Synthesis and reactivity of asymmetrically substituted ansa-bridged zirconocene complexes: X-ray crystal structures of [Zr{R(H)C(η5-C5Me4) (η5-C5H4)}Cl2]

Article abstract of DOI:10.1016/j.jorganchem.2006.02.039

The dialkyl complexes, [ Zr { R ( H ) C ( η⁵ - C₅ Me₄ ) ( η⁵ - C₅ H₄ ) } R₂^′ ] (R = Prⁱ, R′ = Me (2a), CH₂Ph (3a); R = Buⁿ, R′ = Me (2

Full text of DOI:10.1016/j.jorganchem.2006.02.039

Journal of Organometallic Chemistry 691 (2006) 2924–2932
www.elsevier.com/locate/jorganchem
Synthesis and reactivity of asymmetrically substituted ansa-bridged
zirconocene complexes: X-ray crystal structures of
[Zr{R(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (R = Bun, But)
and [Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}(CH2Ph)2]
a
a
a,
b
Antonio Antinolo , Rafael Fernandez-Galan , Antonio Otero *, Sanjiv Prashar ,
´
´
˜
a
c
´
´
Ivan Rivilla , Ana M. Rodrıguez
a
Departamento de Quı´mica Inorga´nica, Orga´nica y Bioquı´mica, Universidad de Castilla-La Mancha, Facultad de Quı´micas, Campus Universitario,
13071 Ciudad Real, Spain
b
Departamento de Quı´mica Inorga´nica y Analı´tica, E.S.C.E.T., Universidad Rey Juan Carlos, C/Tulipan s/n, 28933 Mo´stoles, Madrid, Spain
c
Departamento de Quı´mica Inorga´nica, Orga´nica y Bioquı´mica, ETS Ingenieros Industriales, Universidad de Castilla-La Mancha,
Avd. Camilo Jose´ Cela, 3, 13071-Ciudad Real, Spain
Received 9 December 2005; received in revised form 23 February 2006; accepted 28 February 2006
Available online 6 March 2006
Abstract
The dialkyl complexes, ½ZrfRðHÞCðg5-C5Me4Þðg5-C5H4ÞgR0 ꢀ (R = Pri, R0 = Me (2a), CH2Ph (3a); R = Bun, R0 = Me (2b), CH2Ph
2
(3b); R = But, R0 = Me (2c), CH2Ph (3c); R = Ph, R0 = Me (2d), CH2Ph (3d)), have been synthesized by the reaction of the ansa-metal-
locene dichloride complex, [Zr{R(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (R = Pri (1a), Bun (1b), But (1c), Ph (1d)), and two molar equivalents of
the alkyl Gringard reagent. The insertion reaction of the isocyanide reagent, CNC6H3Me2-2,6, into the zirconium–carbon r-bond of 2
gave the corresponding g2-iminoacyl derivatives, [Zr{R(H)C(g5-C5Me4)(g5-C5H4)}{g2-MeC@NC6H3Me2-2,6}Me] (R = Pri (4a), Bun
(4b), But (4c), Ph (4d)). The molecular structures of 1b, 1c and 3b have been determined by single-crystal X-ray diffraction studies.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Metallocenes; Zirconium; Insertion reactions; Isocyanides
1. Introduction
lysts [4]. Common precursors to these cationic catalysts
include dimethyl- and dibenzyl zirconocene complexes
which are stable species [5].
As part of our ongoing studies in the design of olefin
polymerization catalysts [6], we present in this paper the
synthesis, characterization and reactivity of chiral ansa-
zirconocene complexes. Part of this work has been previ-
ously communicated [7].
Zirconocene complexes owe their place of importance in
organometallic chemistry to their catalytic activity in the
polymerization of olefins [1]. It is now well established that
the structural make up of the catalyst not only plays a part
in its activity in polymerization but also in determining the
microstructure of the polymer [2]. It is therefore evident the
necessity of rational ligand design in order to fulfil differing
polymerization goals [3].
2. Results and discussion
Alkyl zirconocene cations are currently of interest due to
their role as single-site Ziegler–Natta polymerization cata-
We have previously communicated the synthesis of
[Zr{R(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (R = Bun (1b), But
(1c), Ph (1d)) [7] and in a similar manner [Zr{Pri(H)C(g5-
C5Me4)(g5-C5H4)}Cl2] (1a) was prepared (Eq. (1)).
*
Corresponding author. Tel.: +34 926 295326; fax: +34 926 295318.
E-mail address: antonio.otero@uclm.es (A. Otero).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.02.039

A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
2925
R
Li
LiR
K
K
[ZrCl4(THF)2]
ð1Þ
H
R
Cl
Cl
Zr
R = Pri (1a), Bun (1b), But (1c), Ph (1d)
Compound 1a was isolated as a white crystalline solid
1
and characterized spectroscopically. In the H NMR spec-
trum of the C1 symmetric complex 1a four singlets,
between 1.49 and 1.87 ppm, assigned to the four methyl
groups of the tetramethylcyclopentadienyl fragment were
observed. Four multiplets, between 5.06 and 6.48 ppm,
were recorded for the protons of the unsubstituted cyclo-
pentadienyl moiety. The proton at the ansa bridge gave a
doublet at 3.42 ppm. For the isopropyl group the chirality
of the complex makes the two methyl units diastereotopic
and two doublets were observed at 0.87 and 0.91 ppm.
The isopropyl proton gave a multiplet (2.30 ppm) with cou-
pling to both the isopropyl methyl protons and the ansa
bridge proton. The 13C NMR spectrum gave the expected
signals, namely four signals for the methyl substituents of
the C5 ring (between 11.7 and 14.5 ppm), 10 signals for
the carbon atoms of the C5 rings (between 104.1 and
130.0 ppm), three signals for the isopropyl group (20.4,
21.5 and 29.0 ppm) and one signal for the carbon atom
ansa bridge at 48.5 ppm.
Fig. 2. Molecular structure and atom-labeling scheme for
[Zr{But(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (1c) with thermal ellipsoids at
30% probability.
Table 1
˚
Selected bond lengths (A) and angles (ꢁ) for 1b and 1c
Compound
1b
1c
˚
Bond lengths (A)
Zr(1)–Cent(1)
2.193
2.186
Zr(1)–Cent(2)
2.190
2.186
av. Zr(1)–C(C(1)–C(5))*
av. Zr(1)–C(C(10)–C(14))*
Zr(1)–Cl(1)
Zr(1)–Cl(2)
C(1)–C(15)
2.500(6)
2.493(8)
2.415(2)
2.437(2)
1.64(3)
1.48(4)
1.47(6)
2.491(6)
2.486(7)
2.429(2)
2.419(2)
1.559(9)
1.53(1)
1.534(9)
C(10)–C(15)
C(15)–C(16)
Bond angles (ꢁ)
Cent(1)–Zr(1)–Cent(2)
C(15)–C(1)–Cent(1)
C(15)–C(10)–Cent(2)
C(1)–C(15)–C(10)
C(1)–C(15)–C(16)
C(10)–C(15)–C(16)
Cl(1)–Zr(1)–Cent(1)
Cl(1)–Zr(1)–Cent(2)
Cl(2)–Zr(1)–Cent(1)
Cl(2)–Zr(1)–Cent(2)
Cl(1)–Zr(1)–Cl(2)
117.5
118.3
The molecular structures of 1b and 1c were established
by single-crystal X-ray diffraction studies. The molecular
structures and atomic numbering schemes are shown in
Figs. 1 and 2. Selected bond lengths and angles for 1b
and 1c are given in Table 1.
162.23
166.67
98(2)
111(3)
122(4)
109.01
109.05
108.91
108.93
102.37(9)
161.45
163.38
101.0(5)
121.3(7)
123.3(6)
108.95
109.77
108.26
108.89
101.56(8)
Cent(1) and Cent(2) are the centroids of C(1)–C(5) and C(10)–C(14),
respectively; refers to the average bond distance between Zr(1) and the
*
carbon atoms of the C5 ring of the corresponding cyclopentadienyl moiety.
The structures of 1b and 1c exhibit the typical bent
metallocene conformation observed in zirconocene dichlo-
ride complexes with the geometry around the zirconium
atom being pseudo-tetrahedral. The ansa ligand chelates
the zirconium atom and both C5 rings are bound to the
metal in an g5 mode. The centroids of the cyclopentadienyl
rings form an angle with the zirconium atom of 117.5ꢁ 1b,
and 118.3ꢁ 1c, typical for carbon atom bridged ansa-zircon-
ocene complexes (for example, [Zr{Me2C(g5-C5H4)2}Cl2],
Ct–Zr–Ct 116.7ꢁ) [8]. Selected structural data of 1b and
Fig. 1. Molecular structure and atom labelling scheme for
[Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (1b) with thermal ellipsoids at
30% probability.

2926
A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
1c can be compared with similar carbon atom bridged
ansa-zirconocene complexes using Table 2.
alkylation in the complexes with b substituents in one of
the C5 rings. However, when no substituent was present,
e.g., [Zr{Me2Si(g5-C5Me4)(g5-C5H4)}Cl2], dialkylation
took place. One might think that the reduction of the ‘‘bite
angle’’ from the silicon atom to carbon atom ansa bridge
should increase the steric hindrance around the metal atom
and may disfavour dialkylation. This, nevertheless, is not
the case for 1 which behaves in the alkylation reactions
in an identical manner to the silicon ansa-bridged complex.
The molecular structure of 3b was established by single-
crystal X-ray diffraction studies. The molecular structure
and atomic numbering scheme are shown in Fig. 3. Selected
bond lengths and angles for 3b are given in Table 3.
The dialkyl derivatives, ½ZrfRðHÞCðg5-C5Me4Þ-
ðg5-C5H4ÞgR0 ꢀ (R = Pri, R0 = Me (2a), CH2Ph (3a);
2
R = Bun, R0 = Me (2b), CH2Ph (3b); R = But, R0 = Me
(2c), CH2Ph (3c); R = Ph, R0 = Me (2d), CH2Ph (3d)),
were prepared via the reaction of two equivalents of
the corresponding Grignard reagent and the ansa-zircon-
ocene dichloride complex 1a–d (Eq. (2)). Compounds 2
and 3 were characterized by spectroscopic methods (see
1
Section 4). The H and 13C{1H} NMR spectra of 2 gave
two unique signals for the metal bonded methyl groups
(in 2a these signals overlap), thus confirming the dialky-
lation of the ansa-metallocene complex. The chiral nature
of 3, means that the methylene protons of the non-equiv-
alent benzyl ligands are diastereoscopic and thus four
1
doublets were observed in the H NMR spectra.
2MgR'Cl
H
R
Cl
Cl
H
R
R'
R'
Zr
Zr
ð2Þ
R = Pri, R' = Me (2a), CH2Ph (3a);
R = Bun, R' = Me (2b), CH2Ph (3b);
R = But, R' = Me (2c), CH2Ph (3c);
R = Ph, R' = Me (2d), CH2Ph (3d)
We have previously shown that the alkylation process of
silicon bridged ansa-zirconocene complexes is controlled by
steric factors and that this may be due to the alkyl ligand or
the substituents in the b-position of the cyclopentadienyl
ring [6e]. The benzyl group was shown to give only mono-
Fig. 3. Molecular structure and atom-labeling scheme for
[Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}(CH2Ph)2] (3b) with thermal ellipsoids
at 30% probability.
Table 2
Selected structural data of single carbon atom ansa bridge zirconocene complexes
a
˚
˚
Complex
Zr–Cp (A)
Zr–Cl (A)
Cp–Zr–Cp (ꢁ)
Cl–Zr–Cl (ꢁ)
C(cp)–C–C(cp) (ꢁ)
Reference
[Zr{H2C(g5-C5H4)2}Cl2]
116.4
116.7
116.6
116.4
116.3
[9]
[8]
[Zr{Me2C(g5-C5H4)2}Cl2]
2.213
2.191
2.192
2.178
2.4364
2.433
2.445
2.437
2.432
2.427
2.427
2.432
2.4386
2.4379
2.4404
2.4357
2.426
100.25(3)
100.51(7)
99.48(7)
100.0(1)
100.6(3)
100.92(8)
99.17(9)
98.5(2)
102.46(4)
102.98(4)
100.69(4)
101.73(5)
102.37(9)
99.5(2)
99.8(5)
99.7(5)
99.1(2)
99.7
99.2(4)
99.2(6)
99(1)
102.7(2)
102.9(2)
102.2(3)
101.7(3)
98(2)
[Zr{(CH2)4C(g5-C5H4)2}Cl2]
[Zr{(CH2)5C(g5-C5H4)2}Cl2]
[Zr{(CH2)6C(g5-C5H4)2}Cl2]
[Zr{CH2CH2(Me)NCH2CH2C(g5-C5H4)2}Cl2]
[Zr{C12H8C(g5-C5H4)2}Cl2]
[10]
[10]
[10]
[11]
[12]
[13]
[13]
[14]
rac-[Zr{Me2C(g5-C5H3But)2}Cl2]
meso-[Zr{Me2C(g5-C5H3But)2}Cl2]
[Zr{H2C(g5-C5H2Me2-2,5)2}Cl2]b
2.202
2.198
2.198
2.205
2.190 Cp
2.193 Cp*
2.186 Cp
2.186 Cp*
2.187 Cp
2.192 Cp*
2.188 Cp
2.186 CpR
117.13
117.60
117.64
117.59
117.5
[Zr{Me(H)C(g5-C5H2Me2-2,5)2}Cl2]b
[Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (1b)
[Zr{But(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (1c)
[Zr{Ph(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (1d)
[Zr{Me(H)C(g5-C5H4)(g5-C5H2Me2-2,5)}Cl2]
a
[14]
This work
This work
[7]
2.424
118.3
101.56(8)
99.40(2)
102.11(7)
101.0(5)
100.9(2)
100.7(4)
2.434
117.1(1)
117.00
2.4353(10)
[15]
Cp* refers to the C5Me4 moiety; CpR refers to the C5H3R moiety.
There are two independent molecules in the asymmetric cell.
b

A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
2927
Table 3
˚
Selected bond lengths (A) and angles (ꢁ) for 3b
Me
C Me
Me
N Ar
H
R
H
R
Compound
3b
Zr
Zr
˚
Bond lengths (A)
N
C
Zr(1)–Cent(1)
Zr(1)–Cent(2)
av. Zr(1)–C(C(1)–C(5))
av. Zr(1)–C(C(10)–C(14))*
Zr(1)–C(20)
Zr(1)–C(27)
C(15)–C(16)
C(1)–C(15)
C(10)–C(15)
2.210
2.196
Ar
Me
*
2.516(4)
2.498(4)
2.294(5)
2.321(5)
1.494(8)
1.531(7)
1.549(7)
syn-N-outside
syn-N-inside
Me
C Me
Me
N Ar
R
R
Zr
Zr
H
H
N
C
Bond angles (ꢁ)
Ar
Me
Cent(1)–Zr(1)–Cent(2)
C(15)–C(1)–Cent(1)
C(15)–C(10)–Cent(2)
C(1)–C(15)–C(10)
C(1)–C(15)–C(16)
C(10)–C(15)–C(16)
C(20)–Zr(1)–Cent(1)
C(20)–Zr(1)–Cent(2)
C(27)–Zr(1)–Cent(1)
C(27)–Zr(1)–Cent(2)
C(20)–Zr(1)–C(27)
Zr(1)–C(20)–C(21)
Zr(1)–C(27)–C(28)
117.4
164.32
163.59
101.1(4)
117.8(5)
114.1(5)
107.29
111.64
105.07
110.77
103.5(2)
122.1(3)
122.7(3)
anti-N-outside
anti-N-inside
Ar = C6H3Me2-2,6
Fig. 4. Possible conformations for the iminoacyl metal complexes 4.
cyl ligand in 4 on the basis of the IR and 13C NMR
spectroscopy which show the characteristic stretching
vibration m(C@N) at ca. 1600 cmꢁ1 and iminoacyl quater-
nary carbon atom signal at ca. 250 ppm, respectively. The
1H NMR spectra of 4 in addition to the expected signals
for the ansa-metallocene protons, gave signals correspond-
ing to the iminoacyl alkyl group (see Section 4).
Cent(1) and Cent(2) are the centroids of C(1)–C(5) and C(10)–C(14),
respectively; refers to the average bond distance between Zr(1) and the
*
carbon atoms of the C5 ring of the corresponding cyclopentadienyl moiety.
The iminoacyl group can position itself in two distinct
conformations, the ‘‘proximal’’ or ‘‘N-outside’’ and the
‘‘distal’’ or ‘‘N-inside’’ configurations (Fig. 4). In addition,
in 4 the zirconium atom is now a chiral centre and therefore
the formation of two diastereomers (syn and anti) is possi-
ble (Fig. 4). Due to the distance between the zirconium and
the chiral carbon atom, the relative positioning of the sub-
stituents of the ansa bridge most probably will have no
influence in the preferential insertion reaction at the syn
or anti alkyl group. Therefore, we can expect that both
the syn and anti isomers will be present in the final product.
1H and 13C{1H} NMR spectroscopic data indicate the
presence of only two of the four possible conformations.
Although it has been demonstrated that the N-outside iso-
mer is the resulting initial kinetic iminoacyl product of the
insertion reaction, most group 4 metal derivatives show the
structure of the N-inside isomer which results from thermo-
dynamic control [17]. For 4 the isolated product was
observed not to evolve over time and therefore we tenta-
tively propose that they are the products resulting from
thermodynamic control and adopt the N-inside conforma-
tion. A second insertion was not observed even when stoi-
chiometries other than 1:1 were tested.
The structure of 3b shows the typical bent metallocene
conformation observed in zirconocene dichloride com-
plexes. The ansa ligand chelates the zirconium atom and
both C5 rings are bound to the metal in an g5 mode. The
pseudo-tetrahedral environment of the zirconium atom is
completed by the two a-carbon atoms of the benzyl groups.
The structural parameters of 3b are directly comparable
with those of its parent zirconocene dichloride complex 1b.
The reaction of the isocyanide reagent CNC6H3Me2-2,6
with 2 has been studied (Eq. (3)). The products of the
insertion reactions, [Zr{R(H)C(g5-C5Me4)(g5-C5H4)}{g2-
MeC@NC6H3Me2-2,6}Me] (R = Pri (4a), Bun (4b), But
(4c), Ph (4d)) were characterized by 1H and 13C NMR
spectroscopy.
Me
ArNC
H
R
Me
Me
H
R
Zr
Zr
Ar
N
C
ð3Þ
Me
R = Pri (4a), Bun (4b), But (4c), Ph (4d)
Ar = C6H3Me2-2,6
The migratory insertion of alkyl groups towards isocya-
3. Conclusions
nide ligands allow the introduction of iminoacyl groups
which are present in different coordination modes. In fact,
for high valent oxophilic early transition metals, the imi-
noacyl group typically adopts an g2-coordination mode
through both the nitrogen and carbon atoms [16]. Simi-
larly, an g2-coordination mode is proposed for the iminoa-
In this paper, we report the synthesis and X-ray struc-
tures of chiral carbon atom bridged ansa-zirconocene com-
plexes. The preparation and characterization of their
dialkyl derivatives and their reactivity in isocyanide inser-
tion reactions are also described.

2928
A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
4. Experimental
4.1. Materials and procedures
21.9 (HCMe2), 29.0 (HCMe2), 31.2, 31.3 (Zr–Me), 48.4
(PriCH), 103.0, 107.1, 113.0, 115.1, 120.4 (C5H4), 99.3,
107.9, 114.4, 117.8, 121.2 (C5Me4). Anal. Calc. for
C20H30Zr: C, 66.42; H, 8.36. Found: C, 66.09; H, 8.30%.
The preparation of 2b–d and 3a–d was carried out in an
identical manner to 2a.
All reactions were performed using standard Schlenk-
tube techniques in an atmosphere of dry nitrogen. Solvents
were distilled from appropriate drying agents and degassed
before use. [Zr{R(H)C(g5-C5Me4)(g5-C5H4)}Cl2] (R =
Bun, But, Ph) were prepared as described earlier [7].
MgMeCl, Mg(CH2Ph)Cl and CNC6H3Me2-2,6 were pur-
chased from Aldrich and used directly. IR spectra were
recorded on a Perkin–Elmer PE 883 IR spectrophotometer.
1H and 13C{1H} spectra were recorded on a Varian Gemini
FT-400 spectrometer and referenced to the residual pro-
tons in the deuteriated solvent. Microanalyses were carried
out with a Perkin–Elmer 2400 microanalyzer.
4.4. Synthesis of [Zr{Bun(H)C(g5-C5Me4)-
(g5-C5H4)}2Me2] (2b)
From 3 M solution of MgMeBr in THF (0.24 ml,
0.72 mmol) and [Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1b) (0.15 g, 0.36 mmol). Yield: 0.11 g, 80%. 1H NMR
(400 MHz, C6D6): d ꢁ0.31 (3H), ꢁ0.22 (3H) (s, Zr–
Me), 0.83 (2H), 0.86 (3H), 1.32 (4H) (m, CH2CH2-
CH2CH3), 1.51 (3H), 1.68 (3H), 1.85 (3H), 1.87 (3H)
(m, C5Me4), 3.51 (t, 1H, BunCH) (3J(1H–1H) 8.4 Hz),
5.00 (1H), 5.15 (1H), 6.33 (1H), 6.43 (1H) (s, C5H4).
13C{1H} NMR (100 MHz, C6D6): d 10.7, 11.1, 11.9,
13.7 (C5Me4), 14.3, 22.9, 30.2, 31.1 (Bun), 31.0, 31.1
(Zr–Me), 39.1 (BunCH), 113.2, 114.8, 127.8, 128.1,
128.2 (C5H4), 99.0, 108.6, 117.4, 120.3, 121.2 (C5Me4).
Anal. Calc. for C21H32Zr: C, 67.13; H, 8.58. Found: C,
66.91; H, 8.56%.
4.2. Synthesis of [Zr{Pri(H)C(g5-C5Me4)(g5-C5H4)}Cl2]
(1a)
[ZrCl4(THF)2] (1.81 g, 4.80 mmol) in toluene (50 ml)
was added to a solution of LiK{Pri(H)C(g5-C5Me4)(g5-
C5H4)} (1.37 g, 4.80 mmol) in Et2O (100 ml). The reaction
mixture was allowed to stir for 12 h. Solvent was removed
under reduced pressure and hexane (100 ml) added to the
resulting solid. The mixture was filtered and the filtrate
concentrated (10 ml) and cooled to ꢁ30 ꢁC to yield crystals
4.5. Synthesis of [Zr{But(H)C(g5-C5Me4)-
(g5-C5H4)}2Me2] (2c)
1
of the title complex (1.10 g, 60%). H NMR (400 MHz,
C6D6): d 0.87 (3H) (3J(1H–1H) 6.6 Hz), 0.91 (3H)
(3J(1H–1H) 6.2 Hz) (d, HCMe2), 1.49 (3H), 1.65 (3H),
1.86 (3H), 1.87 (3H) (s, C5Me4), 2.30 (m, 1H, HCMe2),
3.42 (d, 1H, PriCH) (3J(1H–1H) 12.1 Hz), 5.06 (1H), 5.13
(1H), 6.37 (1H), 6.48 (1H) (m, C5H4). 13C{1H} NMR
(100 MHz, C6D6): d 11.7, 11.9, 12.7, 14.5 (C5Me4), 20.4,
21.5 (HCMe2), 29.0 (HCMe2), 48.5 (PriCH), 104.1, 107.9,
119.5, 122.3, 128.9 (C5H4), 104.8, 114.8, 117.3, 120.9,
130.0 (C5Me4). Anal. Calc. for C18H24Cl2Zr: C, 53.71; H,
6.01. Found: C, 53.45; H, 5.98%.
From 3 M solution of MgMeBr in THF (0.44 ml,
1.32 mmol) and [Zr{But(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1c) (0.23 g, 0.55 mmol). Yield: 0.15 g, 75%. 1H NMR
(400 MHz, C6D6): d ꢁ0.34 (3H), ꢁ0.32 (3H) (s, Zr–Me),
1.08 (s, 9H, But), 1.51 (3H), 1.68 (3H), 1.85 (3H), 1.87
(3H) (s, C5Me4), 3.41 (s, 1H, ButCH), 4.99 (1H), 5.09
(1H), 6.27 (1H), 6.46 (1H) (m, C5H4). 13C{1H} NMR
(100 MHz, C6D6): d 11.5, 11.6, 12.5, 16.3 (C5Me4), 30.5,
33.6 (But), 31.1, 31.3 (Zr–Me), 51.8 (ButCH), 106.1,
109.8, 111.9, 116.5, 120.3 (C5H4), 100.5, 107.2, 114.1,
119.9, 121.9 (C5Me4). Anal. Calc. for C21H32Zr: C, 67.13;
H, 8.58. Found: C, 66.83; H, 8.50%.
4.3. Synthesis of [Zr{Pri(H)C-
(g5-C5Me4)(g5-C5H4)}2Me2] (2a)
4.6. Synthesis of [Zr{Ph(H)C(g5-C5Me4)-
(g5-C5H4)}2Me2] (2d)
A
3 M solution of MgMeBr in THF (0.50 ml,
1.50 mmol) was added to a stirring solution of [Zr{Pri(H)-
C(g5-C5Me4)(g5-C5H4)}Cl2] (1a) (0.30 g, 0.75 mmol) in
THF (25 ml) at ꢁ78 ꢁC. The solution was allowed to
warm to room temperature and stirred for 4 h. Solvent
was removed in vacuo and the remaining solid extracted
in hexane (30 ml). A white crystalline solid was obtained
by concentrating (5 ml) and cooling (ꢁ30 ꢁC) the solution
Zr–Me), 0.93 (3H) (3J(1H–1H) 6.6 Hz), 0.98 (3H)
(3J(1H–1H) 6.2 Hz) (d, HCMe2), 1.48 (3H), 1.62 (3H),
1.85 (6H) (s, C5Me4), 2.21 (m, 1H, HCMe2), 3.06 (d,
1H, PriCH) (3J(1H–1H) 12.1 Hz), 4.99 (1H), 5.05 (1H),
6.32 (1H), 6.43 (1H) (m, C5H4). 13C{1H} NMR
(100 MHz, C6D6): d 11.1, 11.4, 12.1, 13.9 (C5Me4), 20.8,
From 3 M solution of MgMeBr in THF (0.55 ml,
1.65 mmol) and [Zr{Ph(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1d) (0.20 g, 0.46 mmol). Yield: 0.16 g, 85%. 1H NMR
(400 MHz, C6D6): d ꢁ0.41 (3H), ꢁ0.32 (3H) (s, Zr–Me),
1.12 (3H), 1.46 (3H), 1.58 (3H), 1.74 (3H) (s, C5Me4),
4.80 (s, 1H, PhCH), 5.03 (1H), 5.10 (1H), 6.30 (1H),
6.38 (1H) (m, C5H4), 6.96–7.40 (m, 5H, Ph). 13C{1H}
1
(0.21 g, 80%). H NMR (400 MHz, C6D6): d ꢁ0.32 (s, 6H,
NMR (100 MHz, C6D6): d 11.3, 11.5, 12.4, 14.6
(C5Me4), 31.9, 32.1 (Zr–Me), 43.3 (PhCH), 105.3, 108.2,
113.1, 115.9, 121.9 (C5H4), 99.5, 105.7, 117.8, 120.4,
121.6 (C5Me4), 127.0, 128.0, 128.9, 141.4 (Ph). Anal. Calc.
for C23H28Zr: C, 69.81; H, 7.13. Found: C, 69.69; H,
7.08%.

A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
2929
4.7. Synthesis of [Zr{Pri(H)C(g5-C5Me4)-
(g5-C5H4)}2(CH2Ph)2] (3a)
(C5Me4), 125.9, 126.0, 126.1 (4C), 128.4 (2C), 128.5 (2C),
151.3, 152.5 (CH2Ph). Anal. Calc. for C33H40Zr: C,
75.08; H, 7.64. Found: C, 74.76; H, 7.58%.
From 2 M solution of Mg(CH2Ph)Br in THF (2.6 ml,
1.8 mmol) and [Zr{Pri(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1a) (0.30 g, 0.75 mmol). Yield: 0.33 g, 85%. 1H NMR
(400 MHz, C6D6): d 0.84 (3H) (3J(1H–1H) 7.0 Hz), 0.88
(3H) (3J(1H–1H) 6.9 Hz) (d, HCMe2), 0.96 (1H), 0.97
(1H) (2J(1H–1H) 11.0 Hz), 1.77 (1H), 1.78 (1H)
(2J(1H–1H) 10.6 Hz) (d, CH2Ph), 1.37 (3H), 1.51 (3H),
1.70 (3H), 1.71 (3H) (s, C5Me4), 2.05 (m, 1H, HCMe2),
2.94 (d, 1H, PriCH) (3J(1H–1H) 12.1 Hz), 4.60 (1H), 4.71
(1H), 5.59 (1H), 5.73 (1H) (m, C5H4), 6.71–7.14 (m, 10H,
CH2Ph). 13C{1H} NMR (100 MHz, C6D6): d 11.1, 11.4,
12.1, 13.9 (C5Me4), 20.6, 21.6 (HCMe2), 28.8 (HCMe2),
48.2 (PriCH), 59.6, 59.9 (CH2Ph), 107.8, 116.9, 119.7,
121.2, 122.7 (C5H4), 106.7, 113.6, 117.2, 121.8, 129.9
(C5Me4), 125.9, 126.1, 126.2 (4C), 128.7 (4C), 152.0 (2C)
(CH2Ph). Anal. Calc. for C32H38Zr: C, 74.79; H, 7.45.
Found: C, 74.52; H, 7.37%.
4.10. Synthesis of [Zr{Ph(H)C(g5-C5Me4)-
(g5-C5H4)}2(CH2Ph)2] (3d)
From 2 M solution of Mg(CH2Ph)Br in THF (0.80 ml,
1.63 mmol) and [Zr{Ph(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1d) (0.30 g, 0.68 mmol). Yield: 0.26 g, 70%. 1H NMR
(400 MHz, C6D6): d 0.98 (1H), 1.02 (1H) (2J(1H–1H)
11.7 Hz), 1.72 (1H), 1.88 (1H) (2J(1H–1H) 10.4 Hz) (d,
CH2Ph), 1.12 (3H), 1.45 (3H), 1.67 (3H), 1.78 (3H) (s,
C5Me4), 4.78 (s, 1H, PhCH), 4.75 (1H), 4.92 (1H), 5.67
(1H), 5.78 (1H) (m, C5H4), 6.71–7.19 (m, 15H, CH2Ph
and PhCH). 13C{1H} NMR (100 MHz, C6D6): d 11.1,
11.3, 12.1, 14.5 (C5Me4), 45.2 (PhCH), 58.8, 59.9 (CH2Ph),
103.4, 106.2, 117.0, 119.4, 121.7 (C5H4), 99.9, 106.7, 117.8,
120.7, 121.7 (C5Me4), 125.4, 128.2, 128.8, 141.8 (PhCH),
126.1, 126.6, 127.9 (4C), 128.7 (4C), 156.6 (2C) (CH2Ph).
Anal. Calc. for C35H36Zr: C, 76.73; H, 6.62. Found: C,
76.48; H, 6.54%.
4.8. Synthesis of [Zr{Bun(H)C(g5-C5Me4)-
(g5-C5H4)}2(CH2Ph)2] (3b)
4.11. Synthesis of [Zr{Pri(H)C(g5-C5Me4)-
From 2 M solution of Mg(CH2Ph)Br in THF (1.40 ml,
2.80 mmol) and [Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1b) (0.50 g, 1.20 mmol). Yield: 0.53 g, 85%. 1H NMR
(400 MHz, C6D6): d 0.83 (2H), 0.86 (3H), 1.32 (4H) (m,
CH2CH2CH2CH3), 1.01 (1H), 1.04 (1H) (2J(1H–1H)
10.1 Hz), 1.69 (1H), 1.87 (1H) (2J(1H–1H) 11.6 Hz) (d,
CH2Ph), 1.46 (3H), 1.62 (3H), 1.75 (3H), 1.77 (3H) (s,
C5Me4), 3.43 (d, 1H, BunCH) (3J(1H–1H) 8.4 Hz), 4.70
(1H), 4.90 (1H), 5.67 (1H), 5.79 (1H) (m, C5H4), 6.79–
7.17 (m, 10H, CH2Ph). 13C{1H} NMR (100 MHz,
C6D6): d 11.0, 11.4, 12.1, 14.0 (C5Me4), 14.5, 23.1, 30.3,
31.1 (Bun), 39.2 (BunCH), 59.7, 60.1 (CH2Ph), 104.5,
107.2, 117.1, 119.4, 122.7 (C5H4), 96.9, 106.9, 114.0,
116.7, 121.2 (C5Me4), 125.9, 126.0, 126.3 (2C), 126.4
(2C), 128.5 (2C), 128.6 (2C), 151.9, 152.1 (CH2Ph). Anal.
Calc. for C33H40Zr: C, 75.08; H, 7.64. Found: C, 74.97;
H, 7.65%.
(g5-C5H4)}2{g2-MeC@NC6H3Me2-2,6}Me] (4a)
(2,6-Dimethylphenyl)isocyanide (0.18 g, 1.40 mmol) and
[Zr{Pri(H)C(g5-C5Me4)(g5-C5H4)}2Me2] (2a) (0.50 g,
1.40 mmol) were dissolved in THF (100 ml). The resulting
solution was stirred at room temperature for 2 h. Solvent
was removed in vacuo and the remaining solid extracted
with hexane (30 ml). A yellow solid was obtained by con-
centrating (5 ml) and cooling (ꢁ30 ꢁC) the solution
(0.59 g, 85%). IR (Nujol): m(C@N) 1590 cmꢁ1. H NMR
1
(400 MHz, C6D6; two isomers): d ꢁ0.01 (3H), 0.00 (3H)
(s, Zr–Me), 0.93 (3H) (3J(1H–1H) 6.6 Hz), 0.98 (3H)
(3J(1H–1H) 6.2 Hz) (d, HCMe2), 1.51 (3H), 1.83 (6H),
2.07 (3H), 2.08 (3H), 2.18 (3H), 2.20 (3H), 2.25 (3H) (s,
C5Me4), 1.87 (6H), 1.88 (6H) (s, C6H3Me2), 2.38 (s, 6H,
NCMe), 2.61 (1H), 2.72 (1H) (m, HCMe2), 3.38 (1H)
(3J(1H–1H) 12.1 Hz), 3.52 (1H) (3J(1H–1H) 11.7 Hz) (d,
PriCH), 5.34 (1H), 5.46 (1H), 5.51 (2H), 5.65 (1H), 5.67
(1H), 5.76 (1H), 5.92 (1H) (m, C5H4), 7.01 (m, 6H,
C6H3Me2). 13C{1H} NMR (100 MHz, C6D6; two isomers):
d 10.8, 11.0, 11.1, 11.5, 11.8, 12.7, 13.8, 14.5 (C5Me4), 18.7
(2C), 18.8 (2C) (C6H3Me2), 21.0 (2C), 21.9 (2C) (HCMe2),
27.3, 27.5 (Zr–Me), 22.9, 23.0 (NCMe), 28.7, 29.2
(HCMe2), 48.2, 48.3 (PriCH), 101.6, 105.8, 108.5, 108.8
(2C), 110.6, 111.6, 115.1, 116.9, 117.6 (C5H4), 96.8 (2C),
99.7, 106.9, 107.6, 108.6, 110.5, 111.4, 116.0, 116.6
(C5Me4), 127.6 (4C), 127.9 (2C), 128.4 (2C), 129.1 (2C),
129.3 (2C) (C6H3Me2), 248.2, 248.5 (NC). Anal. Calc. for
C29H39NZr: C, 70.67; H, 7.98; N, 2.84. Found: C, 70.35;
H, 7.99; N, 2.89%.
4.9. Synthesis of [Zr{But(H)C(g5-C5Me4)-
(g5-C5H4)}2(CH2Ph)2] (3c)
From 2 M solution of Mg(CH2Ph)Br in THF (1.15 ml,
2.30 mmol) and [Zr{But(H)C(g5-C5Me4)(g5-C5H4)}2Cl2]
(1c) (0.40 g, 0.96 mmol). Yield: 0.35 g, 70%. 1H NMR
(400 MHz, C6D6): d 1.04 (s, 9H, But), 0.97 (1H), 1.16
(1H) (2J(1H–1H) 11.9 Hz), 1.86 (1H), 1.90 (1H)
(2J(1H–1H) 10.8 Hz) (d, CH2Ph), 1.47 (3H), 1.66 (3H),
1.76 (3H), 1.77 (3H) (s, C5Me4), 3.33 (s, 1H, ButCH),
4.64 (1H), 4.92 (1H), 5.57 (1H), 5.89 (1H) (m, C5H4),
6.75–7.18 (m, 10H, CH2Ph). 13C{1H} NMR (100 MHz,
C6D6): d 11.0, 11.1, 12.2, 15.7 (C5Me4), 29.9, 30.3 (But),
51.3 (ButCH), 59.0, 60.5 (CH2Ph), 106.3, 110.6, 115.2,
120.8, 141.7 (C5H4), 98.2, 105.5, 112.9, 119.3, 123.3
The preparation of 4b–d was carried out in an identical
manner to 4a.

2930
A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
4.12. Synthesis of [Zr{Bun(H)C(g5-C5Me4)-
(g5-C5H4)}2{g2-MeC@NC6H3Me2-2,6}Me] (4b)
4.13. Synthesis of [Zr{But(H)C(g5-C5Me4)-
(g5-C5H4)}2{g2-MeC@NC6H3Me2-2,6}Me] (4c)
From
2,6-dimethylphenyl
isocyanide
(0.17 g,
From
2,6-dimethylphenyl
isocyanide
(0.17 g,
1.33 mmol) and [Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}2Me2]
(2b) (0.50 g, 1.33 mmol). Yield: 0.57 g, 86%. IR (Nujol):
1.33 mmol) and [Zr{Bun(H)C(g5-C5Me4)(g5-C5H4)}2Me2]
(2c) (0.50 g, 1.33 mmol). Yield: 0.53 g, 79%. IR (Nujol):
m(C@N) 1605 cmꢁ1. H NMR (400 MHz, C6D6; two iso-
m(C@N) 1620 cmꢁ1. H NMR (400 MHz, C6D6; two iso-
1
1
mers): d ꢁ0.13 (3H), ꢁ0.12 (3H) (s, Zr–Me), 0.89 (6H),
1.31–1.46 (12H) (m, CH2CH2CH2CH3), 1.35 (3H), 1.38
(3H), 1.69 (6H), 1.90 (3H), 1.95 (3H), 2.09 (3H), 2.12
(3H) (s, C5Me4), 1.72 (6H), 1.73 (6H) (s, C6H3Me2), 2.26
(s, 6H, NCMe), 3.66 (1H) (3J(1H–1H) 8.4 Hz), 3.81 (1H)
(3J(1H–1H) 8.4 Hz) (t, BunCH), 5.20 (1H), 5.31 (1H), 5.37
(1H), 5.47 (1H), 5.50 (1H), 5.63 (2H), 5.76 (1H) (m,
C5H4), 6.86 (m, 6H, C6H3Me2). 13C{1H} NMR
(100 MHz, C6D6; two isomers): d 11.4, 11.5, 11.7, 11.8,
12.2, 13.1, 14.2, 14.9 (C5Me4), 14.7, 14.8, 19.1 23.2, 23.3,
23.4, 30.8, 30.9 (Bun), 19.4 (2C), 19.5 (2C) (C6H3Me2),
31.6, 31.8 (Zr–Me), 30.3, 31.4 (NCMe), 39.4, 39.5
(BunCH), 97.2, 107.5, 108.5, 109.0, 110.1, 110.3, 111.1,
115.3, 115.4, 115.9 (C5H4), 99.3, 102.1, 105.2, 108.2,
108.4, 109.0 (2C), 116.7, 116.9, 117.5 (C5Me4), 124.9
(2C), 128.3 (4C), 128.4 (4C), 129.3 (2C) (C6H3Me2),
247.8, 248.0 (NC). Anal. Calc. for C30H41NZr: C, 71.09;
H, 8.15; N, 2.76. Found: C, 70.86; H, 8.07; N, 2.74%.
mers): d ꢁ0.11 (3H), ꢁ0.10 (3H) (s, Zr–Me), 1.24 (9H),
1.25 (9H) (s, But), 1.37 (3H), 1.38 (3H), 1.68 (3H), 1.69
(3H), 1.70 (3H), 1.71 (3H), 1.72 (3H), 1.74 (3H) (s,
C5Me4), 1.90 (6H), 1.95 (6H) (s, C6H3Me2), 2.30 (s, 6H,
NCMe), 3.61 (1H), 3.77 (1H) (s, ButCH), 5.09 (1H),
5.16 (1H), 5.38 (1H), 5.42 (1H), 5.46 (1H), 5.81 (1H),
6.27 (1H), 6.46 (1H) (m, C5H4), 6.86 (m, 6H,
C6H3Me2). 13C{1H} NMR (100 MHz, C6D6; two iso-
mers): d 11.2, 11.3, 11.5, 11.6, 12.2, 12.3, 15.8, 16.0
(C5Me4), 19.9 (2C), 20.1 (2C) (C6H3Me2), 33.2, 33.3,
33.5, 33.6 (But), 27.3, 27.5 (Zr–Me), 22.9, 23.0 (NCMe),
51.9, 52.0 (ButCH), 106.1, 106.2, 109.9, 110.2, 115.8,
115.9, 116.6, 116.7, 120.2, 120.3 (C5H4), 101.0, 101.5,
112.7, 112.9, 114.1, 115.4, 117.2, 118.2, 123.0, 123.9
(C5Me4), 124.4 (2C), 127.6 (4C), 128.0 (4C), 129.9 (2C)
(C6H3Me2), 248.9, 249.0 (NC). Anal. Calc. for
C30H41NZr: C, 71.09; H, 8.15; N, 2.76. Found: C,
70.72; H, 8.11; N, 2.70%.
Table 4
Crystal data and structure refinement details for 1b, 1c and 3b
Compound
1b
1c
3b
Formula
C
19H26Cl2Zr
C19H26Cl2Zr
416.52
200(2)
0.71073
Monoclinic
P21/n
9.1010(8)
16.593(1)
12.634(3)
C33H40Zr
527.87
100(2)
1.54178
Monoclinic
P21/n
9.7276(1)
17.9351(1)
15.7562(1)
Formula weight
T (K)
416.52
230(2)
0.71073
Triclinic
˚
k (A)
Crystal system
ꢀ
Space group
P1
˚
a (A)
8.531(3)
9.352(3)
12.144(7)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
86.69(2)
83.59(2)
79.57(3)
946.2(5)
97.95(1)
100.756(1)
3
˚
V (A )
1889.6(5)
2700.62(4)
Z
2
4
4
Dcalc (g cmꢁ3
)
1.462
0.858
428
1.464
0.860
856
1.298
3.450
1112
l (mmꢁ1
F(000)
)
Crystal dimensions (mm)
h Range (ꢁ)
hkl Ranges
0.3 · 0.2 · 0.1
2.22–28.05
ꢁ11 6 h 6 11,
ꢁ12 6 k 6 12,
0 6 l 6 16
4530/243
0.3 · 0.2 · 0.2
2.04–27.98
0.20 · 0.15 · 0.15
3.77–70.57
ꢁ10 6 h 6 11,
ꢁ21 6 k 6 19,
ꢁ18 6 l 6 19
4868/366
ꢁ12 6 h 6 11,
0 6 k 6 21,
0 6 l 6 16
4519/203
1.017
R1 = 0.0646, wR2 = 0.1191
R1 = 0.1675, wR2 = 0.1489
1.156 and ꢁ0.518
Data/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
1.029
1.094
R1 = 0.0710, wR2 = 0.1684
R1 = 0.1318, wR2 = 0.2115
1.099 and ꢁ0.950
R1 = 0.0505, wR2 = 0.1273
R1 = 0.0543, wR2 = 0.1301
0.807 and ꢁ0.610
ꢁ3
˚
Largest difference in peak and hole (e A
)
P
P
P
P
2
2 1=2
R1 = iFo| ꢁ |Fci/ |Fo|; wR2 ¼ ½ ½wðF 2o ꢁ F c2Þ ꢀ= ½wðF o2Þ ꢀꢀ
.

A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
2931
4.14. Synthesis of [Zr{Ph(H)C(g5-C5Me4)-
tions, and refined in the riding model. Weights were
optimized in the final cycles. Crystallographic data are
given in Table 4.
(g5-C5H4)}2{g2-MeC@NC6H3Me2-2,6}Me] (4d)
From
2,6-dimethylphenyl
isocyanide
(0.17 g,
1.33 mmol) and [Zr{Ph(H)C(g5-C5Me4)(g5-C5H4)}2Me2]
(2d) (0.52 g, 1.33 mmol). Yield: 0.56 g, 80%. IR (Nujol):
Acknowledgments
m(C@N) 1570 cmꢁ1. H NMR (400 MHz, C6D6; two iso-
1
We gratefully acknowledge financial support from the
mers): d ꢁ0.16 (3H), ꢁ0.14 (3H) (s, Zr–Me), 1.34 (3H),
1.35 (3H), 1.40 (3H), 1.55 (3H), 1.58 (3H), 1.64 (3H),
1.66 (3H), 1.69 (3H) (s, C5Me4), 1.76 (6H), 1.77 (6H) (s,
C6H3Me2), 1.96 (3H), 1.98 (3H) (s, NCMe), 4.99 (1H),
5.27 (1H) (s, PhCH), 4.89 (1H), 5.06 (1H), 5.15 (1H),
5.19 (1H), 5.48 (1H), 5.50 (1H), 5.58 (1H), 5.69 (1H)
(m, C5H4), 6.80–7.20 (m, 11H, C6H3Me2 and Ph).
13C{1H} NMR (100 MHz, C6D6; two isomers): d 11.2,
11.3, 11.4, 11.6, 12.2, 12.4, 14.3, 14.6 (C5Me4), 19.0
(2C), 19.5 (2C) (C6H3Me2), 36.6, 37.2 (Zr–Me), 38.0,
38.4 (NCMe), 44.2, 44.5 (PhCH), 101.1 (2C), 107.9
(2C), 111.0, 113.6, 113.8, 117.5, 119.0, 119.3 (C5H4),
102.0 (2C), 103.7, 108.3, 109.3 (2C), 114.1, 115.6, 115.8,
116.2 (C5Me4), 125.6 (2C), 126.8 (4C), 130.01 (4C),
134.8 (2C) (C6H3Me2), 125.2, 125.4, 128.0 (4C), 128.6
(4C), 141.8 (2C) (PhCH), 247.9, 248.5 (NC). Anal. Calc.
for C32H37NZr: C, 72.95; H, 7.08; N, 2.66. Found: C,
72.59; H, 7.02; N, 2.63%.
´
Ministerio de Educacion y Ciencia, Spain (Grant Nos.
BQU2002-04638-C02-01 and MAT2003-05345) and the
Universidad Rey Juan Carlos (GVC-2004-12). We also
´
thank Dr. Cesar Pastor (Universidad Autonoma de Ma-
drid) for his assistance in the structural resolution of 3b.
Appendix A. Supplementary material
Crystallographic data for the structural analyses of 1b,
1c and 3b have been deposited with the Cambridge Crystal-
lographic Data Centre, CCDC-287186, CCDC-287187 and
CCDC-287188. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223
336 033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk). Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.02.039.
4.15. X-ray structure determinations of [Zr{Bun(H)C-
(g5-C5Me4)(g5-C5H4)}Cl2] (1b), [Zr{But(H)C-
(g5-C5Me4)(g5-C5H4)}Cl2] (1c) and [Zr{Bun(H)C-
(g5-C5Me4)(g5-C5H4)}(CH2Ph)2] (3b)
References
[1] (a) See for example: H.G. Alt, H.A. Ko¨ppl, Chem. Rev. 100 (2000)
1205;
For 1b and 1c, data were collected on a NONIUS-
(b) G.W. Coates, Chem. Rev. 100 (2000) 1223;
(c) H.H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, R.M.
¨
MACH3 diffractometer equipped with a graphite mono-
chromated Mo Ka radiation source (k = 0.71073 A). The
Waymouth, Angew. Chem., Int. Ed. Engl. 36 (1995) 1143.
[2] See for example: L. Resconi, L. Cavallo, A. Fait, F. Piemontesi,
Chem. Rev. 100 (2000) 1253.
˚
crystal data, data collection, structural solution, and refine-
ment parameters for both compounds are summarized in
Table 4. Intensity data were collected using an x/2h scan-
technique. Examination of two standard reflections, moni-
tored after 60 min, showed no sign of crystal deterioration.
Data were corrected for Lorentz and polarization effects,
and a semiempirical absorption correction (w-scans) was
made [18]. The structures were solved by direct methods
using the SIR-92 program [19] and refined by full-matrix
least-squares methods (SHELXL-97) [20] on F2. All non-
hydrogen atoms were refined with anisotropic thermal
parameters. Hydrogen atoms were placed using a ‘‘riding
model’’ and included in the refinement at calculated
positions.
[3] S. Prashar, A. Antinolo, A. Otero, Coord. Chem. Rev. 250 (2006) 133.
˜
[4] R.F. Jordan, Adv. Organomet. Chem. 32 (1991) 325.
[5] (a) M. Bochmann, J. Chem. Soc., Dalton Trans. (1996) 255;
(b) X. Yang, C.L. Stern, T.J. Marks, J. Am. Chem. Soc. 116 (1994)
10015;
(c) D. Veghini, M.W. Day, J.E. Bercaw, Inorg. Chim. Acta 280
(1998) 226.
´
[6] (a) A. Antinolo, I. Lopez-Solera, I. Orive, A. Otero, S. Prashar,
˜
´
A.M. Rodrıguez, E. Villasenor, Organometallics 20 (2001) 71;
˜
´
(b) A. Antinolo, I. Lopez-Solera, A. Otero, S. Prashar, A.M.
˜
´
Rodrıguez, E. Villasenor, Organometallics 21 (2002) 2460;
˜
´
(c) C. Alonso-Moreno, A. Antinolo, I. Lopez-Solera, A. Otero, S.
˜
Prashar, A.M. Rodr´ıguez, E. Villasenor, J. Organomet. Chem. 656
˜
(2002) 129;
´
´
(d) A. Antinolo, R. Fernandez-Galan, I. Orive, A. Otero, S. Prashar,
˜
Eur. J. Inorg. Chem. (2002) 2470;
For 3b, data were collected on a Bruker SMART CCD-
´
´
(e) A. Antinolo, R. Fernandez-Galan, B. Gallego, A. Otero, S.
˜
˚
based diffractometer (Cu Ka radiation, k = 1.54178 A)
´
Prashar, A.M. Rodrıguez, Eur. J. Inorg. Chem. (2003) 2626;
operating at 50 kV and 100 mA, using x/2h scan-tech-
nique. Absorption corrections were applied using the SAD-
ABS program [21]. The structure was solved using the
SHELXTL structure determination package [22] by direct
methods and refined by full-matrix least-squares methods
on F2. All non-hydrogen atoms were refined anisotropi-
cally. Hydrogen atoms were included in calculated posi-
´
´
(f) A. Antinolo, M. Fajardo, S. Gomez-Ruiz, I. Lopez-Solera, A.
˜
´
Otero, S. Prashar, A.M. Rodrıguez, J. Organomet. Chem. 683
(2003) 11;
´
´
(g) A. Antinolo, M. Fajardo, S. Gomez-Ruiz, I. Lopez-Solera, A.
˜
Otero, S. Prashar, Organometallics 23 (2004) 4062;
(h) S. Gomez-Ruiz, S. Prashar, M. Fajardo, A. Antinolo, A. Otero,
˜
M.A. Maestro, V. Volkis, M.S. Eisen, C.J. Pastor, Polyhedron 24
(2005) 1298.
´

2932
A. Antin˜olo et al. / Journal of Organometallic Chemistry 691 (2006) 2924–2932
´
´
[7] A. Antinolo, R. Fernandez-Galan, A. Otero, S. Prashar, I.
[14] B.Y. Lee, Y.H. Kim, Y.C. Won, J.W. Han, I.S. Lee, W.H. Suh,
Y.K. Chung, K.H. Song, Organometallics 21 (2002) 1500.
[15] E.S. Cho, U.G. Joung, B.Y. Lee, H. Lee, Y.-W. Park, C.H. Lee,
D.M. Shin, Organometallics 23 (2004) 4693.
[16] L.D. Durfee, I.P. Rothwell, Chem. Rev. 88 (1988) 1059.
[17] G. Erker, Acc. Chem. Res. 17 (1984) 103.
˜
´
Rivilla, A.M. Rodrıguez, M.A. Maestro, Organometallics 23
(2004) 5108.
[8] T. Koch, S. Blaurock, F.B. Somoza, A. Voigt, R. Kirmse, E. Hey-
Hawkins, Organometallics 19 (2000) 2556.
[9] C.E. Zachmanoglou, A. Docrat, B.M. Bridgewater, G. Parkin, C.G.
Brandow, J.E. Bercaw, C.N. Jardine, M. Lyall, J.C. Green, J.B.
Keister, J. Am. Chem. Soc. 124 (2002) 9525.
[18] A.C.T. North, D.C. Phillips, F.S. Mathews, Acta Crystallogr., Sect.
A 24 (1968) 351.
[10] B. Wang, B. Mu, X. Deng, H. Cui, S. Xu, X. Zhou, F. Zou, Y. Li,
L. Yang, Y. Li, Y. Hu, Chem. Eur. J. 11 (2005) 669.
[11] I.E. Nifant’ev, P.V. Ivchenko, V.V. Bagrov, L.G. Kuz’mina, Organo-
metallics 17 (1998) 4734.
[12] N.B. Ivchenko, P.V. Ivchenko, I.E. Nifant’ev, V.V. Bagrov, L.G.
Kuz’mina, Russ. Chem. Bull. 49 (2000) 1287.
[13] I.F. Urazowski, L.O. Atovmyan, S.G. Mkoyan, R. Broussier, P.
Perron, B. Gautheron, F. Robert, J. Organomet. Chem. 536/537
(1997) 531.
[19] SIR-92 A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 26 (1993) 343.
[20] G.M. Sheldrick, Program for the Refinement of Crystal Structure from
Diffraction Data, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[21] G.M. Sheldrick, SADABS Version 2.03: A Program for Empirical
Absorption Correction, Universita¨t Go¨ttingen, Go¨ttingen, Germany,
1997–2001.
[22] Bruker AXS, SHELXTL Version 6.10: Structure Determination
Package, Bruker AXS, Madison, USA, 2000.