
metallocene complex [M{(R)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti
and R = CH2CH2CH3 (14) or R = CH2CH(CH3)2 (15); M = Zr and
R = CH2CH2CH3 (16) or R = CH2CH(CH3)2 (17)] as the product
(Scheme 4). However, when the hydrogenation reactions of 3 and
Ct(1) is the centroid of the Cp ring and Ct(2) is the centroid of the Cp* ring.

1962
A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
Scheme 4.
ated with the n-propyl group arising from hydrogenation of the al-
lyl substituent (see Section 4), which were observed in the 1H NMR
spectrum as three signals at ca. 0.82, 1.31 and 1.81 ppm. Hydroge-
nation of 15 and 17 gave the i-butyl moieties, which gave rise to
two doublets at ca. 0.82 ppm and two multiplets at ca. 1.65 and
1.91 ppm (corroborate by g-COSY experiment).
Compounds 18–20 were characterized by homo- (1H and
13C{1H}) and heteronuclear (g-COSY and g-HSQC) spectroscopic
correlation techniques. The 1H NMR spectra of 18–20 showed
changes in the signals previously attributed to the allyl group (in
2, 4 and 5). The new propane-1,3-diyl chain generated in 18 and
19 gave three multiplets at ca. d 1.40 (C ), 1.63 (Cb) and 2.00 (C )
c
a
The molecular structures of 16 and 17 were established by
X-ray studies. The molecular structures and atomic numbering
schemes are shown in Fig. 3. Selected bond lengths and angles
are given in Table 2.
and the additional protons of the borane moiety gave rise to four
multiplets in the range d 1.11–1.84 (see Section 4).
In the 1H NMR spectrum of 20 the signals corresponding to two
different diastereoisomers were observed due to the presence of a
new chiral centre at Cb of the satured chain between the carbon
atom bridge and the 9-BBN group. The presence of these two iso-
Compound 16 crystallizes in the space group P21/n and 17 crys-
ꢀ
tallizes in the P1 space group. It is interesting to note the bond dis-
tance between carbon atoms C17–C18 in 16 [1.498(6) Å], which is
longer than the corresponding distance in complex 4 with the al-
kene group [1.25(4) Å]. This observation confirms that hydrogena-
tion occurred on this bond. A similar distance between carbon
atoms C17–C18 is found for complex 17 [1.470(5) Å], this data
are in agreement with a saturated bond for 16 and 17 [12b]. A
selection of bond distance and angles for complexes 16 and 17 is
given in Table 3.
Table 2
Bond lengths (Å) and angles (°) for 16 and 17.
16
17
Zr(1)–Cl(1)
Zr(1)–Cl(2)
Zr(1)–Ct(1)
Zr(1)–Ct(2)
C(1)–C(6)
2.430(1)
2.447(1)
2.492(4)
2.502(3)
1.540(5)
1.539(5)
1.493(5)
1.527(5)
1.498(6)
Zr(1)–Cl(1)
Zr(1)–Cl(2)
Zr(1)–Ct(1)
Zr(1)–Ct(2)
C(1)–C(6)
2.4437(7)
2.4246(7)
2.494(3)
2.501(2)
1.523(4)
1.536(4)
1.511(4)
1.522(4)
1.470(5)
1.492(4)
Hydroboration at the double bond of the allyl group of the ansa-
metallocene complexes 2–5 was carried out in a similar manner to
that published by our group [11d,f] or Erker, Piers or Alt for metal-
locene complexes of group 4 [14] or Schumann for lantanocene
complexes [15]. 9-BBN was used as the reagent with complexes
2–5 to give mainly anti-Markonikov products [M{(9-BBN-
C(6)–C(7)
C(6)–C(7)
C(6)–C(16)
C(16)–C(17)
C(17)–C(18)
C(6)–C(16)
C(16)–C(17)
C(17)–C(18)
C(17)–C(19)
CH2CH(R)CH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] [M = Ti and R = H
Cl(1)–Zr(1)–Cl(2)
Ct(1)–Zr(1)–Ct(2)
C(1)–C(6)–C(16)
C(7)–C(6)–C(16)
C(1)–C(6)–C(7)
101.00(4)
117.2(2)
116.0(3)
116.6(3)
99.9(3)
Cl(1)–Zr(1)–Cl(2)
Ct(1)–Zr(1)–Ct(2)
C(1)–C(6)–C(16)
C(7)–C(6)–C(16)
C(1)–C(6)–C(7)
C(6)–C(16)–C(17)
C(16)–C(17)–C(18)
C(16)–C(17)–C(19)
C(18)–C(17)–C(19)
102.55(3)
117.4(2)
115.5(2)
116.8(2)
100.7(2)
114.6(2)
114.4(3)
111.3(3)
113.1(3)
(18); M = Zr and R = H (19) or R = CH3 (20)] (Scheme 5). The reac-
tion takes place readily at room temperature without altering the
metal centre (Ti or Zr) and in all cases the borane selectively at-
tacks the terminal olefinic carbon atom. However, when the titano-
cene complex with the CH2CH@CH2 group at the bridge was used
(i.e. 2), it was necessary to warm the reaction mixture to 60 °C.
The hydroboration reaction of 3 under the same conditions did
not take place.
C(6)–C(16)–C(17)
C(16)–C(17)–C(18)
113.1(3)
113.6(4)
Ct(1) is the centroid of the Cp ring and Ct(2) is the centroid of the Cp* ring.
Fig. 3. Molecular structure and atom labelling scheme for (a) [Zr{(CH3CH2CH2)CH(g g g g
5-C5Me4)( 5-C5H4)Cl2] (16) and (b) [Zr{(CH3)2CHCH2)CH( 5-C5Me4)( 5-C5H4)}Cl2] (17)
with thermal ellipsoids at the 30% probability.

A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
1963
Table 3
Crystal data and structure refinement for 4, 11, 16 and 17.
4
11
16
17
Empirical formula
Formula weight
T (K)
C18H22Cl2Zr
400.48
180(2)
C32H36Zr
511.83
180(2)
C18H24Cl2Zr
402.49
180(2)
C19H26Cl2Zr
416.52
180(2)
Wavelength (Å)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
0.71073
Triclinic
P1
0.71073
Monoclinic
P21/n
9.5108(7)
8.9184(7)
30.096(2)
0.71073
Monoclinic
P21/n
9.562(2)
15.875(3)
11.795(2)
0.71073
Triclinic
P1
ꢀ
ꢀ
9.358(5)
8.6035(3)
9.3728(2)
12.1372(4)
85.341(2)
82.416(2)
75.784(2)
939.25(5)
2
1.473
0.865
428
0.41 ꢁ 0.19 ꢁ 0.18
ꢀ9 6 h 6 10
ꢀ11 6 k 6 10
ꢀ13 6 l 6 14
5891
11.985(6)
15.713(8)
92.128(7)
92.854(8)
92.193(9)
1757(2)
a
(°)
b (°)
98.813(1)
91.793(3)
c
(°)
V (Å3)
2522.6(3)
4
1.348
0.454
1072
0.46 ꢁ 0.32 ꢁ 0.27
ꢀ11 6 h 6 11
10 6 k 6 10
ꢀ34 6 l 6 35
15873
1789.6(6)
4
1.494
0.905
824
0.19 ꢁ 0.15 ꢁ 0.11
ꢀ11 6 h 6 11
ꢀ17 6 k 6 18
ꢀ14 6 l 6 14
9567
Z
4
Density (calculated) (g/cm3)
Absorption coefficient (mmꢀ1
F(000)
1.514
0.921
816
0.32 ꢁ 0.27 ꢁ 0.14
ꢀ11 6 h 6 11
ꢀ14 6 k 6 14
ꢀ19 6 l 6 19
12801
)
Crystal size (mm3)
Index ranges
Reflections collected
Independent reflections [R(int)
Data/restraints/parameters
Goodness-of-fit on F2
]
6908 [0.1400]
6908/0/209
1.347
4442 [0.0420]
4442/0/302
1.099
3106 [0.0379]
3106/0/195
1.052
3242 [0.0188]
3242/0/205
1.081
Final R indices [I > 2
r
(I)]
R1 = 0.1839
wR2 = 0.4483
2.330 and ꢀ1.383
R1 = 0.0349,
wR2 = 0.0857
0.507 and ꢀ0.261
R1 = 0.0389
wR2 = 0.0900
0.666 and ꢀ0.477
R1 = 0.0293
wR2 = 0.0725
0.399 and ꢀ0.507
Largest difference peak and hole (e Åꢀ3
)
Scheme 5.
mers can be clearly observed in the NMR spectrum due to the
appearance of two triplets of similar intensity at 4.08 and
4.13 ppm with JH–H = 8.2 and JH–H = 8.1 Hz, respectively, which
corresponds with the proton of group CH bridge. Moreover, for
the i-butylene chain two sets of three multiplets at ca. d 2.04–
When the Speier catalyst was used the reactions between 4
and HSiMe2Cl were carried out in toluene and with heating for
12 h at 60–80 °C. It is worth noting the lack of reactivity of 2, 3
and 5 with this catalyst, a situation that is probably due to the
steric effects of the allyl-substituted group and the poor reactivity
of this catalyst.
3
3
2.15 (C ), 1.85–2.10 (Cb) and 1.29–1.42 (C ) and two doublets at
a
c
ca. 0.92–0.97 ppm (CH3) were observed for isomers I and II, respec-
tively (see Fig. 4). The signals due to the borane moiety were ob-
served in the same region and gave the pattern in 18. In order to
assign the signals more accurately some g-COSY and g-HSQC
experiments were carried out.
The hydrosilylation reaction can also give the regioisomer
[M{CH3CH(SiMe2Cl)CH2CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (R = Me or
H; M = Ti or Zr) by Markovnikov or 1,2-addition [16]. This minor
product was detected in quantities of less than 5–10% by 1H
NMR spectroscopy.
Hydrosilylation reactions on metallocene compounds with a vi-
nyl or allyl group in the bridge allow the study of the ability of
these complexes to produce model molecules similar those that
are probably formed by the interaction of ansa-metallocene com-
plexes supported on an inorganic surface such as silica.
Compounds 21–23 were isolated and characterized by NMR
spectroscopy. The reaction leads to the loss of signals in the 1H
and 13C{1H} NMR spectra corresponding to the allyl groups of the
parent complexes. The NMR spectra show the expected resonances
for the C5H4 and C5Me4 moieties. In addition, a set of multiplets,
corresponding to the propane-1,3-diyl (21 and 22) or i-butylene
(23) chains, and two singlets assigned to the methyl groups of Si-
Me2Cl were also observed. The proton of the CH bridge gave rise
to an ABB0 system consisting of two doublets for each isomer in
the 1H NMR spectrum. This is due to the coupling with the two
The hydrosilylation reactions of 2–5 with HSiMe2Cl were carried
out in the presence of the Karstedt catalyst [platinum(0) divin-
yltetramethylsiloxane] at room temperature, following our previ-
ous used synthetic method [11e,13b]. These reactions gave
complexes [M{ClMe2SiCH2CH(R)CH2CH(g g
5-C5Me4)( 5-C5H4)}Cl2]
[M = Ti and R = H (21); M = Zr and R = H (22) or R = CH3 (23)],
formed by the anti-Markovnikov or 1,2-addition on the double
bonds of the allyl substrate (Scheme 6). Hydrosilylation reactions
involving 3 did not take place.
non-equivalent protons of the C H2 group. A more accurate spec-
a
troscopic NMR assignment of the signals corresponding to each
isomer was made by H–H and H–C correlation experiments.
Compound 23 has a new chiral centre at the carbon in the b-posi-

1964
A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
Fig. 4. Isomers of [Zr{R0CH2CH(CH3)CH2CH( 5-C5Me4)( 5-C5H4)}Cl]2 R0 = SiMe2Cl or 9-BBN.
g g
Scheme 6.
tion of the i-butylene moiety and this gives rise to the presence of
two diastereoisomers (Fig. 4).
A new study on insertion reactions into the Zr–C bonds of the
chiral carbon-bridged dialkyl ansa-zirconocene complexes was
performed.
The 29Si{1H} NMR spectroscopic data of 21–23 confirmed the
proposed structure (see Section 4), with a resonance observed at
31.02, 30.01 and 30.28 ppm for 21, 22 and 23, respectively, due
to the new silicon atom.
Gambarotta et al. [18] studied the insertion reactions of PhNCO
into the Zr–C bond of zirconocene complexes and described the
synthesis and characterization of the complex [Cp2Zr{Me}{OC-
We and others have previously reported the reaction of chloros-
ilane metallocene compounds with silanol as surface model
[13b,17]. Here is reported the ability of ansa hydrosilylated metal-
locene complex 23, which has a Si–Cl anchor, to form Si–O–Si
bonds by a homogeneous reaction with a silanol compound as a
model surface support. In this way, a solution of complex 23 was
reacted with t-BuMe2SiOH in toluene in the presence of NEt3 at
60 °C. This reaction gave [Zr{t-BuMe2SiOSi(Me2)CH2CH2CH2-
(Me)NPh}]. These authors proposed a j
2-coordination mode for
the phenyl isocyanate ligand on the basis of the IR and 13C NMR
spectroscopy and an X-ray study. The structure has a conformation
in which the N atom is in an ‘‘N-inside” configuration and the O
atom is in an ‘‘O-outside” configuration.
We carried out an analogous reaction of phenyl isocyanate with
a solution of [Zr{(n-Bu)(H)C(g g
5-C5Me4)( 5-C5H4)}2Me2] (25) in tol-
uene at room temperature. In this particular case the chirality of
CH(g
5-C5Me4)(
g
5-C5H4)}Cl2] (24) as a pale yellow solid in excel-
the complex at the bridge carbon atom gives two isomers [Zr{(n-
lent yield.
Bu)CH(g g j
5-C5Me4)( 5-C5H4)}( 2-O,N-C(Me)P)}Me] (26a–b) from
In the 1H NMR spectra of 24, all of the signals were shifted to
lower field, a situation that could be due to the presence of an oxy-
gen atom in the chain producing a –I effect throughout the chain.
Thus, the proton of the bridge group appears at 4.15 ppm along
with three multiplets at 0.71, 1.65 and 2.29 ppm for the protons
of the n-propylene chain. The t-butyl protons were observed as a
singlet at 1.10 ppm. The 29Si{1H} NMR spectra contained two sig-
nals at 10.11 ppm and 9.54 ppm and these are assigned to the
two different silicon atoms. These observations indicate that the
–OH group had reacted with the Si–Cl group. This is the first
ansa-zirconocene complex with a methylene ansa bridge tethered
onto a silanol surface model.
the insertion reactions (Scheme 1). Complexes 26a–b were charac-
terized by NMR and IR spectroscopy as well as mass spectrometry.
The 1H and 13C{1H} NMR spectroscopic data indicate the presence
of only two of the possible conformers. For 26 the isolated product
was observed not to evolve over time and therefore we tentatively
propose that these are the products resulting from thermodynamic
control and, as such, they adopt the N-inside conformation. A sec-
ond insertion was not observed even when stoichiometries other
than 1:1 were tested. The
j
2-coordination mode is proposed for
the phenyl isocyanate ligand in 26 on the basis of IR and 13C
NMR data, which show the characteristic stretching vibration
m
(C–O) at ca. 1705 cmꢀ1 and (C–N) at 1660 cmꢀ1 and the carbonyl
m

A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
1965
4.2. Synthesis of [Ti{(CH2@CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (2)
A solid mixture of [TiCl4(thf)2] (1.41 g, 4.23 mmol) and 1a
(1.72 g, 4.23 mmol) was added to THF (100 mL) at 0 °C. The solu-
tion was allowed to warm up to room temperature and was stirred
for 15 h. The solvent was removed under reduced pressure and tol-
uene (100 mL) was added to the resulting brown solid. The mixture
was filtered, the solvent from the filtrate was removed in vacuo and
the remaining solid was extracted into hexane (30 mL). The filtered
solution was concentrated and cooled to ꢀ30 °C to give the title
complex as a brown crystalline solid. Yield: 1.11 g, 73%. 1H NMR
(500 MHz, C6D6, 25 °C): d 1.27, 1.47, 1.92 (3s, 3:3:6H, C5Me4),
n
Scheme 7.
quaternary carbon atom signal at d 180.8 and 180.9 ppm, respec-
tively, for the two isomers. The 1H and 13C{1H} NMR spectra of 26
show, in addition to the expected signals for the ansa-metallocene
protons, signals corresponding to these isomers (see Section 4).
It is known that the migratory insertion of alkyl groups towards
carbon monoxide ligands allows the introduction of acyl groups
that can show different coordination modes [19,11c] and this reac-
tion pathway is well known [20]. In fact, for early transition metals
3
2.55 (m, 2H, CY2@CHCH2), 3.80 (t, 1H, CH, JH–H = 9.0 Hz), 4.96,
5.02 (2m, each 1H, CY2@CHCH2), 4.80, 5.00, 6.68, 6.76 (4m, each
1H, C5H4); 5.68 (m, CH2@CHCH2). 13C{1H} NMR (125 MHz, C6D6,
25 °C): d 12.5, 12.8, 13.5, 15.6 (C5Me4), 34.2 (CY2@CHCH2), 38.09
(CH), 117.0 (CH2@CHCH2), 107.6, 110.1, 128.4, 129.2, 138.1
(C5H4); 134.9 (CH2@CHCH2), 98.7, 107.0, 123.1, 125.7, 137.4
(C5Me4). Mass spectrometry [electron impact m/e (relative inten-
sity)]: 357 (36) [M+], 321 (100) [M+ꢀCl], 279 (21)
[M+ꢀClꢀCH2@CH2CH2]. Anal. Calc. for C18H22Cl2Ti: C, 60.53; H,
6.21. Found C, 59.71; H, 6.01%.
the acyl group typically adopts a
both the oxygen and carbon atoms in an exo conformation. In this
context we carried out the reaction of [Zr{(n-Bu)(H)C(g5
C5Me4)(
5-C5H4)}(PhCH2)2] (27) with CO in toluene at room tem-
perature. This process also provided a mixture of two isomers of
the complex [{(n-Bu)CH(
5-C5Me4)( 5-C5H4)]}Zr(PhCH2){ 2-O,C-
COCH2Ph}] (28a–b) (Scheme 7). The
2-coordination mode is pro-
posed for the acyl ligand in 28 on the basis of IR and 13C NMR data,
j
2-coordination mode through
-
g
4.3. Synthesis of [Ti{(CH2@C(CH3)CH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (3)
g
g
j
g
The preparation of 3 was carried out in an identical manner to 2,
from a solution of 1b (1.76 g, 4.18 mmol) and [TiCl4(thf)2] (1.43 g,
4.18 mmol) in thf (100 mL) Yield: 0.98 g, 63%. 1H NMR (500 MHz,
which show the characteristic stretching vibration m(C–O) at ca.
1594 cmꢀ1 and the carbonyl quaternary carbon atom signals at
156.5 and 156.7 ppm, respectively, for the two isomers 28a and
28b. The 1H NMR spectra of 28 shows, in addition to the expected
signals for the ansa-metallocene protons, signals corresponding to
these isomers (see Section 4).
C6D6, 25 °C): d 1.31, 1.49, 1.92, 1.93 (4s, each 3H, C5Me4), 1.58 (s,
3
3H, CH3), 2.58 (m, 2H, CH2@CCY3CH2), 4.00 (t, 1H, CH, JH–H
=
8.4), 4.77 (bs, 2H, CH2@CCY3CH2), 4.82, 5.03, 6.68, 6.78 (4m, each
1H, C5H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d 12.5, 12.8,
13.4, 15.7 (C5Me4), 22.7 (CH3), 37.0 (CH), 37.9 (CH2@CCY3CH2),
98.9, 107.2, 123.2, 125.6, 137.3 (C5Me4), 107.6, 110.1, 126.8,
129.2, 138.2 (C5H4), 112.3 (CH2@CCY3CH2), 142.4 (CH2@CCY3CH2).
Mass spectrometry [electron impact m/e (relative intensity)]: 371
(100) [M+], 335 (84) [M+ꢀCl], 280 (79) [M+ꢀClꢀCH2@C(CH3)CH2].
Anal. Calc. for C19H24Cl2Ti: C, 61.48; H, 6.52. Found C, 62.12; H,
6.24%.
3. Conclusions
In this paper we report the preparation and characterization of
a new family of ansa-metallocene group 4 complexes containing
an alkenyl substituent in the carbon bridge atom. The reactivity
of these compounds in catalytic hydrogenation, hydrosilylation
and hydroboration processes is also described. It was observed
that a steric factor is involved in the synthesis of unsaturated com-
pounds because the face of the alkene that is tied to the catalyst
could be hindered by the presence of the methyl group in the b-
position.
4.4. Synthesis of [Zr{(CH2@CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (4)
[ZrCl4(thf)2] (1.85 g, 4.91 mmol) in toluene (50 mL) was added
to a solution of 1a (2 g, 4.91 mmol) in Et2O (50 mL) at ꢀ78 °C.
The solution was allowed to warm up to room temperature and
stirred for 10 h. The solvent was partially removed under reduced
pressure and the mixture was filtered to give a deep orange solu-
tion. The filtered solution was concentrated and cooled to ꢀ30 °C
to yield crystals of the title complex. Yield: 1.41 g, 72%. 1H NMR
(500 MHz, C6D6, 25 °C): d 1.45, 1.63, 1.83, 1.84 (4s, each 3H,
4. Experimental
4.1. Materials and procedures
3
All reactions were performed using standard Schlenk tube
techniques in an atmosphere of dry nitrogen. Solvents were dis-
tilled from appropriate drying agents and degassed before use.
C5Me4), 2.59 (m, 2H, CY2@CHCH2), 3.87 (t, 1H, CH, JH–H = 8.4 Hz),
4.95, 5.05 (2m, each 1H, CY2@CHCH2), 5.01, 5.17, 6.35, 6.45 (4m,
each 1H, C5H4), 5.69 (m, CH2@CHCH2). 13C{1H} NMR (125 MHz,
C6D6, 25 °C): d 11.0, 11.2, 12.7, 14.7 (C5Me4), 35.1 (CY2@CHCH2),
39.2 (CH), 116.9 (CH2@CHCH2), 104.1, 114.1, 117.7, 120.3, 129.0
(C5H4); 135.3 (CH2@CHCH2); 104.5, 107.2, 119.8, 121.9, 129.8
(C5Me4). Mass spectrometry [electron impact m/e (relative inten-
sity)]: 398 (60) [M+], 363 (51) [M+ꢀCl], 321 (48) [M+ꢀCH2@
CHCH2ꢀCl]. Anal. Calc. for C18H22Cl2Zr: C, 53.98; H, 5.54. Found:
C, 51.67; H, 5.68%.
K[(C5H4)CH@(C5Me4)], [Zr{(n-Bu)CH(
g g
5-C5Me4)( 5-C5H4)}2Me2]
(25) and [Zr{(n-Bu)CH(
g
5-C5Me4)( 5-C5H4)}(PhCH2)2] (27) were
g
prepared as described earlier [12b]. MgCl(CH2@CHCH2), MgCl-
(CH2@C(CH3)CH2), MgBrMe, MgCl(CH2Ph), 9-borabicyclo[3.3.1]-
nonane (9-BBN), Wilkinson’s catalyst, Pd/C (10% palladium)
catalyst, HSiMe2Cl, Karstedt catalyst, Spiers catalyst, t-BuMe2-
SiOH, NEt3, [TiCl4(thf)2] and [ZrCl4(thf)2] were purchased from Al-
drich and used directly. Mg{CH2@CHCH2CH(C5Me4)(C5H4)} (1a)
and Mg{CH2@C(CH3)CH2CH(C5Me4)(C5H4)} (1b) solutions were
prepared as reported [21] and used in situ. 1H and 13C{1H} NMR
spectra were recorded on a Varian Inova FT-500 spectrometer
and referenced to the residual deuteriated solvent. Microanalyses
were carried out with a Perkin–Elmer 2400 microanalyzer.
4.5. Synthesis of [Zr{(CH2@C(CH3)CH2)CH(
(5)
g g
5-C5Me4)( 5-C5H4)}Cl2]
The preparation of 5 was carried out in an identical manner to
that of 4, from a solution of 1b (2 g, 4.75 mmol) in Et2O (50 mL)

1966
A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
and [ZrCl4(thf)2] (1.79 g, 4.75 mmol). Yield: 1.35 g, 69%. 1H NMR
(500 MHz, C6D6, 25 °C): d 1.50, 1.66, 1.84, 1.85 (4s, each 3H,
C5Me4), 1.58 (s, 3H, CH2@C(CH3)CH2), 2.61 (m, 2H,
6H, TiMe2), 1.23, 1.40, 1.94, 1.96 (4s, each 3H, C5Me4), 1.60 (s, 3H,
CH3), 2.47 (m, 2H, CH2@CCY3CH2), 3.44 (t, 1H, CH, JH–H = 8.3 Hz),
3
4.77 (bs, 2H, CH2@CCY3CH2), 4.62, 4.82, 6.85, 6.92 (4m, each 1H,
C5H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d 10.2, 10.5, 10.9,
13.1 (C5Me4), 21.5 (CH3), 35.4 (CH), 37.1 (CH2@CCY3CH2)), 43.6,
43,7 (TiMe2), 97.7, 104.2, 116.1, 118.3, 123.9 (C5Me4), 104.2,
106.4, 117.7, 119.4, 124.7 (C5H4), 110.5 (CH2@C(CH3)CH2), 142.1
(CH2@C(CH3)CH2). Anal. Calc. for C21H30Ti: C, 76.36; H, 9.15. Found:
C, 75.77; H, 8.64%.
3
CY2@C(CH3)CH2), 4.08 (t, 1H, CH, JH–H = 8.3 Hz), 4.77 [bs, 2H,
CH2@C(CH3)CH2], 5.03, 5.20, 6.36, 6.47 (4m, each 1H, C5H4).
13C{1H} NMR (125 MHz, C6D6, 25 °C): d 11.6, 11.9, 12.6, 14.9
(C5Me4), 23.0 (CH2@C(CH3)CH2), 38.0 (CH2@C(CH3)CH2), 38.8
(CH), 113.4 (CH2@C(CH3)CH2), 104.5, 112.4, 119.7, 122.1, 130.0
(C5H4), 140.6 (CH2@CCH3)CH2), 107.2, 114.5, 117.8, 120.1, 128.9
(C5Me4). Mass spectrometry [electron impact m/e (relative inten-
sity)]: 412 (100) [M+], 377 (94) [M+ꢀCl], 357 (96)
[M+ꢀCH2@C(CH3)CH2], 321 (73) [M+ꢀCH2@C(CH3)CH2ꢀCl].
Anal. Calc. for C19H24Cl2Zr: C, 55.05; H, 5.84. Found: C, 55.71; H,
5.96%.
4.9. Synthesis of [Ti{(CH2@C(CH3)CH2)CH(
(9)
g g
5-C5Me4)( 5-C5H4)}(CH2Ph)2]
The preparation of 9 was carried out in an identical manner to
that of 7, from a solution of 3 (0.30 g, 0.80 mmol) and a 2 M solu-
tion of MgCl(CH2Ph) (0.96 mL, 1.92 mmol). Yield: 0.31 g, 64%. 1H
NMR (500 MHz, C6D6, 25 °C): d 1.21, 1.38, 1.87, 1.90 (4s, each 3H,
4.6. Synthesis of [Ti{(CH2@CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Me2] (6)
2
A 1.4 M solution of MeMgBr in thf/toluene (1.44 mL, 2.01 mmol)
was added to a stirred solution of 2 (0.30 g, 0.84 mmol) in thf
(50 mL) at ꢀ78 °C. The solution was allowed to warm up to room
temperature and stirred for 6 h. The solvent was removed in vacuo
and the remaining orange oil was extracted into hexane
(2 ꢁ 25 mL). The solution was filtered and the solvent was re-
moved in vacuo to yield the title complex as an orange solid. Yield
(0.18 g, 68%). 1H NMR (500 MHz, C6D6, 25 °C): d ꢀ0.12, ꢀ0.11 (2s,
each 3H, TiMe2), 1.19, 1.38, 1.94, 1.96 (4s, each 3H, C5Me4), 2.46
C5Me4), 1.32 (2d, each 1H, CH2Ph, JH–H = 9.5 Hz), 1.58 (1s, 3H,
CH3), 1.68 (d, 2H, CH2Ph, 2JH–H = 9.0 Hz), 2.37 (m, 2H,
3
CH2@C(CH3)CH2), 3.38 (t, 1H, CH, JH–H = 8.1 Hz), 4.30, 4.57, 6.39,
6.51 (4m, each 1H, C5H4), 4.77 (bs, 2H, CH2@C(CH3)CH2,), 6.76–
7.21 (m, 10H, (2CH2Ph)). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d
11.6, 11.9, 12.2, 14.4 (C5Me4), 22.9 (CH3), 36.5 (CH), 38.1
(CH2@C(CH3)CH2), 74.3, 74.7 (CH2Ph)2), 95.6, 104.7, 117.0, 119.4,
126.0 (C5Me4), 106.9, 109.2, 122.9, 125.4, 128.2 (C5H4), 111.8
(CH2@C(CH3)CH2), 141.9 (CH2@C(CH3)CH2), 121.5, 125.8, 125.9,
126.1, 126.1, 128.3, 128.4, 128.5, 128.7, 143.2, 155.8, 155.9
((CH2Ph)2). Anal. Calc. for C33H38Ti: C, 82.14; H, 7.94. Found: C,
82.68; H, 8.09%.
3
(m, 2H, CH2@CHCH2), 3.27 (t, 1H, CH, JH–H = 8.6 Hz), 4.61, 4.80,
6.84, 6.92 (4m, each 1H, C5H4), 4.95, 5.03 (2m, each 1H,
CH2@CHCH2), 5.76 (m, 1H, CH2@CHCH2). 13C{1H} NMR (125 MHz,
C6D6, 25 °C): d 10.2, 10.5, 10.9, 12.9 (C5Me4), 33.4, 36.6 (TiMe2),
43.6 (CH2@CHCH2), 43.7 (CH), 97.4, 104.7, 116.1, 118.5, 124.7
(C5Me4), 104.2, 106.5, 117.8, 119.3, 123.9 (C5H4), 114.9
(CH2@CHCH2), 134.9 (CH2@CHCH2). Anal. Calc. for C20H28Ti: C,
75.94; H, 8.92. Found: C, 75.31; H, 9.17%.
4.10. Synthesis of [Zr{(CH2@CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Me2] (10)
The preparation of 10 was carried out in an identical manner
with that for 6, from a solution of 4 (0.30 g, 0.75 mmol) and a
1.4 M solution of MgBrMe (1.28 mL, 1.79 mmol). Yield: 0.20 g,
75%. 1H NMR (500 MHz, C6D6, 25 °C): d ꢀ0.29, ꢀ0.30 (2s, each
3H, ZrMe2), 1.44, 1.62, 1.82, 1.83 (4s, each 3H, C5Me4), 2.59 (m,
4.7. Synthesis of [Ti{(CH2@CHCH2)CH(
(7)
g g
5-C5Me4)( 5-C5H4)}(CH2Ph)2]
3
2H, CY2@CHCH2), 3.58 (t, CH, JH–H = 8.4 Hz); 5.04, 5.09 (2m, each
A 2 M solution of MgCl(CH2Ph) in thf (1.00 mL, 2.01 mmol) was
added to a stirred solution of 2 (0.30 g, 0.84 mmol) in thf (50 mL) at
ꢀ78 °C. The solution was allowed to warm up to room temperature
and stirred for 6 h. The solvent was removed in vacuo and the
remaining red solid was extracted into hexane (2 ꢁ 25 mL). The
solution was filtered and the solvent was removed in vacuo to yield
the title complex as a red solid. Yield (0.26 g, 66%). 1H NMR
(500 MHz, C6D6, 25 °C): d 1.16, 1.34, 1.87, 1.88 (4s, each 3H,
1H, CY2@CHCH2), 4.97, 5.11, 6.32, 6.41 (4m, each 1H, C5H4); 5.80
(m, CH2@CHCH2). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d 10.7,
11.1, 11.79, 13.8 (C5Me4), 31.1, 31.3 (ZrMe2), 35.4 (CY2@CHCH2),
38.8 (CH), 113.2 (CY2@CHCH2), 104.1, 114.1, 117.7, 120.2, 128.9
(C5H4), 136.3 (CH2@CHCH2), 103.8, 106.27, 114.8, 116.3, 129.9
(C5Me4). Anal. Calc. for C20H28Zr: C, 66.79; H, 7.85. Found: C,
67.33; H, 8.12%.
2
C5Me4), 1.31 (2d, each 1H, CH2Ph, JH–H = 9.5 Hz), 1.66 (2d, each
4.11. Synthesis of [Zr{(CH2@CHCH2)CH(
(11)
g g
5-C5Me4)( 5-C5H4)}(CH2Ph)2]
2
1H, CH2Ph, JH–H = 9.7 Hz), 2.36 (m, 2H, CH2@CHCH2), 3.20 (t, 1H,
3
CH, JH–H = 8.6 Hz), 4.28, 4.51, 6.38, 6.48 (4m, each 1H, C5H4),
4.93, 5.01 (2m, each 1H, CH2@CHCH2), 5.69 (m, 1H, CH2@CHCH2),
6.78–7.17 (m, 10H, 2CH2Ph). 13C{1H} NMR (125 MHz, C6D6,
25 °C): d 11.6, 11.9, 12.3, 14.3 (C5Me4), 34.4 (CH2@CHCH2), 37.8
(CH), 74.5, 74.7 ((CH2Ph)2), 95.3, 104.5, 116.9, 119.6, 126.2
(C5Me4), 106.9, 109.3, 123.2, 125.3, 128.5 (C5H4), 116.3
(CH2@CHCH2), 135.9 (CH2@CHCH2), 121.5, 121.6, 126.0, 126.3,
128.5, 128.6, 128.7, 129.3, 141.9, 155.8, 155.9 ((CH2Ph)2).
Anal. Calc. for C32H36Ti: C, 82.04; H, 7.75. Found: C, 82.85; H,
8.12%.
The preparation of 11 was carried out in an identical manner to
that of 7, from a solution of 4 (1.00 g, 2.50 mmol) and a 2 M solu-
tion of MgCl(CH2Ph) (2.90 mL, 5.80 mmol). Yield: 1.02 g, 81%. 1H
NMR (500 MHz, C6D6, 25 °C): d 0.98, 1.01 (2d, each 1H, CH2Ph,
2JH–H = 7.3 Hz), 1.40, 1.57, 1.72, 1.73 (4s, each 3H, C5Me4), 1.82,
2
1.85 (2d, each 1H, CH2Ph, JH–H = 11.6 Hz, 11.4 Hz), 2.50 (m, 2H,
3
CY2@CHCH2), 3.52 (t, 1H, CH, JH–H = 8.5 Hz), 4.96, 5.05 (2m, each
1H, CY2@CHCH2), 4.66, 4.85, 5.65, 5.77 (4m, each 1H, C5H4), 5.74
(m, CH2@CHCH2), 6.77, 6.87, 7.17 (3m, 10H, 2CH2Ph). 13C{1H}
NMR (125 MHz, C6D6, 25 °C): d 10.7, 11.1, 11.8, 13.7 (C5Me4),
35.1 (CY2@CHCH2), 38.5 (CH), 59.5, 59.7 ((CH2Ph)2), 116.4
(CH2@CHCH2), 104.4, 113.9, 117.2, 119.3, 123.1 (C5H4); 135.9
(CH2@CHCH2), 105.9, 106.9, 119.3, 121.8, 129.2 (C5Me4), 125.6,
126.0, 127.6, 127.7, 127.7, 127.9, 128.1, 128.6, 128.5, 128.6
((CH2Ph)2 Cipso not observed). Anal. Calc. for C32H36Zr: C, 75.09;
H, 7.09. Found: C, 75.91; H, 7.30%.
4.8. Synthesis of [Ti{(CH2@C(CH3)CH2)CH(
(8)
g g
5-C5Me4)( 5-C5H4)}Me2]
The preparation of 8 was carried out in an identical manner to
that of 6, from a solution of 3 (0.30 g, 0.80 mmol) in thf (50 mL)
and a 1.4 M solution of MgBrMe (1.38 mL, 1.92 mmol) in THF/tolu-
ene. Yield: 0.17 g, 64%. 1H NMR (500 MHz, C6D6, 25 °C): d ꢀ0.11 (s,

A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
1967
4.12. Synthesis of [Zr{(CH2@C(CH3)CH2)CH(
(12)
g
5-C5Me4)(
g
5-C5H4)}Me2]
C5Me4)(
g
5-C5H4)}Cl2], 322 (79) [M+ꢀCl], 314 (75) [M+ꢀ(CH2-
CH2CH3)], 279 (46) [M+ꢀ(CH2CH2CH3ꢀCl]. Anal. Calc. for
C18H24Cl2Ti: C, 60.19; H, 6.74. Found: C, 60.39; H, 6.89%.
The preparation of 12 was carried out in an identical manner
to that of 6, from a solution of 5 (1.00 g, 2.41 mmol) and a
1.4 M solution of MgBrMe in toluene/thf (4.00 mL, 5.60 mmol).
Yield: 0.63 g, 71%. 1H NMR (500 MHz, C6D6, 25 °C): d ꢀ0.31,
ꢀ0.32 (2s, each 3H, ZrMe2), 1.49, 1.64, 1.81, 1.83 (4s, each 3H,
C5Me4), 1.62 (s, 3H, CH2@C(CH3)CH2), 2.61 (m, 2H, CH2@
4.15. Synthesis of [Ti {(Me2CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (15)
Compound 3 (0.30 g, 0.80 mmol) was dissolved in toluene
(25 mL) and Wilkinson’s catalyst was added (5 mg). Hydrogen
was passed through the solution at a pressure of 3 bar with stirring
for 4 h at room temperature. The solvent was removed under re-
duced pressure and the remaining solid was extracted into hexane
(2 ꢁ 25 mL). The mixture was filtered and the filtrate was removed
in vacuo to give the title complex as a red crystalline solid. Yield:
0.21 g, 70%. 1H NMR (500 MHz, C6D6, 25 °C) d: 0.80, 0.84 (2d, each
3
C(CH3)CH2), 3.76 (t, CH, JH–H = 8.3 Hz); 4.78, 4.84 [2s, each 1H,
CY2@C(CH3)CH2], 4.98, 5.15, 6.31, 6.42 (4m, each 1H, C5H4).
13C{1H} NMR (125 MHz, C6D6, 25 °C):
d 9.3, 9.7, 10.4, 12.6
(C5Me4), 21.5 (CH2@C(CH3)CH2), 29.7, 29.8 (ZrMe2), 37.8 (CH2@
C(CH3)CH2), 36.1 (CH), 113.5 (CY2@C(CH3)CH2), 103.9, 106.2,
112.0, 113.1, 114.8 (C5H4), 142.1 (CH2@C(CH3)CH2), 106.8, 115.7,
118.9, 119.9, 128.3 (C5Me4). Anal. Calc. for C21H30Zr: C, 67.50;
H, 8.09. Found: C, 67.78; H, 8.22%.
3
3
3H, (CH3)2CHCH2), JH–H = 6.8, JH–H = 6.3 Hz), 1.34, 1.49, 1.95 (3s,
3:3:6H, C5Me4), 1.64 (m, 1H, (CH3)2CHCH2), 1.90 (m, 2H,
3
(CH3)2CHCH2), 3.87 (t, 1H, CH, JH–H = 8.1 Hz), 4.83, 5.03, 6.69,
6.79 (4m, each 1H, C5H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C) d:
12.6, 12.9, 13.5, 15.7 (C5Me4), 22.0, 23.1 (CH3), 26.8 ((CH3)2CHCH2),
36.9 (CH), 39.2 ((CH3)2CHCH2), 99.0, 108.0, 123.2, 125.8, 138.2
(C5Me4), 107.8, 110.3, 126.8, 129.4, 137.4 (C5H4). EI MS:
4.13. Synthesis of [Zr{(CH2@C(CH3)CH2)CH(
C5H4)}(CH2Ph)2] (13)
g -
5-C5Me4)(g5
m/z (%) = 372 (100) [M+, [Ti{(CH3)2CHCH2)HC( 5-C5Me4)-
g
The preparation of 13 was carried out in an identical manner to
that of 7, from a solution of 5 (1.00 g, 2.41 mmol) and a 2 M solu-
tion of MgBr(CH2Ph) (2.80 mL, 5.60 mmol). Yield: 0.95 g, 75%. 1H
NMR (500 MHz, C6D6, 25 °C): d 0.98, 1.02 (2d, each 1H, CH2Ph,
(
g
5-C5H4)}Cl2], 336 (79) [M+ꢀCl], 279 (41) [M+ꢀClꢀC4H9].
Anal. Calc. for C19H26Cl2Ti: C, 61.15; H, 7.02. Found: C, 61.52; H,
7.13%.
2JH–H = 10.4 Hz, 10.3 Hz), 1.44 [s, 3H, CH2@C(CH3)CH2], 1.60, 1.72,
2
1.74 (3s, 6:3:3H, C5Me4), 1.90, 1.88 (2d, each 1H, CH2Ph, JH–H
=
4.16. Synthesis of [Zr{(CH3CH2CH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (16)
11.9 Hz, 12.00 Hz), 2.57 [m, 2H, CY2@C(CH3)CH2], 3.75 (t,
3
1H, CH, JH–H = 8.3 Hz), 4.87, 4.83 [2m, each 1H, CY2@C(CH3)CH2],
The preparation of 16 was carried out in an identical manner to
4.72, 4.95, 5.65, 5.78 (4m, 4 each 1H C5H4), 6.80–7.25 (m, 10H,
2CH2Ph). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d 10.7, 11.1, 13.9
(C5Me4), 11.7 (CH2@C(CH3)CH2), 38.8 (CY2@C(CH3)CH2), 37.3
(CH), 59.4, 59.7, 2CH2Ph), 112.2 (CH2@C(CH3)CH2), 106.9, 112.1,
117.0, 119.4, 143.2 (C5H4); 137.8 (CH2@C(CH3)CH2), 114.0, 116.3,
121.7, 122.7, 143.2 (C5Me4), 125.9, 126.0, 127.9, 128.1, 128.3,
128.7, 128.5, 129.3, 151.9, 152.0 (CH2Ph). Anal. Calc. for C33H38Zr:
C, 75.37; H, 7.28. Found: C, 74.76; H, 7.08%.
14.
Pd/C catalyst. From 4 (0.20 g, 0.50 mmol) Yield: 0.19 g, 95%.
Wilkinson’s catalyst. From 4 (0.20 g, 0.50 mmol) Yield: 0.18 g,
93%.
1H NMR (500 MHz, C6D6, 25 °C): d 0.82 (t, 3H, CH3CH2CH2,
3JH–H = 7.3 Hz), 1.31 (m, CH3CH2CH2, 2H), 1.49, 1.65, 1.86, 1.87
(4s, each 3H, C5Me4), 1.81 (m, 2H, CH3CH2CH2), 3.81 (t, 1H, CH,
3JH–H = 8.4 Hz), 5.04, 5.19, 6.37, 6.47 (4m, each 1H, C5H4). 13C{1H}
NMR (125 MHz, C6D6, 25 °C): d 11.4, 11.7, 12.4, 13.9 (C5Me4),
14.3 (CH3CH2CH2), 20.8 (CH3CH2CH2), 32.9 (CH3CH2CH2), 39.1
(CH), 104.2, 107.3, 119.7, 121.9, 128.9 (C5H4), 105.6, 114.8, 117.7,
121.9, 129.7 (C5Me4). Mass spectrometry [electron impact (m/e
(relative intensity)]: 400 (100) [M+], 358 (64) [M+ꢀCH3CH2CH2],
322 (42) [M+ꢀCH3CH2CH2ꢀCl]. Anal. Calc. for C18H24Cl2Zr: C,
53.71; H, 6.01. Found: C, 54.78; H, 6.11%.
4.14. Synthesis of [Ti{(CH3CH2CH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (14)
Pd/C catalyst. Compound 2 (0.30 g, 0.84 mmol) was dissolved in
toluene (25 mL) and the Pd/C (10% palladium) catalyst was added
(5 mg). Hydrogen was passed through the solution at a pressure
of 2 bar with stirring for 2 h at room temperature. The resulting
suspension was filtered and the solvent was removed from the fil-
trate under reduced pressure. The remaining solid was extracted
with hexane (2 ꢁ 25 mL). The solvent from the filtered solution
was removed in vacuo to yield the title complex as a brown crystal-
line solid. Yield: 0.05 g, 18%.
4.17. Synthesis of [Zr{(Me2CHCH2)CH(g g
5-C5Me4)( 5-C5H4)}Cl2] (17)
The preparation of 17 was carried out in an identical manner to
14.
Wilkinson’s catalyst. Compound 2 (0.30 g, 0.84 mmol) was dis-
solved in toluene (25 mL) and Wilkinson’s catalyst was added
(5 mg). Hydrogen was passed through the solution at a pressure
of 2 bar with stirring for 2 h at room temperature. The solvent
was removed under reduced pressure and the remaining solid
was extracted with hexane (2 ꢁ 25 mL). The mixture was filtered
and the solvent was removed in vacuo to give the title complex
Pd/C catalyst. From 5 (0.20 g, 0.48 mmol) Yield: 0.10 g, 50%.
Wilkinson’s catalyst. From 5 (0.20 g, 0.48 mmol) Yield: 0.19 g,
96%.
1H NMR (500 MHz, C6D6, 25 °C): d 0.80, 0.85 (2d, each 3H,
2
(CH3)2CHCH2, JH–H = 7.2 Hz), 1.43, 1.54, 1.71, 1.85, (4s, each 3H,
C5Me4), 1.65 (m, 1H, (CH3)2CHCH2), 1.91 (m, 2H, (CH3)2CHCH2),
3.96 (t, 1H, CH, JH–H = 8.4 Hz), 5.04, 5.21, 5.28 (3m, 2:1:1H,
3
as
a
brown crystalline solid. Yield: 0.23 g, 76%. 1H NMR
C5H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d 11.7, 11.9, 12.9,
14.9 (C5Me4), 22.5, 23.6 ((CH3)2CHCH2), 27.0 ((CH3)2CHCH2), 38.1
((CH3)2CHCH2), 40.3 (CH), 105.1, 119.8, 119.8, 122.3, 129.1
(C5H4), 106.8, 107.4, 122.2, 123.5, 130.7 (C5Me4). Mass spectrome-
try [electron impact (m/e (relative intensity)]: 414 (100) [M+], 379
(89) [M+ꢀCl], 356 (90) [M+ꢀ(CH3)2CHCH2], 322 (63)
[M+ꢀ(CH3)2CHCH2ꢀCl]. Anal. Calc. for C19H26Cl2Zr: C, 54.79; H,
6.29. Found: C, 55.61; H, 6.41%.
3
(500 MHz, C6D6, 25 °C): d 0.83 (t, 3H, CH3CH2CH2, JH–H = 7.0 Hz),
1.28 (m, 2H, CH3CH2CH2), 1.32, 1.49, 1.92 (3s, 3:3:6H, C5Me4),
3
1.78 (m, 2H, CH3CH2CH2), 3.73 (t, 1H, CH, JH–H = 8.2 Hz), 4.83,
5.02, 6.70, 6.78 (4m, each 1H, C5H4). 13C{1H} NMR (125 MHz,
C6D6, 25 °C): d 11.3, 11.6, 12.2, 14.2 (C5Me4), 12.6 (CH3CH2CH2),
19.5 (CH3CH2CH2), 31.0 (CH3CH2CH2), 37.1 (CH), 97.8, 106.5,
121.9, 124.5, 138.4 (C5Me4), 106.4, 109.0, 125.6, 127.9, 138.9
(C5H4). EI MS: m/z (%) = 358 (100) [M+, [Ti{(CH2@CHCH2)HC(g5
-

1968
A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
4.18. Synthesis of [Ti{(9-BBN-CH2CH2CH2)CH(
C5H4)}Cl2] (18)
g
5-C5Me4)(g5
-
25.7, 28.7, 31.7, 31.9 (CH2, 9-BBN), 22.6, 22.9 (CH3), 23.5, 25.6
(CH2CH(CH3)CH2), 37.4, 37.7 (CH), 41.6, 41.9 (CH2CH(CH3)CH2),
104.7, 104.9, 115.0, 115.2, 116.8, 117.7, 120.2, 120.3, 128.8, 130.0
(C5H4), 104.5, 104.6, 107.2, 107.4, 118.7, 119.6, 122.1, 122.2,
128.9, 130.0 (C5Me4). Mass spectrometry (MALDI) [m/z (relative
intensity)]: 534 (30) [M+]; 500 (25) [M+ꢀCl]; 373 (100) [M+ꢀ(9-
BBN)CH2CH(CH3)CH2)]. Anal. Calc. for C27H39BCl2Zr: C, 60.44; H,
7.33. Found: C, 60.71; H, 7.36%.
A solution of 2 (0.30 mL, 0.84 mmol) in toluene (50 mL) was
added to a stirred 0.4 M solution of 9-borabicyclo[3.3.1]nonane
in hexane (0.15 g, 1.26 mmol) and the solution was stirred at
60 °C for 15 h. The solvent was removed in vacuo and the remain-
ing brown solid was extracted into hexane (2 ꢁ 25 mL) to give the
title complex as a red solid. Yield: 0.15 g, 38%. 1H NMR (500 MHz,
C6D6, 25 °C): d 1.51 (m, 2H, 9-BBNCH2CH2CH2), 1.34, 1.83 (2m, each
4.21. Synthesis of [Ti{(ClMe2SiCH2CH2CH2)CH(g -
5-C5Me4)(g5
C5H4)}Cl2] (21)
2H,
c-Y of 9-BBN), 1.63, 1.83 (2m, each 4H, b-H and d-H of 9-BBN),
1.80 (m, 2H,
a
-Y of 9-BBN), 1.76, 1.87, 2.10 (3s, 3:3:6H, C5Me4), 1.90
(m, 2H, CH2CH2CH2), 2.42 (m, 2H, CH2CH2CH2), 4.40 (t, 1H, CH,
3JH–H = 8.2 Hz), 5.27, 5.48, 6.86, 6.96 (4m, each 1H, C5H4). 13C{1H}
NMR (125 MHz, C6D6, 25 °C): d 12.6, 12.9, 14.0, 15.8 (C5Me4),
27.2 (BBN-CH2CH2CH2), 33.7 (BBN-CH2CH2CH2), 34.8 (BBN-
CH2CH2CH2), 39.0 (CH), 22.9, 23.0, 23.1, 23.2 (9-BBN), 99.5, 108.0,
124.2, 126.8, 138.1 (C5Me4), 108.3, 111.0, 127.2, 129.3, 139.0
(C5H4). Mass spectrometry (MALDI) [m/z (relative intensity)]: 479
(23) [M+], 359 (100) [M+ꢀ9-BBN], 327 (38) [M+ꢀ9-BBNꢀCl], 316
(40) [M+ꢀ9-BBNꢀCH2CH2CH2]. Anal. Calc. for C26H37BCl2Ti: C,
65.17; H, 7.78. Found: C, 64.38; H, 7.55%.
To a solution of 2 (0.30 g, 0.84 mmol) in toluene (50 mL) was
added dropwise HSiMe2Cl (0.12 g, 1.26 mmol) in toluene (25 mL).
To this solution was added three drops of the Karstedt catalyst
[platinum(0) divinyltetramethylsiloxane in xylene (3–3.5%)] and
the mixture was stirred for 15 h at room temperature. The solvent
was removed under reduced pressure and the residue extracted
with hexane (3 ꢁ 25 mL). The mixture was filtered and the filtrate
was removed in vacuo to give the title complex as a brown solid
(0.09 g, 24%). 1H NMR (500 MHz, C6D6, 25 °C): d 0.40, 0.41 (2s, each
3H, SiMe2), 0.72 (m, 2H, SiCH2CH2CH2), 1.71 (m, 2H, SiCH2CH2CH2),
1.75, 1.86, 2.09, 2.10 (4s, each 3H, C5Me4), 2.37 (m, 2H,
3
SiCH2CH2CH2), 4.36 (t, 1H, CH, JH–H = 8.3 Hz), 5.25, 5.46, 6.85,
4.19. Synthesis of [Zr{(9-BBN-CH2CH2CH2)CH(g -
5-C5Me4)(g5
C5H4)}Cl2] (19)
6.95 (4m, each 1H, C5H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C): d
1.0 (SiMe2); 12.6, 12.9, 14.1, 15.8 (C5Me4), 18.4 (SiCH2CH2CH2),
21.7 (SiCH2CH2CH2), 34.1 (SiCH2CH2CH2), 38.7 (CH), 107.9, 108.3,
124.0, 126.7, 138.4 (C5Me4), 108.2, 110.9, 127.2, 129.3, 138.9
(C5H4). 29Si{1H} NMR (125 MHz, C6D6, 25 °C) d 31.02 (SiMe2Cl).
Mass spectrometry (MALDI) [m/z (relative intensity)]: 453 (21)
[M+], 417 (7) [M+ꢀCl], 357 (100) [M+ꢀSiMe2Cl], 316 (32)
[M+ꢀSiMe2ClꢀCH2CH2CH2]. Anal. Calc. for C20H29Cl3SiTi: C, 53.17;
H, 6.47. Found: C, 53.38; H, 6.34%.
A solution of 4 (0.40 mL, 1.00 mmol) in toluene (50 mL) was
added to a stirred 0.4 M solution of 9-borabicyclo[3.3.1]nonane
in hexane (3.75 mL, 1.00 mmol) and the solution was stirred at
room temperature for 12 h. The solvent was removed under re-
duced pressure and the remaining solid was washed with hexane
(3 ꢁ 25 mL) to give the title compound as a yellow solid. Yield
0.44 g, 84%. 1H NMR (500 MHz, C6D6, 25 °C) d: 1.32, 1.83 (2m, each
2H,
1.81 (m, 2H,
c
-Y of 9-BBN), 1.63, 1.88 (2m, each 4H, b-H and d-H of 9-BBN),
4.22. Synthesis of [Zr{(ClMe2SiCH2CH2CH2)CH(g -
5-C5Me4)(g5
C5H4)}Cl2] (22)
a-Y of 9-BBN), 1.40 (m, 2H, BBN-CH2CH2CH2), 1.53,
1.75, 1.86, 1.90 (4s, each 3H, C5Me4),1.63 (m, 2H, CH2CH2CH2),
2.04 (m, 2H, CH2CH2CH2), 3.95 (t, 1H, CH, JH–H = 8,2 Hz); 5.29,
3
5.10, 6.39, 6.49 (4m, each 1H, C5H4). 13C{1H} NMR (125 MHz,
C6D6, 25 °C) d: 11.3, 11.6, 12.4, 13.9 (C5Me4), 27.9 (9-BBNCH2),
33.1 (CH2CH2CH2), 34.2 (CH2CH2CH2), 39.1 (CH), 23.2, 33.2, 33.4
(9-BBN), 104.3, 107.2, 119.7, 121.9, 128.9 (C5H4), 104.5 114.8,
117.6, 120.3, 129.9 (C5Me4). Mass spectrometry (MALDI) [m/z (rel-
ative intensity)]: 520(50) [M+]; 485 (95) [M+ꢀCl]; 357 (100)
[M+ꢀ(9-BBN)CH2CH(CH3)CH2)]. Anal. Calc. for C26H37BCl2Zr: C,
59.76; H, 7.14. Found: C, 60.35; H, 7.24%.
Karstedt catalyst. To a solution of 4 (0.50 g, 1.24 mmol) in tolu-
ene (50 mL) was added dropwise HSiMe2Cl (0.13 g, 1.36 mmol) in
toluene (25 mL). To this solution was added three drops of the Kar-
stedt catalyst [platinum (0) divinyltetramethylsiloxane in xylene
(3–3.5%)] and the mixture was stirred for 10 h at 60 °C and then
cooled to room temperature. The solvent was removed under re-
duced pressure to give the title compound as a brown solid. Yield:
0.46 g, 76%.
H2PtCl6 catalyst. To a solution of 4 (0.50 g, 1.24 mmol) in toluene
(50 mL) was added dropwise HSiMe2Cl (0.13 g, 1.36 mmol) in tolu-
ene (10 mL). To this solution was added three drops of the H2PtCl6
catalyst and the mixture was stirred for 12 h at 80 °C and then
cooled to room temperature. The solvent was removed under re-
duced pressure to give the title compound as a brown solid. Yield:
0.36 g, 60%.
4.20. Synthesis of [Zr{(9-BBN-CH2CH(CH3)CH2)CH(g -
5-C5Me4)(g5
C5H4)}Cl2] (20)
The preparation of 20 was carried out in an identical manner to
19, from 5 (0.40 g, 0.96 mmol) and a 0.4 M solution of 9-borabicy-
clo[3.3.1]nonane in hexane (3.60 mL, 0.96 mmol). Yield: 0.45 g,
87%. 1H NMR (500 MHz, C6D6, 25 °C) d: Isomer I and II: 0.92,
1H NMR (500 MHz, C6D6, 25 °C): d 0.15 (s, 6H, SiMe2), 0.64 (m,
2H, SiCH2CH2CH2), 1.46 (m, 2H, SiCH2CH2CH2), 1.51, 1.73, 1.85,
1.86 (4s, 3H, C5Me4), 1.95 (m, 2H, SiCH2CH2CH2); 3.83 (t,1H, CH,
3JH–H = 8.3 Hz), 5.07, 5.25, 6.38, 6.48 (4m, each 1H, C5H4). 13C{1H}
NMR (125 MHz, C6D6, 25 °C): d 1.5 (SiMe2); 11.6, 11.9, 12.7, 14.6
(C5Me4), 19.2 (SiCH2CH2CH2), 21.6 (SiCH2CH2CH2), 34.5 (SiCH2-
CH2CH2), 39.4 (CH), 14.6, 107.5, 120.1, 122.2, 129.3 (C5H4),
104.5, 114.8, 117.9, 120.6, 130.2 (C5Me4). 29Si{1H} NMR (125 MHz,
3
3
0.97 (2d, each 3H, JH–H = 6.6 Hz, JH–H = 6.2 Hz, CH2CH(CH3)CH2),
1.34, 1.82 (2m, each 4H, -Y of 9-BBN), 1.64, 1.87 (2m, each 8H,
b-H and d-H of 9-BBN), 1.79 (m, 4H, -Y of 9-BBN), 1.29, 1.42
c
a
(2m, each 2H, 9-BBNCH2CH2CH2), 1.57, 1.58,1.58, 1.76, 1.78, 1.85,
1.86, 1.87 (8s, each 3H, C5Me4), 1.85, 2.10 (m, each 1H,
CH2CH(CH3)CH2), 2.04–2.15 [m, 4H, CH2CH(CH3)CH2], 4.08, 4.13
3
3
C6D6, 25 °C)
d 30.01 (SiMe2Cl). Mass spectrometry (MALDI)
(2t, each 1H, CH, JH–H = 8.2 Hz, JH–H = 8.1 Hz), 5.09, 5.11, 5.30,
5.32, 6.38, 6.49 (6m, 8H, C5H4). 13C{1H} NMR (125 MHz, C6D6,
25 °C) d: Isomer I and II: 11.3, 11.4, 11.6, 11.6, 12.3, 12.4, 14.3,
14.5 (C5Me4), 33.4, 34.1 (CH2CH(CH3)CH2), 23.0, 23.2, 23.6, 23.7,
[m/z (relative intensity)]: 492 (10) [M+], 458 (59) [M+ꢀCl].
Anal. Calc. for C20H29Cl3SiZr: C, 52.26; H, 6.36. Found: C, 51.38; H,
5.92%.

A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
1969
4.23. Synthesis of [Zr{(ClMe2SiCH2CH(CH3)CH2)CH(
C5H4)}Cl2] (23)
g
5-C5Me4)(g5
-
30.2 ((CH2)3CH3), 30.4, 30.8 (OC(Me)NPh), 31.3, 31.5 (ZrMe), 39.3,
39.4 (CH), 99.5, 101.9, 102.9, 105.6, 108.3, 11.6, 113.8, 115.9,
118.7, 119.4, 119.5, 119.7, 119.8, 119.9, 120.1, 129.9 (C5Me4 and
C5H4), 128.8, 128.9, 129.1, 129.2, 129.3, 129.4, 129.9, 130.0 (OC-
The synthesis of 23 was carried out in an identical manner to 22
with Karstedt catalyst, from 5 (0.50 g, 1.20 mmol) and HSiMe2Cl
(0.12 g, 1.32 mmol). Yield: 0.44 g, 71%. 1H NMR (500 MHz, C6D6,
25 °C) Isomer I and II d: 0.16, 0.21 (s, each 6H, SiMe2), 0.51, 0.66
(2m, each 2H, SiCH2CH(CH3)CH2), 0.86, 0.93, (2d, each 3H,
(Me)NPh), 180.8, 180.9 (OC(Me)NPh). IR (Nujol): mC–N 1660 cmꢀ1
,
mC–O 1705 cmꢀ1. Anal. Calc. for C28H37NOZr: C, 67.96; H, 7.54.
Found: C, 68.41; H, 8.17%.
3
3
4.26. Synthesis of [{(n-Bu)CH(g g g
5-C5Me4)( 5-C5H4)]}Zr(CH2Ph){ 2-O,
C-COCH2Ph}] (28)
SiCH2CH(CH3)CH2, JH–H = 6.6 Hz, JH–H = 6.5 Hz), 1.55, 1.56, 1.58,
1.74, 1.77, 1.84, 1.85, 1.86 (8s, each 3H, C5Me4), 1.73, 1.84 (2m,
each 1H, SiCH2CH(CH3)CH2), 2.12, 2.17 (2m, each 2H,
3
SiCH2CH(CH3)CH2), 4.00, 4.05 (2t, each 1H, CH, JH–H = 8.4 Hz),
Compound 27 (1.00 g, 2.66 mmol) was dissolved in toluene
(50 mL) and CO was passed through the solution at a pressure
of 2 bar with stirring for 30 min at room temperature. Pentane
(25 mL) was added to the resulting solution to obtain an orange
solid and a yellow solution. The mixture was filtered and the or-
ange solid dried in vacuo to give the title complex. Yield: 1.18 g,
80%. 1H NMR (500 MHz, C6D6, 25 °C) Isomer cis n-Bu and Isomer
trans n-Bu: d: 0.85 (m, 6H, (CH2)3CH3), 1.05, 1.08 (2s, each 2H,
(CH2Ph), 1.32, 1.55, 1.56, 1.61, 1.80, 1.84, 1.98, 2.06 (8s, each
3H, C5Me4), 1.34, 1.89, 1.92 (3m, each 4H, (CH2)3CH3), 1.96, 2.00
5.09, 5.27, 5.32, 6.37, 6.48 (5m, each 1H, C5H4). 13C{1H} NMR
(125 MHz, C6D6, 25 °C) Isomer I and II: d 2.4, 2.7 (SiMe2), 11.4,
11.7, 12.0, 12.2, 12.3, 13.0, 12.3, 13.1 (C5Me4), 22.3, 23.8
(SiCH2CH(CH3)CH2), 27.6, 28.3 (SiCH2CH(CH3)CH2), 37.3, 37.9
(CH), 40.8, 41.0 (SiCH2CH(CH3)CH2), 41.1, 41.3 (SiCH2CH(CH3)CH2),
104.8, 105.0, 115.3, 115.5, 118.3, 118.6, 120.8, 120.9, 135.3, 137.1
(C5H4), 104.5, 105.1, 107.8, 107.9, 118.7, 120.2, 122.3, 122.7,
129.5, 130.0 (C5Me4). 29Si{1H} NMR (125 MHz, C6D6, 25 °C) d
30.28 (SiMe2Cl). Mass spectrometry (MALDI) [m/z (relative inten-
sity)]: 506 (79) [M+], 471(12) [M+ꢀCl], 378 (100) [M+ꢀMe2ClSiꢀCl].
Anal. Calc. for C21H31Cl3SiZr: C, 49.54; H, 6.14. Found: C, 51.02; H,
6.35%.
2
(2d, each 2H, PhCH2CO, JH–H = 12.0 Hz), 3.49, 3.53 (2t, each 1H,
3
CH, JH–H = 8.4 Hz), 4.57, 4.70, 4.79, 5.05, 5.11, 5.15, 6.77, 6.87
(8s, each 1H, C5H4), 6.95, 7.07, 7.17, 7.42, 7.26 (5m, 10H,
PhCH2CO). 13C{1H} NMR (125 MHz, C6D6, 25 °C) d: 9.9, 10.1,
10.4, 12.1, 12.5, 13.7, 14.0, 14.1 (C5Me4), 14.3, 14.4 ((CH2)3CH3),
22.9, 23.0, 30.8, 31.0, 31.2, 31.5 ((CH2)3CH3), 38.1 (PhCH2CO),
39.2, 39.4 (CH), 47.5, 47.7 (CH2Ph), 99.3, 100.9, 101.7, 101.9,
103.9, 107.1, 107.8, 109.6, 110.8, 113.0, 113.3, 113.6, 114.4,
115.2, 116.6, 117.7, 119.0, 119.8 (C5Me4 and C5H4), 125.1, 125.3,
125.6, 126.1, 128.7, 128.9, 129.2, 130.2, 130.3, 134.0, 134.1,
137.8, 141.9 (PhCH2CO), 156.5, 156.7 (PhCH2CO). IR (Nujol): mC–O
1594 cmꢀ1. Anal. Calc. for C34H40OZr: C, 73.46; H, 7.25. Found:
C, 75.02; H, 7.94%.
4.24. Synthesis of [Zr{(t-BuMe2SiOSi(Me2)CH2CH2CH2)CH(
5-C5H4)}Cl2] (24)
g
5-C5Me4)-
(g
To a solution of 4 (0.20 g, 0.40 mmol) in toluene (50 mL) was
added t-BuMe2SiOH (0.05 g, 0.40 mmol). To this solution was
added NEt3 (0.02 g, 0.40 mmol) and the mixture was stirred for
3 h at 60 °C and then cooled to room temperature. The resulting
suspension was filtered and the solvent was removed from the fil-
trate under reduced pressure to give the title complex as yellow
oil. Yield: 0.17 g, 75%. 1H NMR (500 MHz, C6D6, 25 °C) d: 0.20,
0.18 (2s, each 3H, SiMe2), 0.21 (s, 6H, tBuMe2Si), 0.71 (m, 2H,
4.27. X-ray structure determinations of [Zr{(CH2@CHCH2)CH(g5
-
t
SiCH2CH2CH2), 1.10 (s, 9H, BuMeSi), 1.65 (m, 2H, SiCH2CH2CH2),
C5Me4)(
C5H4)}(CH2Ph)2] (11), [Zr{(CH3CH2CH2)CH(
(16) and [Zr{(CH3)2CHCH2)CH(
5-C5Me4)(
g
5-C5H4)}Cl2] (4), [Zr{(CH2@CHCH2)CH(
g
5-C5Me4)(g5
-
1.73, 1.74, 1.78, 1.97 (4s, each 3H, C5Me4), 2.29 (m, 2H,
g
5-C5Me4)(
g
5-C5H4)}Cl2]
3
SiCH2CH2CH2), 4.15 (t, CH, JH–H = 8.5 Hz), 5.42, 5.64, 6.22, 6.35
g
g
5-C5H4)}Cl2] (17)
(4m, each 1H, C5H4). 13C{1H} NMR (125 MHz, C6D6, 25 °C) d:
ꢀ0.8, ꢀ0.8 (SiMe2), ꢀ0.6, ꢀ0.5 (tBuMe2Si), 25.9 ((Me3)CMe2Si),
26.9 ((Me3)CMe2Si), 12.0 11.1, 11.5, 13.9 (C5Me4), 19.3
(SiCH2CH2CH2), 22.2 (SiCH2CH2CH2), 35.2 (SiCH2CH2CH2), 39.4
(CH), 101.3, 104.5, 114.4, 117.0, 134 .4 (C5H4), 112.0, 112.2,
114.8 116.9, 132.1 (C5Me4). 29Si{1H} NMR (125 MHz, C6D6, 25 °C)
d: 10.11, 9.54 (SiOSi). Anal. Calc. for C22H36Cl2OSi2Zr: C, 50.12; H,
6.96. Found: C, 49.41; H, 6.78%.
A summary of crystal data collection and refinement parame-
ters for all compounds is given in Tables 1 and 2. The single-crys-
tals of 4, 11, 16 and 17 were mounted on a glass fibre and
transferred to a Bruker X8 APEX II CCD-based diffractometer
equipped with a graphite monochromated Mo K
(k = 0.71073 Å). Several sets of narrow data ‘‘frames” were col-
lected using 0.3° wide scan frames covering the complete
a radiation source
x
spheres of the reciprocal space with a crystal-to-detector distance
of 6.0 cm. Data were integrated using SAINT [22] and an absorption
correction was based on multiple scans with the program SADABS
[23]. The software package SHELXTL version 6.12 [24] was used for
space group determination, structure solution and refinement by
full-matrix least-squares methods based on F2. All non-hydrogen
atoms were refined with anisotropic thermal parameters. Hydro-
gen atoms were placed using a ‘‘riding model” and included in
the refinement at calculated positions. The asymmetric unit of 4
contains two independent molecules. Special features/exceptions:
single-crystals of 4 were obtained from a concentrated toluene
solution. Despite several crystal measurements, all crystals were
of very poor quality and only led to a structural solution with an
R value of 18.4%. Only the Zr and Cl atoms were refined with aniso-
tropic displacement parameters. Despite these poor results from
the crystallographic point of view, the results obtained are suffi-
cient to adequately establish the atom connectivity.
4.25. Synthesis of [{(n-Bu)CH(g g j
5-C5Me4)( 5-C5H4)]}Zr{Me{ 2-O,N-
OC(Me)NPh}] (26)
To a solution of 25 (0.50 g, 1.33 mmol) in toluene (50 mL) was
added PhNCO (0.14 mL, 1.33 mmol) and the mixture was stirred
for 10 h at room temperature. The resulting suspension was filtered
and the solvent was removed from the filtrate under reduced pres-
sure to give the title complex as red oil. Yield: 0.38 g, 59%. 1H NMR
(500 MHz, C6D6, 25 °C) Isomer A and Isomer B d: ꢀ0.37, ꢀ0.38 (2s,
each 3H, ZrMe), 0.87 (m, 6H, (CH2)3CH3), 1.34, 1.77, 1.93 (3m, each
4H, (CH2)3CH3), 1.38, 1.41, 1.59, 1.61, 1.63, 1.73, 1.74, 2.05 (8s, each
3H, C5Me4), 2.12, 2.13 (2s, each 3H, OC(Me)NPh), 3.52, 3.59 (2t, each
3
1H, JH–H = 8.4 Hz, CH), 4.89, 4.93, 4.97, 5.42, 5.59, 5.78, 5.84, 5.95
(8s, each 1H, C5H4), 6.96, 7.01, 7.37 (3m, 5H, OC(Me)NPh). 13C{1H}
NMR (125 MHz, C6D6, 25 °C) d: 10.3, 10.7, 10.8, 11.3, 11.6, 11.6,
12.0, 13.9 (C5Me4), 14.2 ((CH2)3CH3), 20.7, 20.8, 21.3, 21.4, 30.0,

1970
A. Antiñolo et al. / Journal of Organometallic Chemistry 694 (2009) 1959–1970
[8] D. Seyferth, R. Wyrwa, US Patent 5969073, 1999.
Acknowledgements
[9] H.G. Alt, R. Ernst, I. Böhmer, J. Mol. Catal. A: Chem. 191 (2003) 177–185.
[10] (a) K. Soga, T. Arai, H. Nozawa, T. Uozumi, Macromol. Symp. 97 (1995) 53;
(b) H.G. Alt, P. Schertl, A. Köppl, J. Organomet. Chem. 568 (1998) 263–269;
(c) E.I. Iiskola, S. Timonen, T.T. Pakkanen, O. Härkki, P. Lehmus, J.V. Seppälä,
Macromolecules 30 (1997) 2853–2859.
We gratefully acknowledge financial support from the Ministe-
rio de Educación y Ciencia, Spain (Grant No. CTQ2006-11845),
the Junta de Comunidades de Castilla La Mancha (Grant No.
PCI08-0032-0957) and the program Consolider-Ingenio 2010
ORFEO CSD2007-00006.
[11] (a) A. Antiñolo, I. López-Solera, I. Orive, A. Otero, S. Prashar, A.M. Rodríguez, E.
Villaseñor, Organometallics 20 (2001) 71–78;
(b) A. Antiñolo, I. López-Solera, A. Otero, S. Prashar, A.M. Rodríguez, E.
Villaseñor, Organometallics 21 (2002) 2460–2467;
(c) A. Antiñolo, R. Fernández-Galán, B. Gallego, A. Otero, S. Prashar, A.M.
Rodríguez, Eur. J. Inorg. Chem. (2003) 2626–2632;
(d) A. Antiñolo, M. Fajardo, S. Gómez-Ruiz, I. López-Solera, A. Otero, S. Prashar,
Organometallics 23 (2004) 4062–4069;
Appendix A. Supplementary material
CCDC 710532, 710533, 710534 and 710535 contain the supple-
mentary crystallographic data for 4, 11, 16 and 17. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplemen-
tary data associated with this article can be found, in the online
version, at doi:10.1016/j.jorganchem.2009.01.038.
(e) S. Gómez-Ruiz, S. Prashar, M. Fajardo, A. Antiñolo, A. Otero, M.A. Maestro,
V. Volkis, M.S. Eisen, C.J. Pastor, Polyhedron 24 (2005) 1298–1313;
(f) D. Polo-Cerón, S. Gómez-Ruiz, S. Prashar, M. Fajardo, A. Antiñolo, A. Otero, I.
López-Solera, M.L. Reyes, J. Mol. Catal. A 268 (2007) 264–276.
[12] (a) A. Antiñolo, R. Fernández-Galán, A. Otero, S. Prashar, I. Rivilla, A.M.
Rodríguez, M.A. Maestro, Organometallics 23 (2004) 5108–5111;
(b) A. Antiñolo, R. Fernández-Galán, A. Otero, S. Prashar, I. Rivilla, A.M.
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carried out in an identical manner to 1a, from
MgCl(CH2C(CH3)@CH2) in thf (15.21 mL,
K[(C5H4)CH@(C5Me4)] (1.50 g, 6.34 mmol) in thf (50 mL).
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0.5 M solution of
7.60 mmol) and
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