Synthesis and reactivity of alkylzirconium complexes incorporating asymmetrically substituted ansa ligands - X-ray crystal structure of [Zr{Me2Si(η5-C5Me4) (η5-C5H3Me)} (CH2

Article abstract of DOI:10.1002/ejic.200300150

The monoalkyl complexes [Zr{Me₂Si(η⁵-C₅Me₄) (η⁵-C₅H₃R)}(R′)Cl] [R = Me, R′ = CH₂Ph (1); R = Me, R′ = CH₂SiMe₃ (2); R = iPr, R′ = CH₂Ph

Full text of DOI:10.1002/ejic.200300150

FULL PAPER
Synthesis and Reactivity of Alkylzirconium Complexes Incorporating
Asymmetrically Substituted ansa Ligands ؊ X-ray Crystal Structure of
[Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}(CH2Ph)Cl]
[a]
[a]
[a]
[a]
´
´
˜
Antonio Antinolo, Rafael Fernandez-Galan, Beatriz Gallego, Antonio Otero,*
[b]
[c]
´
Sanjiv Prashar, and Ana M. Rodrıguez
Keywords: Metallocenes / Zirconium / Insertion reactions / Isocyanides
The
monoalkyl
complexes
[Zr{Me2Si(η5-C5Me4)(η5-
of the isocyanide reagent CNC6H3Me2-2,6 into the
C5H3R)}(RЈ)Cl] [R = Me, RЈ = CH2Ph (1); R = Me, RЈ =
zirconium−carbon σ-bond of complexes 1−8 gave the corres-
CH2SiMe3 (2); R = iPr, RЈ = CH2Ph (3); R = iPr, RЈ = CH2SiMe3 ponding η2-iminoacyl compound [Zr{Me2Si(η5-C5Me4)(η5-
(4); R = SiMe3, RЈ = CH2Ph (5); R = SiMe3, RЈ = CH2SiMe3
(6)] have been synthesized by the reaction of the correspond-
ing ansa-metallocene dichloride complex and 1 equiv of the
alkyl Grignard reagent. Dialkyl complexes with large alkyl
groups only formed for the zirconocene complex containing
the ansa ligand Me2Si(η5-C5Me4)(η5-C5H4) and with the
C5H3R)}{η2-RЈC=NC6H3Me2-2,6}Cl] [R = Me, RЈ = CH2Ph (9);
R = Me, RЈ = CH2SiMe3 (10); R = iPr, RЈ = CH2Ph (11); R =
iPr, RЈ = CH2SiMe3 (12); R = SiMe3, RЈ = CH2Ph (13); R =
SiMe3, RЈ = CH2SiMe3 (14); R = H, RЈ = CH2SiMe3 (16)] and
[Zr{Me2Si(η5-C5Me4)(η5-C5H4)}{η2-PhCH2C=NC6H3Me2-
2,6}(CH2Ph)] (15). The molecular structure of 1 has been de-
termined by single-crystal X-ray diffraction studies.
benzyl
substituent
giving
[Zr{Me2Si(η5-C5Me4)(η5-
C5H4)}(CH2Ph)2] (7). When the alkyl substituent is CH2SiMe3
only the monoalkyl derivative, [Zr{Me2Si(η5-C5Me4)(η5-
C5H4)}(CH2SiMe3)Cl] (8), was formed. The insertion reaction
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
quires an approach in which the electron density at the me-
tal atom and the shape of a coordination site can be pre-
dicted.[5] Recent studies have demonstrated that the incor-
poration of an ansa bridge may have a profound influence
on the chemistry of metallocene systems.[6] The electro-
chemical properties of group-4 ansa-metallocene complexes
have previously been reported[7] and indicate that a positive
shift of E° occurs versus their non-ansa analogues. For ex-
ample, the complex [Zr{Me2Si(η5-C5H4)2}Cl2] is reduced at
a lesser negative potential than [Zr(η5-C5H5)2Cl2] (by
0.1 V).[7a] Therefore it is well established that the electron
density at the metal atom is modified by the alkyl group
substituents of the cyclopentadienyl ligand. In methyl-
substituted zirconocene dihalide complexes [Zr(η5-
C5H5ϪnMen)2Cl2] (n ϭ 0Ϫ5) such trends were observed in
shifts of electrochemical reduction potentials.[8] We have ob-
served the same effect in our recently presented study on the
electrochemistry of niobium() dichloride complexes which
contain the same ansa ligands as those discussed presently
in this paper.[9]
Zirconocene complexes are of considerable interest due
to their synthetic and catalytic applications.[1] The relation-
ship between the properties of different zirconocene cata-
lysts and their molecular structures has been the subject of
in-depth studies. The main emphasis of these studies has
centred on the steric effects of various ring substituents and
bridging units on the properties of the catalysts and their
polymer products.[2] However, considerably less work has
been carried out into the electronic effects that different li-
gands exert on the relative electron densities at the zir-
conium centre,[3] even though they will influence the reac-
tivity of the catalysts.[4]
Although modifications of cyclopentadienyl ligands sim-
ultaneously change both the steric and electronic effects, a
rational design of new olefin polymerization catalysts re-
[a]
´
´
´
´
Departamento de Quımica Inorganica, Organica y Bioquımica,
´
Universidad de Castilla-La Mancha, Facultad de Quımicas,
Campus Universitario, 13071 Ciudad Real, Spain
Fax: (internat.) ϩ 34-926/295-318
Alkylzirconocene cations are currently of interest due to
their role as single-site ZieglerϪNatta olefin polymerization
catalysis.[10] Common precursors to these cationic catalysts
include dimethyl- and dibenzylzirconocenes which are
stable species.[10,11]
E-mail: Antonio.Otero@uclm.es
[b]
[c]
´
´
Departamento de Tecnologıa Quımica, Ambiental y de los
Materiales, E.S.C.E.T., Universidad Rey Juan Carlos,
´
28933 Mostoles (Madrid), Spain
ETS Ingenieros Industriales,
´
Avd. Camilo Jose Cela, 3, 13071 Ciudad Real, Spain
2626
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200300150
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632

Alkylzirconium Complexes Incorporating Asymmetrically Substituted ansa Ligands
FULL PAPER
We recently developed a general synthesis of some SiMe2- groups (cyclopentadienyl- and metal-substituted) were also
bridged asymmetric ansa-zirconocene complexes[12] and this observed.
series of highly active C1-symmetric catalysts polymerize
The corresponding dialkyl complexes were not obtained
propylene with a high level of stereospecificity.[12b] Our re- even when an excess of the alkylating reagent was used.
search in this area is now focused on the elucidation of the This fact may be due to the bulky nature of the metal-
mechanism of olefin polymerization as well as on the use bonded alkyl substituent or the presence of the β-alkyl sub-
of new types of metallocene complexes in stereoselective ca- stituent of the monosubstituted cyclopentadienyl moiety or
talysis.[13]
In this paper we report our studies on the synthesis,
indeed attributed to a combination of the two factors.
In the previously reported dimethyl complexes
characterization, and reactivity of new benzyl- and [(tri- [Zr{Me2Si(η5-C5Me4)(η5-C5H3R)}Me2] (R ϭ H, Me, iPr,
methylsilyl)methyl]zirconium derivatives containing asym- SiMe3), dialkyl substitution was shown to readily occur.[12b]
metric ansa ligands. Special attention is paid to the steric The obvious reason for this reactivity can be attributed to
factors that govern the alkylation reactions due to the im- the small size of the methyl group which allows the easy
plication that this may have on the stereoselective mecha- entry to the metal centre of two alkyl ligands which in ad-
nism in α-olefin polymerization.
dition also seem to be unaffected by the absence or presence
of the β-cyclopentadienyl substituent.
For
the
ansa-zirconocene
dichloride
complex
[Zr{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2] (i.e. no β-substituent
present) the alkylation reaction with the benzyl group gave
the disubstituted derivative, [Zr{Me2Si(η5-C5Me4)(η5-
C5H4)}(CH2Ph)2] (7) (Scheme 2). This indicates that in the
case of benzylation that the conditioning factor leading to
mono- or disubstitution corresponds to the nature of β-sub-
stitution in the ansa-cyclopentadienyl ligand.
Results and Discussion
The synthesis of the monoalkyl complexes, [Zr{Me2Si(η5-
C5Me4)(η5-C5H3R)}(RЈ)Cl] [R ϭ Me, RЈ ϭ CH2Ph (1);
R ϭ Me, RЈ ϭ CH2SiMe3 (2); R ϭ iPr, RЈ ϭ CH2Ph (3);
R ϭ iPr, RЈ ϭ CH2SiMe3 (4); R ϭ SiMe3, RЈ ϭ CH2Ph
(5); R ϭ SiMe3, RЈ ϭ CH2SiMe3 (6)], was carried out by
the reaction of 1 equiv. of the alkyl Grignard reagent with
the corresponding ansa-metallocene dichloride derivative
(Scheme 1).
Scheme 2
When the same reaction was carried out but using
Mg(CH2SiMe3)Cl as the alkylating agent only the mono-
alkyl derivative, [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}(CH2Si-
Me3)Cl] (8), was isolated (Scheme 3). Therefore we can infer
that for the bulkier CH2SiMe3 ligand, its voluminous nature
(and not the substituent present in the cyclopentadienyl
moiety) is the primary factor in the steric demands imposed
on the final product.
Scheme 1
The planar chirality exhibited by the ansa-zirconocene di-
chloride complexes, [Zr{Me2Si(η5-C5Me4)(η5-C5H3R)}Cl2]
(R ϭ Me, iPr, SiMe3),[12] means that the two chloride posi-
tions are not equivalent. Thus, in the monoalkyl substi-
tution reaction there exists the possibility of the formation
1
of two stereoisomers. In all cases H NMR spectroscopy
revealed that only one of these isomers was present. In ad-
dition signals were observed for the nonequivalent methyl
groups of the permethylated cyclopentadienyl moiety (4 sin-
Scheme 3
The syntheses of bis(CH2SiMe3) derivatives of non-ansa-
glets), the methyl groups of the SiMe2 bridge (2 singlets), zirconocene complexes, [Zr(η5-C5H4R)2(CH2SiMe3)2] (R ϭ
and the three protons of the monosubstituted cyclopen- H, Me, Et, iPr, tBu), have been reported.[14] However, the
tadienyl fragment (3 multiplets) (see Exp. Sect.). The meth- attempted preparation of the hafnium analogue with R ϭ
ylene protons of the alkyl group (CH2SiMe3 or CH2Ph) are tBu proved unsuccessful and gave only the monosubstituted
diastereotopic due to the chiral nature of the metal centre derivative [Hf(η5-C5H4tBu)2(CH2SiMe3)Cl].[14a] In ad-
and thus two doublets were observed in the 1H NMR spec- dition, when the size of the alkyl ligand was increased to
tra of 1Ϫ6. The signals corresponding to the differing alkyl CH(SiMe3)2, only the synthesis of the monoalkyl deriva-
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2627

A. Otero et al.
FULL PAPER
tives, [Zr(η5-C5H4R)2{CH(SiMe3)2}Cl] (R ϭ H, Me, Et,
iPr, tBu, SiMe3), was possible.[15] It seems obvious therefore
that steric constraints and not electronic effects are respon-
sible for the substitution reaction behaviour. In the ansa
complexes where there is no free rotation of the C5 rings,
their substituents are located in fixed positions and thus
˚
Table 1. Selected bond lengths [A] and angles [°] for 1; Cent(1)
and Cent(2) are the centroids of C(10)ϪC(14) and C(20)ϪC(24),
respectively; * refers to the average bond length between Zr(1) and
the carbon atoms of the C5 ring of the corresponding cyclopen-
tadienyl moiety
Zr(1)ϪCent(1)
2.221
those located in the β-positions will always influence steri- Zr(1)ϪCent(2)
2.226
2.525
2.533
2.4261(9)
2.327(3)
1.475(4)
av Zr(1)ϪC[Cent(1)]*
cally the reactions at the metal centre. In addition, one can
imagine that the flexibility of the cyclopentadienyl rings in
non-ansa derivatives makes them less sensitive to steric fac-
tors than their more rigid ansa-metallocene analogues and
this may explain why we only obtained the monoalkyl com-
pound [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}(CH2SiMe3)Cl] (8)
and that dialkyl derivatives [Zr(η5-C5H4R)2(CH2SiMe3)2]
(R ϭ H, Me, Et, iPr, tBu)[15] could be readily formed for
the non-ansa analogues.
av Zr(1)ϪC[Cent(2)]*
Zr(1)ϪCl(1)
Zr(1)ϪC(1)
C(1)ϪC(2)
Cent(1)ϪZr(1)ϪCent(2)
Si(1)ϪC(10)ϪCent(1)
Si(1)ϪC(20)ϪCent(2)
C(10)ϪSi(1)ϪC(20)
Cl(1)ϪZr(1)ϪCent(1)
Cl(1)ϪZr(1)ϪCent(2)
C(1)ϪZr(1)ϪCent(1)
C(1)ϪZr(1)ϪCent(2)
Cl(1)ϪZr(1)ϪC(1)
126.50
162.02
162.23
94.72(11)
109.43
109.96
106.94
103.47
95.90(9)
118.3(2)
1
For 7 and 8 H NMR spectroscopy confirms the di- and
monoalkyl substitution, respectively. The difference in sym-
1
metry of 7 (bis, Cs) and 8 (mono, C1) is reflected in the H
NMR spectra. For the Cs symmetry in 7 only two signals
were observed for the four protons of the unsubstituted
cyclopentadienyl ring, two signals for the four methyl
groups of the tetramethylcyclopentadienyl ring, one singlet
for the two methyl groups of the ansa-SiMe2 bridge, and
one singlet for the methylene protons corresponding to the
two benzyl ligands. For the C1 symmetry in 8 four signals
were observed for the four protons of the unsubstituted
cyclopentadienyl ring, four signals for the four methyl
groups of the tetramethylcyclopentadienyl ring, two singlets
for the two methyl groups of the ansa-SiMe2 bridge and
two multiplets for the diastereoscopic methylene protons
corresponding to the CH2SiMe3 ligand.
Zr(1)ϪC(1)ϪC(2)
plexes. The ansa ligand chelates the zirconium atom and
both C5 rings are bound to the metal atom in an η5-mode.
The environment of the zirconium atom is completed by a
chlorine atom and the α-carbon atom of the benzyl group.
The structure also reveals that the methyl substituent of the
monosubstituted C5 ring is orientated away from the benzyl
group in a manner similar to that recently reported for im-
ido ansa-niobocene complexes.[12a] The structural param-
eters of 1 are directly similar to those of its parent zir-
conocene dichloride complex [Zr{Me2Si(η5-C5Me4)(η5-
C5H3Me)}Cl2].[12a]
The reaction of the isocyanide reagent CNC6H3Me2-2,6
with 1Ϫ8 has been studied (Scheme 4). The products of the
insertion reactions [Zr{Me2Si(η5-C5Me4)(η5-C5H3R)}{η2-
RЈCϭNC6H3Me2-2,6}Cl] [R ϭ Me, RЈ ϭ CH2Ph (9); R ϭ
Me, RЈ ϭ CH2SiMe3 (10); R ϭ iPr, RЈ ϭ CH2Ph (11); R ϭ
iPr, RЈ ϭ CH2SiMe3 (12); R ϭ SiMe3, RЈ ϭ CH2Ph (13);
R ϭ SiMe3, RЈ ϭ CH2SiMe3 (14); R ϭ H, RЈ ϭ CH2SiMe3
(16)] and [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}{η2-PhCH2Cϭ
NC6H3Me2-2,6}(CH2Ph)] (15) were characterized by 1H
and 13C NMR spectroscopy.
The molecular structure of 1 was established by single-
crystal X-ray diffraction studies. The molecular structure
and atomic numbering scheme are shown in Figure 1. Selec-
ted bond lengths and angles for 1 are given in Table 1.
Figure 1. Molecular structure and atom-labeling scheme for
[Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}(CH2Ph)Cl] (1) with thermal
ellipsoids at 30% probability
The structure of 1 shows the typical bent metallocene
conformation observed in zirconocene dichloride com- Scheme 4
2628  2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632

Alkylzirconium Complexes Incorporating Asymmetrically Substituted ansa Ligands
FULL PAPER
The migratory insertion of alkyl groups towards isocyan- Experimental Section
ide ligands allows the introduction of iminoacyl groups
General Remarks: All reactions were performed using standard
Schlenk tube techniques under dry nitrogen. Solvents were distilled
from appropriate drying agents and degassed before use. Com-
pounds [Zr{Me2Si(η5-C5Me4)(η5-C5H3R)}Cl2] (R ϭ H, Me, iPr,
SiMe3) were prepared as described earlier.[12a] Mg(CH2Ph)Cl,
Mg(CH2SiMe3)Cl, and CNC6H3Me2-2,6 were purchased from Ald-
which are present in different coordination modes. In fact,
for high-valent oxophilic early transition metals, the im-
inoacyl group typically adopts an η2-coordination mode
through both the nitrogen and carbon atoms.[16] Similarly,
an η2-coordination mode is proposed for the iminoacyl li-
gand in 9Ϫ16 on the basis of IR and 13C NMR spec-
troscopy which show the characteristic stretching vibration
ν(CϭN) at ca. 1600 cmϪ1 and iminoacyl quaternary carbon
rich and used directly. IR spectra were recorded with
a
PerkinϪElmer PE 883 IR spectrophotometer. H and 13C spectra
were recorded with a Varian FT-300 spectrometer and referenced
to the residual deuterated solvent. Microanalyses were carried out
with a PerkinϪElmer 2400 microanalyzer.
1
1
atom signal at δ ഠ 250 ppm, respectively. The H NMR
spectra of 9Ϫ16 in addition to the expected signals for the
ansa-metallocene protons, gave signals corresponding to the
iminoacyl alkyl group (see Exp. Sect.).
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}(CH2Ph)Cl] (1):
A 2  solution of Mg(CH2Ph)Cl in THF (0.60 mL, 1.19 mmol) was
added at Ϫ78 °C to a stirred solution of [Zr{Me2Si(η5-C5Me4)(η5-
C5H3Me)}Cl2] (0.50 g, 1.19 mmol) in THF (50 mL). The solution
was allowed to warm to room temperature and stirred for 6 h. The
solvent was removed in vacuo and the remaining solid extracted in
hexane. A orange crystalline solid was obtained by concentrating
and cooling (Ϫ30 °C) the solution (0.45 g, 79%). 1H NMR
(300 MHz, C6D6, 25 °C): δ ϭ 0.19 and 0.28 (2 s, each 3 H, SiMe2),
1.52, 1.58, 1.66, and 1.95 (4 s, each 3 H, C5Me4), 2.07 (s, 3 H,
The iminoacyl group can position itself in two distinct
conformations, the ‘‘proximal’’ or ‘‘N-outside’’ and the
‘‘distal’’ or ‘‘N-inside’’ configurations (see Figure 2). 1H
and 13C NMR spectroscopic data indicate the presence of
only one of the two possible conformations. Although it
has been demonstrated that the N-outside isomer is the re-
sulting initial kinetic iminoacyl product of the insertion re-
action, most group-4 metal derivatives show the structure
of the N-inside isomer which results from thermodynamic
control.[17] For 9Ϫ16 the isolated product was observed not
to evolve over time and therefore we tentatively propose
that they are the products resulting from thermodynamic
control and adopt the N-inside conformation.
2
C5H3Me), 1.70 and 1.86 (2 d, JH,H ϭ 18.9 Hz, each 1 H, CH2Ph),
4.91, 5.06, and 5.47 (3 m, each 1 H, C5H3), 6.75Ϫ7.25 (m, 5 H,
CH2Ph) ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.5,
Ϫ0.6 (SiMe2), 11.2, 12.3, 14.6, 14.7 (C5Me4), 15.3 (C5H3Me), 38.2
(CH2Ph), 102.1, 112.1, 113.9, 121.4, 134.9 (C5H3), 93.7, 121.9,
126.2, 131.1, 131.5 (C5Me4), 124.0, 126.9, 127.0, 128.5, 128.7, 153.6
(CH2Ph) ppm. C24H31ClSiZr (474.3): calcd. C 60.78, H 6.59; found
C 60.59, H 6.54.
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}(CH2SiMe3)Cl]
(2): A 1  solution of Mg(CH2SiMe3)Cl in Et2O (0.96 mL,
0.96 mmol) was added at Ϫ78 °C to a stirred solution of
[Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}Cl2] (0.40 g, 0.96 mmol) in
THF (50 mL). The solution was allowed to warm to room tempera-
ture and stirred for 16 h. The resulting yellow solution was stirred
under reflux for 2 h. The solvent was removed in vacuo and hexane
added to the resulting solid. The mixture was filtered and the fil-
trate concentrated and cooled to Ϫ30 °C. The yellow solid that
precipitated from the solution was isolated by filtration (0.37 g,
81%). 1H NMR (300 MHz, C6D6, 25 °C): δ ϭ 0.23 (s, 9 H,
CH2SiMe3), 0.29 and 0.34 (2 s, each 3 H, SiMe2), 1.48, 1.65, 1.92,
and 2.00 (4 s, each 3 H, C5Me4), 2.30 (s, 3 H, C5H3Me), 1.77 and
Figure 2. Two possible conformations for the (iminoacyl)metal
complexes 9Ϫ16
A second insertion was not observed even when stoichio-
metries other than 1:1 were tested.
2
1.91 (2 d, JH,H ϭ 21.6 Hz, each 1 H, CH2SiMe3), 5.02, 5.09, and
6.60 (3 m, each 1 H, C5H3) ppm. 13C{1H} NMR (75 MHz, C6D6,
25 °C): δ ϭ Ϫ0.4, Ϫ0.7 (SiMe2), 2.9 (CH2SiMe3), 12.2, 12.3, 14.5,
14.6 (C5Me4), 15.5 (C5H3Me), 42.1 (CH2SiMe3), 103.4, 111.4,
112.5, 122.8, 134.6 (C5H3), 93.7, 122.2, 122.5, 130.1, 131.6 (C5Me4)
ppm. C21H35ClSi2Zr (470.4): calcd. C 53.62, H 7.50; found C 53.36,
H 7.43.
Conclusions
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3iPr)}(CH2Ph)Cl] (3):
The synthesis of 3 was carried out in an identical manner to that
of 1: 2  solution of Mg(CH2Ph)Cl in THF (0.38 mL, 0.76 mmol)
and [Zr{Me2Si(η5-C5Me4)(η5-C5H3iPr)}Cl2] (0.34 g, 0.76 mmol).
Yield 0.26 g, 69%. 1H NMR (300 MHz, C6D6, 25 °C): δ ϭ 0.32
and 0.34 (2 s, each 3 H, SiMe2), 1.03 and 1.07 (2 d, 3JH,H ϭ 7.1 Hz,
each 3 H, HCMe2), 1.61, 1.67, 1.74, and 2.00 (4 s, each 3 H,
In this paper we report our studies of the steric factors
involved in the synthesis of alkylzirconocene complexes
containing asymmetric ansa ligands. The preparation and
characterization of mono- and dialkyl derivatives is de-
scribed. The structural characterization of the monoalkyl
complexes show the disposition of the β-alkyl substituent
of the monosubstituted cyclopentadienyl moiety is such to
orientate it away from the metal-bonded alkyl ligand. Inser-
tion reactions with a bulky isocyanide, to give η2-iminoacyl
complexes, are also described.
2
C5Me4), 1.72 and 1.84 (2 d, JH,H ϭ 17.2 Hz, each 1 H, CH2Ph)
3.13 (sept, 1 H, HCMe2), 5.05, 5.32, and 5.65 (3 m, each 1 H,
C5H3), 6.88Ϫ7.33 (m, 5 H, CH2Ph) ppm. 13C{1H} NMR (75 MHz,
C6D6, 25 °C): δ ϭ Ϫ0.8, Ϫ0.3 (SiMe2), 11.2, 12.4, 14.4, 14.8
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2629

A. Otero et al.
FULL PAPER
(C5Me4), 22.1, 24.1 (HCMe2), 28.0 (HCMe2), 38.1 (CH2Ph), 102.5,
110.9, 112.2, 121.4, 122.7 (C5H3), 94.1, 125.7, 126.1, 131.1, 131.8
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}(CH2SiMe3)Cl] (8):
The synthesis of 8 was carried out in an identical manner to that
(C5Me4), 122.6, 126.9, 127.0, 128.7, 128.8, 153.2 (CH2Ph) ppm. of 2: 1  solution of Mg(CH2SiMe3)Cl in Et2O (0.74 mL,
C26H35ClSiZr (502.3): calcd. C 62.17, H 7.02; found C 61.89, H
6.99.
0.74 mmol) and [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2] (0.30 g,
0.74 mmol). Yield 0.25 g, 75%. 1H NMR (300 MHz, C6D6, 25 °C):
δ ϭ 0.25 (s, 9 H, CH2SiMe3), 0.23 and 0.28 (2 s, each 3 H, SiMe2),
1.43, 1.70, 1.86, and 1.95 (4 s, each 3 H, C5Me4), 1.79 and 1.95 (2
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3iPr)}(CH2SiMe3)Cl]
(4): The synthesis of 4 was carried out in an identical manner to
that of 2: 1  solution of Mg(CH2SiMe3)Cl in Et2O (0.85 mL,
0.85 mmol) and [Zr{Me2Si(η5-C5Me4)(η5-C5H3iPr)}Cl2] (0.38 g,
0.85 mmol). Yield 0.28 g, 65%. 1H NMR (300 MHz, C6D6, 25 °C):
δ ϭ 0.23 (s, 9 H, CH2SiMe3), 0.44 and 0.55 (2 s, each 3 H, SiMe2),
2
d, JH,H ϭ 18.3 Hz, each 1 H, CH2SiMe3), 5.01, 5.48, 6.71, and
6.95 (4 m, each 1 H, C5H4) ppm. 13C{1H} NMR (75 MHz, C6D6,
25 °C): δ ϭ Ϫ0.6, Ϫ0.5 (SiMe2), 2.8 (CH2SiMe3), 12.1, 12.2, 14.5,
14.8 (C5Me4), 42.9 (CH2SiMe3), 104.4, 110.8, 111.5, 123.0, 123.7
(C5H4), 94.9, 123.9, 125.6, 130.8, 131.4 (C5Me4) ppm.
C20H33ClSi2Zr (456.3): calcd. C 52.64, H 7.29; found C 52.29, H
7.23.
3
1.17 and 1.36 (2 d, JH,H ϭ 6.8 Hz, each 3 H, HCMe2), 1.72, 1.76,
2
1.86, and 1.90 (4 s, each 3 H, C5Me4), 1.80 and 1.94 (2 d, JH,H
ϭ
21.6 Hz, each 1 H, CH2SiMe3), 3.85 (sept, 1 H, HCMe2), 5.30,
5.50, and 6.31 (3 m, each 1 H, C5H3) ppm. 13C{1H} NMR
(75 MHz, C6D6, 25 °C): δ ϭ Ϫ1.0, Ϫ0.4 (SiMe2), 3.2 (SiMe3), 12.4,
12.5, 15.1, 15.4 (C5Me4), 22.0, 24.4 (HCMe2), 28.5 (HCMe2), 44.0
(CH2SiMe3), 100.2, 112.4, 113.9, 120.6, 122.6 (C5H3), 98.4, 125.6,
126.8, 132.3, 132.4 (C5Me4) ppm. C23H39ClSi2Zr (498.4): calcd. C
55.43, H 7.89; found C 55.09, H 7.78.
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}{η2-PhCH2C؍
N(C6H3Me2-2,6)}Cl] (9): 2,6-Dimethylphenyl isocyanide (0.14 g,
1.05 mmol) and 1 (0.50 g, 1.05 mmol) were dissolved in THF
(100 mL). The resulting orange solution was stirred at room tem-
perature for 18 h. The solvent was removed in vacuo and the re-
maining solid extracted with toluene (30 mL). An orange solid was
obtained by concentrating (5 mL) and cooling (Ϫ30 °C) the solu-
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3SiMe3)}(CH2Ph)Cl]
(5): The synthesis of 5 was carried out in an identical manner to
that of 1: 2  solution of Mg(CH2Ph)Cl in THF (0.32 mL,
1
tion (0.54 g, 84%). IR (Nujol): ν˜ ϭ 1590 (νCϭN) cmϪ1. H NMR
(300 MHz, C6D6, 25 °C): δ ϭ 0.43 and 0.45 (2 s, each 3 H, SiMe2),
1.46, 1.71, 1.88, and 1.97 (4 s, each 3 H, C5Me4), 2.03 (s, 3 H,
C5H3Me), 2.17 and 2.20 (2 s, each 3 H, C6H3Me2), 3.22 and 3.59
0.64 mmol)
and
[Zr{Me2Si(η5-C5Me4)(η5-C5H3SiMe3)}Cl2]
(0.30 g, 0.64 mmol). Yield 0.26 g, 76%. 1H NMR (300 MHz, C6D6,
25 °C): δ ϭ 0.27 (s, 9 H, SiMe3), 0.32 and 0.39 (2 s, each 3 H,
SiMe2), 1.62, 1.73, 1.74, and 1.94 (4 s, each 3 H, C5Me4), 1.96 and
2.00 (2 d, 2JH,H ϭ 18.5 Hz, each 1 H, CH2Ph), 5.36, 5.71, and 5.90
(3 m, each 1 H, C5H3), 6.91Ϫ7.30 (m, 5 H, CH2Ph) ppm. 13C{1H}
NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.9, Ϫ0.6 (SiMe2), Ϫ0.5
(SiMe3) 11.1, 12.6, 14.3, 14.9 (C5Me4), 38.15 (CH2Ph), 108.0, 116.3,
117.2, 121.5, 123.4 (C5H3), 95.7, 129.3, 130.6, 133.1, 136.4 (C5Me4),
126.1, 127.4, 127.5, 128.8, 129.5, 152.8 (CH2Ph) ppm.
C26H37ClSi2Zr (532.4): calcd. C 58.65, H 7.00; found C 58.46, H
6.96.
2
(2 d, JH,H ϭ 18.0 Hz, each 1 H, CH2Ph), 5.50, 5.62, and 5.73 (3
m, each 1 H, C5H3), 6.55 (2 H), 6.69 (1 H) (2 m, C6H3Me2),
6.83Ϫ7.15 (m, 5 H, CH2Ph) ppm. 13C{1H} NMR (75 MHz, C6D6,
25 °C): δ ϭ Ϫ0.7, Ϫ0.2 (SiMe2), 12.4, 12.5, 15.1, 15.3, 15.5 (C5Me4,
C5H3Me), 20.0, 20.1 (C6H3Me2), 38.2 (CH2Ph), 104.1, 104.4, 114.4,
119.4, 137.3 (C5H3), 108.0, 115.1, 120.9, 131.1, 134.9 (C5Me4),
125.6, 127.6, 127.7, 128.8, 128.9, 144.2 (CH2Ph), 126.2, 126.3,
126.9, 127.0, 128.4, 128.7, 171.0 (C6H3Me2), 246.7 (CCH2Ph) ppm.
C33H40ClNSiZr (605.4): calcd. C 65.47, H 6.66, N 2.31; found C
65.21, H 6.58, N 2.29.
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3Me)}{η2-Me3Si-
CH2C؍N(C6H3Me2-2,6)}Cl] (10): The synthesis of 10 was carried
out in an identical manner to that of 9: 2 (0.50 g, 1.06 mmol) and
2,6-dimethylphenyl isocyanide (0.14 g, 1.06 mmol). Yield 0.49 g,
Preparation
of
[Zr{Me2Si(η5-C5Me4)(η5-C5H3SiMe3)}
(CH2SiMe3)Cl] (6): The synthesis of 6 was carried out in an ident-
ical manner to that of 2: 1  solution of Mg(CH2SiMe3)Cl in Et2O
(0.63 mL,
0.63 mmol)
and
[Zr{Me2Si(η5-C5Me4)(η5-
77%. IR (Nujol): ν˜ ϭ 1620 (νCϭN) cmϪ1 1H NMR (300 MHz,
.
1
C5H3SiMe3)}Cl2] (0.30 g, 0.63 mmol). Yield 0.28 g, 85%. H NMR
C6D6, 25 °C): δ ϭ Ϫ0.05 (s, 9 H, CH2SiMe3), 0.50 and 0.54 (2 s,
each 3 H, SiMe2), 1.50, 1.89, 1.95, and 1.99 (4 s, each 3 H, C5Me4),
2.28 (s, 3 H, C5H3Me), 2.16 and 2.17 (2 s, each 3 H, C6H3Me2),
(300 MHz, C6D6, 25 °C): δ ϭ 0.21 (s, 9 H, CH2SiMe3), Ϫ0.05 and
0.24 (2 s, each 3 H, SiMe2), 0.41 (s, 9 H, C5H3SiMe3), 1.60, 1.78,
2
1.85, and 1.92 (4 s, each 3 H, C5Me4), 1.81 and 1.98 (2 d, JH,H
ϭ
2
1.95 and 2.41 (2 d, JH,H ϭ 18.5 Hz, each 1 H, CH2SiMe3), 5.50,
19.4 Hz, each 1 H, CH2SiMe3), 5.43, 5.91, and 7.30 (3 m, each 1
H, C5H3) ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.9,
Ϫ0.6 (SiMe2), 0.0 (CH2SiMe3), 1.4 (C5H3SiMe3), 12.2, 12.4, 15.1,
15.2 (C5Me4), 48.9 (CH2SiMe3), 107.9, 115.9, 118.9, 122.5, 126.5
(C5H3), 95.8, 124.3, 124.9, 130.7, 131.3 (C5Me4) ppm.
C23H41ClSi3Zr (528.5): calcd. C 52.27, H 7.82; found C 52.00, H
7.74.
5.62, and 5.73 (3 m, each 1 H, C5H3), 6.86 (s, 3 H, C6H3Me2) ppm.
13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.4, 0.3 (SiMe2), 0.8
(CH2SiMe3), 12.5, 12.7, 14.8, 15.6, 15.8 (C5Me4, C5H3Me), 19.8,
20.7 (C6H3Me2), 32.2 (CH2SiMe3), 100.2, 103.8, 113.5, 118.8, 130.7
(C5H3), 108.5, 114.7, 118.3, 130.2, 130.3 (C5Me4) 125.6, 127.3,
127.4, 128.3, 128.4, 144.2 (C6H3Me2), 245.4 (CCH2SiMe3) ppm.
C30H44ClNSi2Zr (601.5): calcd. C 59.90, H 7.37, N 2.33; found C
59.63, H 7.32, N 2.28.
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}(CH2Ph)2] (7): The
synthesis of 7 was carried out in an identical manner to that of 1:
2  solution of Mg(CH2Ph)Cl in THF (0.74 mL, 1.48 mmol) and Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3iPr)}{η2-PhCH2C؍
[Zr{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2] (0.30 g, 0.74 mmol). Yield
N(C6H3Me2-2,6)}Cl] (11): The synthesis of 11 was carried out in
an identical manner to that of 9: 3 (0.40 g, 0.80 mmol) and 2,6-
1
0.30 g, 79%. H NMR (300 MHz, C6D6, 25 °C): δ ϭ 0.26 (s, 6 H,
SiMe2), 1.58 and 1.80 (2 s, each 6 H, C5Me4), 2.69 (s, 4 H, 2 ϫ dimethylphenyl isocyanide (0.10 g, 0.80 mmol). Yield 0.39 g, 78%.
CH2Ph), 5.06 and 6.14 (2 m, each 2 H, C5H4), 6.82Ϫ7.25 (m, 10 IR (Nujol): ν˜ ϭ 1605 (νCϭN) cmϪ1. 1H NMR (300 MHz, C6D6, 25
H, 2 ϫ CH2Ph) ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ
°C): δ ϭ 0.39 and 0.44 (2 s, each 3 H, SiMe2), 0.99 and 1.25 (2 d,
Ϫ0.6 (SiMe2), 11.6, 14.6 (C5Me4), 38.1 (CH2Ph), 100.5, 113.0, 3JH,H ϭ 7.1 Hz, each 3 H, HCMe2), 1.42, 1.69, 1.93, and 1.97 (4 s,
121.1, (C5H4), 98.2, 124.4, 135.7 (C5Me4), 125.9, 126.8, 129.2, 153.7 each 3 H, C5Me4), 2.12 and 2.14 (2 s, each 3 H, C6H3Me2), 3.12
2
(CH2Ph) ppm. C30H36SiZr (515.9): calcd. C 69.84, H 7.03; found and 3.76 (2 d, JH,H ϭ 17.1 Hz, each 1 H, CH2Ph), 3.35 (sept, 1
C 69.66, H 6.91.
H, HCMe2), 5.67 (2 H), 5.92 (1 H) (2 m, C5H3), 6.52 (2 H), 6.69
2630
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632

Alkylzirconium Complexes Incorporating Asymmetrically Substituted ansa Ligands
FULL PAPER
(1 H) (2 m, C6H3Me2), 6.88Ϫ7.26 (m, 5 H, CH2Ph) ppm. 13C{1H} Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}{η2-PhCH2C؍
NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.6, Ϫ0.2 (SiMe2), 12.4, 12.8, N(C6H3Me2-2,6)}(CH2Ph)] (15): The synthesis of 15 was carried
15.0, 15.2 (C5Me4), 22.5, 24.6 (HCMe2), 29.1 (HCMe2), 39.3 out in an identical manner to that of 9: 7 (0.30 g, 0.58 mmol) and
(CH2Ph), 19.5, 20.4 (C6H3Me2), 100.7, 112.6, 114.1, 122.6, 123.4
(C5H3), 105.3, 126.7, 127.2, 133.4, 134.4 (C5Me4), 125.3, 127.4, 80%. IR (Nujol): ν˜ ϭ 1590 (νCϭN) cmϪ1
127.6, 128.8, 128.9, 152.2 (CH2Ph), 126.1, 126.9, 127.0, 128.9, C6D6, 25 °C): δ ϭ 0.47 and 0.49 (2 s, each 3 H, SiMe2), 1.39, 1.47,
2,6-dimethylphenyl isocyanide (0.08 g, 0.58 mmol). Yield 0.30 g,
.
1H NMR (300 MHz,
129.0, 165.3 (C6H3Me2), 246.3 (CCH2Ph) ppm. C35H44ClNSiZr
(633.5): calcd. C 66.36, H 7.00, N 2.21; found C 66.01, H 6.91,
N 2.18.
1.83, and 1.77 (4 s, each 3 H, C5Me4), 2.06 and 2.07 (2 s, each 3
2
H, C6H3Me2), 1.62 and 2.12 (2 d, JH,H ϭ 16.5 Hz, each 1 H,
2
CH2Ph), 3.05 and 3.40 (2 d, JH,H ϭ 18.4 Hz, each 1 H,
NCCH2Ph), 5.13, 5.46, 5.63, and 5.92 (4 m, each 1 H, C5H4), 6.78
(2 H), 6.87 (1 H) (m, C6H3Me2), 6.90Ϫ7.26 (m, 10 H, 2 ϫ CH2Ph)
ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.9, 0.3
(SiMe2), 12.3, 12.4, 15.1, 15.4 (C5Me4), 19.5, 19.6 (C6H3Me2), 38.2,
44.8 (CH2Ph), 100.9, 112.4, 114.9, 118.4, 119.4 (C5H4), 106.0,
125.4, 125.6, 131.2, 134.8 (C5Me4), 125.0, 125.7, 127.0, 127.1,
128.6, 128.7, 141.9, 146.2 (CH2Ph), 126.4, 126.7, 127.7, 128.9,
129.0, 156.6 (C6H3Me2), 247.8 (CCH2Ph) ppm. C39H45NSiZr
(647.1): calcd. C 72.39, H 7.01, N 2.16; found C 72.11, H 6.92,
N 2.15.
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3iPr)}{η2-Me3Si-
CH2C؍N(C6H3Me2-2,6)}Cl] (12): The synthesis of 12 was carried
out in an identical manner to that of 9: 4 (0.45 g, 0.90 mmol) and
2,6-dimethylphenyl isocyanide (0.12 g, 0.90 mmol). Yield 0.43 g,
75% IR (Nujol): ν˜ ϭ 1570 (νCϭN) cmϪ1 1H NMR (300 MHz,
.
C6D6, 25 °C): δ ϭ 0.35 and 0.39 (2s, each 3 H, SiMe2), 0.25 (s, 9
3
H, CH2SiMe3), 1.05 and 1.33 (2 d, JH,H ϭ 7.1 Hz, each 1 H,
HCMe2), 1.48, 1.72, 1.95, and 2.00 (4 s, each 3 H, C5Me4), 2.15
2
and 2.16 (2 s, each 3 H, C6H3Me2), 3.01 and 3.54 (2 d, JH,H
ϭ
18.0 Hz, each 1 H, CH2SiMe3), 3.42 (sept, 1 H, HCMe2), 5.60,
5.63, and 5.92 (3 m, each 1 H, C5H3), 6.60 (2 H), 6.84 (1 H) (2 m,
C6H3Me2) ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ1.0,
Ϫ0.7 (SiMe2), 2.6 (SiMe3), 12.9, 13.0, 16.5, 16.6 (C5Me4), 22.7, 25.3
(HCMe2), 30.0 (HCMe2), 35.1 (CH2SiMe3), 19.3, 20.3 (C6H3Me2),
98.7, 112.7, 114.9, 124.2, 125.6 (C5H3), 104.9, 125.8, 126.4, 133.8,
133.9 (C5Me4), 126.9, 127.8, 128.1, 131.4, 131.6, 160.7 (C6H3Me2),
248.1 (CCH2SiMe3) ppm. C32H48ClNSi2Zr (629.6): calcd. C 61.05,
H 7.68, N 2.22; found C 60.72, H 7.62, N 2.23.
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H4)}{η2-Me3SiCH2C؍
N(C6H3Me2-2,6)}ZrCl] (16): The synthesis of 16 was carried out in
an identical manner to that of 9: 8 (0.25 g, 0.55 mmol) and 2,6-
dimethylphenyl isocyanide (0.07 g, 0.55 mmol). Yield 0.25 g, 77%.
IR (Nujol): ν˜ ϭ 1600 (νCϭN) cmϪ1. 1H NMR (300 MHz, C6D6, 25
°C): δ ϭ Ϫ0.09 (s, 9 H, CH2SiMe3), 0.51 and 0.54 (2 s, each 3 H,
SiMe2), 1.58, 1.81, 1.85, and 2.14 (4 s, each 3 H, C5Me4), 2.21 and
2.26 (2 s, each 3 H, C6H3Me2), 3.79 and 3.96 (2 d, 2JH,H ϭ 15.5 Hz,
each 1 H, CH2SiMe3), 5.65, 5.97, 6.23, and 6.47 (3 m, each 1 H,
C5H3), 6.86 (m, 3 H, C6H3Me2) ppm. 13C{1H} NMR (75 MHz,
C6D6, 25 °C): δ ϭ Ϫ0.6, Ϫ0.2 (SiMe2), 15.5 (CH2SiMe3), 12.4,
12.5, 15.1, 15.3 (C5Me4), 20.0, 20.1 (C6H3Me2), 38.2 (CH2SiMe3),
101.9, 104.4, 114.4, 119.3, 125.6 (C5H3), 104.0, 131.0, 134.8, 137.2,
144.1 (C5Me4), 126.2, 126.9, 127.0, 128.8, 128.9, 171.2 (C6H3Me2),
246.7 (CCH2SiMe3) ppm. C29H42ClNSi2Zr (587.50): calcd. C
59.29, H 7.21, N 2.38; found C 59.00, H 7.15, N 2.35.
Preparation
of
[Zr{Me2Si(η5-C5Me4)(η5-C5H3SiMe3)}{η2-
PhCH2C؍N(C6H3Me2-2,6)}Cl] (13): The synthesis of 13 was car-
ried out in an identical manner to that of 9: 5 (0.45 g, 0.85 mmol)
and 2,6-dimethylphenyl isocyanide (0.11 g, 0.85 mmol). Yield
0.45 g, 81%. IR (Nujol): ν˜ ϭ 1590 (νCϭN) cmϪ1 1H NMR
.
(300 MHz, C6D6, 25 °C): δ ϭ 0.31 (s, 9 H, SiMe3), 0.37 and 0.41
(2 s, each 3 H, SiMe2), 1.39, 1.59, 1.88, and 1.96 (4 s, each 3 H,
C5Me4), 2.11 and 2.13 (2 s, each 3 H, C6H3Me2), 3.03 and 3.85 (2
2
d, JH,H ϭ 18.0 Hz, each 1 H, CH2Ph), 5.81, 6.10, and 6.45 (3 m,
each 1 H, C5H3), 6.56 (2 H), 6.70 (1 H) (m, C6H3Me2), 6.88Ϫ7.26
(m, 5 H, CH2Ph) ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C):
δ ϭ Ϫ0.6, Ϫ0.3 (SiMe2), 0.7 (SiMe3), 11.9, 12.4, 15.0, 15.2
(C5Me4), 19.9, 20.5 (C6H3Me2), 38.1 (CH2Ph), 104.2, 108.0, 110.9,
Table 2. Crystal data and structure refinement for 1
Empirical formula
C24H31ClSiZr
474.25
118.3, 125.8 (C5H3), 107.2, 118.7, 119.6, 134.8, 135.7 (C5Me4), Formula mass
Temperature [K]
Wavelength [A]
250(2)
0.71073
triclinic, P1
8.853(8)
11.134(3)
11.998(2)
102.55(2)
100.09(3)
90.23(4)
1135(1)
1, 1.387
6.61
125.6, 127.0, 127.1, 128.6, 128.7, 144.1 (CH2Ph), 126.1, 126.9,
127.7, 129.2, 129.9, 171.0 (C6H3Me2), 247.8 (CCH2Ph) ppm.
C35H46ClNSi2Zr (663.6): calcd. C 63.35, H 6.99, N 2.11; found C
63.17, H 6.94, N 2.10.
˚
¯
Crystal system, space group
˚
a [A]
˚
b [A]
˚
Preparation of [Zr{Me2Si(η5-C5Me4)(η5-C5H3SiMe3)}{η2-Me3Si-
CH2C؍N(C6H3Me2-2,6)}Cl] (14): The synthesis of 14 was carried
out in an identical manner to that of 9: 6 (0.40 g, 0.76 mmol) and
2,6-dimethylphenyl isocyanide (0.10 g, 0.76 mmol). Yield 0.40 g,
c [A]
α [°]
β [°]
γ [°]
3
˚
Volume [A ]
80%. IR (Nujol): ν˜ ϭ 1605 (νCϭN) cmϪ1 1H NMR (300 MHz,
.
Z, calculated density [g/cm3]
Absorption coefficient [cmϪ1
F(000)
C6D6, 25 °C): δ ϭ 0.00 (s, 9 H, CH2SiMe3), 0.31 (s, 9 H, SiMe3),
0.53 and 0.54 (2 s, each 3 H, SiMe2), 1.39, 1.89, 1.96, and 2.04 (4
s, each 3 H, C5Me4), 2.14 and 2.16 (2 s, each 3 H, C6H3Me2), 2.13
]
492
Crystal size [mm]
Limiting indices
0.3 ϫ 0.2 ϫ 0.2
Ϫ11 Յ h Յ 11
Ϫ14 Յ k Յ 14
0 Յ l Յ 12
5313/5057 [R(int) ϭ 0.0366]
5057/0/248
2
and 2.41 (2 d, JH,H ϭ 12.5 Hz, each 1 H, CH2SiMe3), 5.85, 6.05,
and 6.24 (3 m, each 1 H, C5H3), 6.85 (2 H), 7.11 (1 H) (m,
C6H3Me2) ppm. 13C{1H} NMR (75 MHz, C6D6, 25 °C): δ ϭ Ϫ0.0,
0.1 (SiMe2), 0.6 (CH2SiMe3), 1.4 (C5H3SiMe3), 12.1, 12.5, 14.8,
15.9 (C5Me4), 19.8, 21.0 (C6H3Me2), 31.5 (CH2SiMe3), 103.9,
107.5, 109.8, 111.1, 115.3, 116.9 (C5H3), 103.9, 124.2, 125.0, 131.6,
132.4 (C5Me4), 125.5, 127.1, 127.5, 129.1, 129.8, 171.0 (C6H3Me2),
246.4 (CCH2SiMe3) ppm. C32H50ClNSi3Zr (659.7): calcd. C 58.26,
H 7.64, N 2.12; found C 57.97, H 7.57, N 2.08.
Reflections collected/unique
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
1.058
R1 ϭ 0.0338, wR2 ϭ 0.0879
R1 ϭ 0.0468, wR2 ϭ 0.0975
0.444 and Ϫ0.798
Ϫ3
˚
Largest diff. peak and hole [e·A
]
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2631

A. Otero et al.
FULL PAPER
X-ray Crystal-Structure Determination of [Zr{Me2Si(η5-C5Me4)(η5-
C5H3Me)}(CH2Ph)Cl] (1): Intensity data were collected with a
NONIUS-MACH3 diffractometer equipped with a graphite mono-
K. C. H. Lange, R. Weimann, E. Hahn, J. Organomet. Chem.
1995, 501, 219Ϫ234.
[5]
[6]
Ziegler Catalysts (Eds.: G. Fink, R. Mülhaupt, H. H. Brintz-
inger), Springer-Verlag, Berlin, 1995.
˚
chromator and Mo-Kα radiation source (λ ϭ 0.71073 A) using an
[6a] S. L. J. Conway, T. Dijkstra, L. H. Doerrer, J. C. Green, M.
ω/2θ-scan technique. The final unit cell parameters were deter-
mined from 25 well-centered reflections and refined by least-
squares methods. Data were corrected for Lorentz and polarization
effects but not for absorption. The structure was solved by direct
methods using the SHELXS computer program[18] and refined on
F2 by full-matrix least squares (SHELXL-97).[19] All non-hydrogen
atoms were refined with anisotropic thermal parameters. The hy-
drogen atoms were included in calculated positions and were re-
fined with an overall isotropic temperature factor using a riding
model. Weights were optimized in the final cycles. Crystallographic
data are given in Table 2. CCDC-205931 contains the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
[or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223/336-
033; E-mail: deposit@ccdc.cam.ac.uk].
L. H. Green, A. H. H. Stephens, J. Chem. Soc., Dalton Trans.
[6b]
1998, 2689Ϫ2695.
J. H. Shin, G. Parkin, Chem. Commun.
[6c]
1999, 887Ϫ888.
H. Lee, B. M. Bridgewater, G. Parkin, J.
[6d]
Chem. Soc., Dalton Trans. 2000, 4490Ϫ4493.
P. J. Shapiro,
Coord. Chem. Rev. 2002, 231, 67Ϫ81.
[7] [7a]
J. Langmaier, Z. Samec, V. Varga, M. Horacek, R. Chou-
kroun, K. Mach, J. Organomet. Chem. 1999, 584, 323Ϫ328. [7b]
J. Langmaier, Z. Samec, V. Varga, M. Horacek, K. Mach, J.
[7c]
Organomet. Chem. 1999, 579, 348Ϫ355.
U. Wieser, D. Ba-
bushkin, H.-H. Brintzinger, Organometallics 2002, 21,
920Ϫ923.
[8]
[9]
P. G. Gassman, D. W. Macomber, J. W. Hershberger, Or-
ganometallics 1983, 2, 1470Ϫ1472.
´
A. Antin˜olo, T. Exposito, I. del Hierro, D. Lucas, Y. Mugnier,
I. Orive, A. Otero, S. Prashar, J. Organomet. Chem. 2002,
655, 63Ϫ69.
R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325Ϫ387.
[10]
[11] [11a]
M. Bochmann, J. Chem. Soc., Dalton Trans. 1996,
255Ϫ270. [11b] X. Yang, C. L. Stern, T. J. Marks, J. Am. Chem.
[11c]
Soc. 1994, 116, 10015Ϫ10031.
D. Veghini, M. W. Day, J.
Acknowledgments
E. Bercaw, Inorg. Chim. Acta 1998, 280, 226Ϫ232.
[12] [12a]
´
We gratefully acknowledge financial support from the Direccion
´
A. Antin˜olo, I. Lopez-Solera, I. Orive, A. Otero, S. Pra-
´
´
General de Ensen˜anza Superior e Investigacion Cientıfica, Spain
(Grants no. BQU2002-04638-C02-01 and no. BQU2000-0463), the
Junta de Comunidades de Castilla-La Mancha (PAC-02-003) and
the Universidad Rey Juan Carlos (PIPR-02-09).
´
shar, A. M. Rodrıguez, E. Villasen˜or, Organometallics 2001, 20,
71Ϫ78. [12b] A. Antin
˜olo, I. Lopez-Solera, A. Otero, S. Prashar,
´
´
A. M. Rodrıguez, E. Villasen˜or, Organometallics 2002, 21,
2460Ϫ2467.
[13] [13a]
´
C. Alonso-Moreno, A. Antin˜olo, I. Lopez-Solera, A. Ot-
´
ero, S. Prashar, A. M. Rodrıguez, E. Villasen˜or, J. Organomet.
Chem. 2002, 656, 129Ϫ138.
[1]
[13b]
´
A. Antin˜olo, R. Fernandez-
Comprehensive Organometallic Chemistry II (Eds.: E. W. Abel,
´
F. G. A. Stone, G. Wilkinson), Pergamon Press, Oxford, 1995,
Galan, I. Orive, A. Otero, S. Prashar, Eur. J. Inorg. Chem.
2002, 2470Ϫ2476.
[14] [14a]
vol. 4.
[2] [2a]
L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev.
2000, 100, 1253Ϫ1346.
M. R. Collier, M. F. Lappert, R. Pearce, J. Chem. Soc.,
Dalton Trans. 1973, 445Ϫ451. [14b] M. F. Lappert, C. J. Pickett,
P. I. Riley, P. I. W. Yarrow, J. Chem. Soc., Dalton Trans. 1981,
805Ϫ813.
[2b]
H. H. Brintzinger, D. Fischer, R.
Mülhaupt, B. Reiger, R. M. Waymouth, Angew. Chem. 1995,
107, 1255Ϫ1283; Angew. Chem. Int. Ed. Engl. 1995, 36,
1143Ϫ1170.
[15] [15a]
J. L. Atwood, G. K. Barker, J. Holton, W. E. Hunter, M.
[3]
[4]
M. Bühl, G. Hopp, W. von Philipsborn, S. Beck, M. H. Pro-
senc, U. Rief, H. H. Brintzinger, Organometallics 1996, 15,
778Ϫ785.
F. Lappert, R. Pearce, J. Am. Chem. Soc. 1977, 99, 6645Ϫ6652.
[15b]
M. F. Lappert, P. I. Riley, P. I. W. Yarrow, J. L. Atwood,
W. E. Hunter, M. J. Zaworotko, J. Chem. Soc., Dalton Trans.
1981, 814Ϫ821.
[4a] P. C. M öhring, N. J. Coville, J. Organomet. Chem. 1994, 479,
1Ϫ29. [4b] N. Piccolrovazzi, P. Pino, G. Consiglio, A. Sironi, M.
L. D. Durfee, I. P. Rothwell, Chem. Rev. 1988, 88, 1059Ϫ1079.
G. Erker, Acc. Chem. Res. 1984, 17, 103Ϫ109.
G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467Ϫ473.
G. M. Sheldrick, Program for the Refinement of Crystal Struc-
tures from Diffraction Data, University of Göttingen,
Göttingen, Germany, 1997.
[16]
[17]
[18]
[19]
[4c]
Moret, Organometallics 1990, 9, 3098Ϫ3105.
J. Okuda, R.
W. Albach, E. Herdtweck, Polyhedron 1991, 10, 1741Ϫ1748.
[4d]
W. Kaminsky, R. Engehausen, K. Zoumis, W. Spaleck, J.
Rohrmann, Makromol. Chem. 1992, 193, 1643Ϫ1651. [4e] I. M.
Lee, W. J. Gauthier, J. M. Ball, B. Iyengar, S. Collins, Or-
[4f]
ganometallics 1992, 11, 2115Ϫ2122.
C. Janiak, U. Versteeg,
Received March 20, 2003
2632
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 2626Ϫ2632