Triazamethylenemethane complexes of zirconium and tantalum

Article abstract of DOI:10.1016/S1381-1169(97)00159-3

Addition of [Li₂(THF)₄][C(NPh)₃] (2) to a THF solution of Cp *ZrCl₃ (Cp * = C₅Me₅) yields, after recrystallization in Et₂O, the zwitterionic species Cp* [C(NPh)₃]ZrCl₂Li(Et₂O)(THF) (3). Treating 3 with excess methylaluminoxane (MAO) affords a homogeneous Ziegler-Natta catalyst for ethylene polymerization. Addition of LiNPh₂ to 3 allows for Cl substitution to give the new product Cp*[C(NPh)₃]Zr(NPh₂)C1Li(THF)₂ (4). A single crystal diffraction study of 4 reveals that the [C(NPh)₃] ligand is η²-bound. The group 5 complex Cp*[C(NPh)₃]TaMe₂ (5) was prepared by addition of 2 to Cp * TaMe₂Cl(OSO₃CF₃). The X-ray diffraction structure of 5 shows that the [C(NPh)₃] ligand is η²-bound to tantalum and that, when compared to 4, there is less electron delocalization across the inner core of [C(NPh)₃].

Full text of DOI:10.1016/S1381-1169(97)00159-3

Ž
.
Journal of Molecular Catalysis A: Chemical 128 1998 5–28
Triazamethylenemethane complexes of zirconium and tantalum
)
George Rodriguez, Caroline K. Sperry, Guillermo C. Bazan
Department of Chemistry, UniÕersity of Rochester, Rochester, NY 14627-0216, USA
Abstract
)
)
w
Ž
. xw Ž
. x Ž .
Ž
.
Addition of Li2 THF C NPh
2 to a THF solution of Cp ZrCl3 Cp sC5Me5 yields, after recrystallization in
4
)w3 Ž
. x .Ž . Ž .
Ž
Ž
.
Et2O, the zwitterionic species Cp C NPh ZrCl2Li Et2O THF 3 . Treating 3 with excess methylaluminoxane MAO
3
affords a homogeneous Ziegler–Natta catalyst for ethylene polymerization. Addition of LiNPh2 to 3 allows for Cl
)w Ž
. x . Ž .
Ž
.
Ž
substitution to give the new product Cp C NPh Zr NPh2 ClLi THF 4 . A single crystal diffraction study of 4 reveals
3
2
2
w Ž
. x
)w Ž
. x
Ž .
that the C NPh ligand is h -bound. The group 5 complex Cp C NPh TaMe2 5 was prepared by addition of 2 to
3
3 w Ž
. x
)
2
Ž
.
Cp TaMe2Cl OSO3CF3 . The X-ray diffraction structure of 5 shows that the C NPh ligand is h -bound to tantalum and
that, when compared to 4, there is less electron delocalization across the inner core of C NPh . q 1998 Elsevier Science
3 w Ž
. x
3
B.V.
Keywords: Ziegler–Natta polymerization; Zirconium catalysts; Metallocene mimics; Dianionic ligands
1. Introduction
The discovery of new metallocene-based polymerization catalysts rests on the development and
1
application of new ligands for electrophilic transition metals . Modification of the metallocene ligand
2
environment leads to different catalysts and ultimately different product structures . Chiral and
Ž
.
C2-symmetric modifications of the cyclopentadienyl Cp ligand are sought for stereoregular poly-
merization. The ansa-motif, whereby two Cp cores are joined by a transannular bridge, imparts
considerable stability and rigidity to the catalytic site. Ansa-metallocenes can be used in the synthesis
of polyolefins with highly isotactic, syndiotactic or hemiisotactic structures. Exchanging amides for
Cp has been shown to reduce the steric congestion about the metal and increase the electrophilic
w
x
behavior. Amide containing catalysts 8,9 have special propensity for copolymerizing 1-alkenes with
w
x
w x
ethylene 10 and for living polymerization of 1-alkenes 11 .
Despite the successes in improving and modulating polymerization activity and specificity by
changes in the ligand environment, the menu of ancillary ligands remains relatively restricted. One
)
Corresponding author. Tel.: q1-716-2751626; fax: q1-716-4736889; e-mail: bazan@chem.chem.rochester.edu
1
w x
For a recent overview, see 1 .
2
w
x
Comprehensive reviews: Refs. 2–7 .
1381-1169r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.
Ž
.
PII S1381-1169 97 00159-3

(
)
6
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
strategy to expand the list of available choices consists of using dianionic fragments that donate six p
electrons to the metal. As Jordan originally pointed out, replacing a Cp ligand in a metallocene for
one of these mimics leaves gross structural and orbital features intact but changes the overall charge
w
x
12 . It is possible with these metallocene mimics to probe the effect of charge on reactivity. Group 4
2
i
2
Ž
w
xy
.
w
x
Ž
w
xy
.
12–15 , aminoborollide C4H43BN Pr2
complexes containing the dicarbollide C2 B9H11
2
w
x
Ž
w
xy
. w x
16 , and carborane i.e., nido- 2,3-R2C2 B4H4
where RsH or SiMe3 17 ligands have been
prepared in this context. Ligand functionalities which are nonessential for metal bonding, such as the
exocyclic nitrogen in aminoborollides and the Lewis-basic B–H bonds in carborane cages, have the
potential of binding to the metal and inhibiting substrate approach.
Substitution of a cyclopentadienyl ligand for a dianionic six electron ligand also permits the
synthesis of metallocene-like complexes incorporating group 5 metals. To this end,
4
i
Ž
.Ž
.
w
x
)Ž
.
w
x
)Ž
.
C5H4Me C2 B9H11 TaMe2, 14 Cp h -1,3-butadiene TaMe2 19 and Cp C4H4B-N Pr2 TaMe2
w
x
20 , containing the dianionic dicarbollide, diene and aminoborollide ligands, respectively, have been
prepared. The aminoborollide ligand is ‘ambivalent’ and allows for a Ta III resonance contribution
21 . This electronic feature, coupled with the more covalent Ta–C bond, accounts for the lower
activity of aminoborollide–Ta complexes. The diene–Ta combination is especially interesting since it
Ž
.
w
x
w
x
allows for the living polymerization of ethylene 22 .
Our group has been interested in exploring the utility of trimethylenemethane TMM and
Ž
.
Ž
.
w x
tribenzylidenemethane TBM dianions as Cp-mimics 23 . These fragments do not contain het-
eroatom functionalities and are strictly dianionic. They therefore enforce only high oxidation state
characteristics to the metal.
w
)Ž
.
xw
Ž
.
2 x Ž .
1 , are zwitterionic and catalyze the
Group 4 complexes such as Cp TBM ZrCl2 Li TMEDA
Ž
. w x
polymerization of olefins when mixed with a large excess of methylaluminoxane MAO 24 . The
TBM ligand in 1 is h4-bound to zirconium thereby donating six electrons. Complexes of general
composition Cp TBM TaMe2 also have a metallocene-like geometry and an h -bound TBM fragment
25 . These tantalum complexes are chemically robust and have shown polymerization activity when
treated with MAO. The catalytic species however, are shorter lived than in the case of standard group
4 metallocenes.
4
Ž
.
w
x
3
w
x
For related work refer to Ref. 18 .

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
7
2
w
Ž
.
3xy
It was of interest to us to examine how the triazamethylenemethane analog of TBM, C NPh
binds to early transition metals.
,
2
w
Ž
.
3xy
Only two transition metal complexes with the ligand type C NPh
have been previously reported.
2
w
Ž
.
x
Ž
.
Ž
.
In m - C NCy Fe2 CO Cyscyclohexyl , the triazamethylenemethane fragment uses two of its
3
6
w
x
Ž
.
w
Ž
.3x Ž
nitrogen atoms to bridge the two tricarbonyl–iron cores 26 . Mononuclear cod Pt C NPh cods
.
w
Ž
.
3x
cyclooctadiene contains the C NPh
fragment bound in an h2-fashion, forming an essentially
4
planar four-membered PtNCN metallacycle . The inner carbon forms a double bond to the exo-cyclic
nitrogen and two single bonds to the nitrogen atoms at the a sites of the metallacycle. The X-ray
Ä
w
Ž
.
3x2
Ž
. 4
THF shows two dianionic units bridged by two lithiums cations 35 .
6
w x
structure of Li4 C NPh
w
Ž
. x
Metrical parameters within the core of C NPh suggest delocalization through the inner carbon and
are consistent with ‘Y-conjugation’ 36,37 . It is also interesting to note that the relative disposition of
phenyl groups in C NPh generates local Cs symmetry whereas for TBM Li TMEDA the more
symmetric C3h arrangement is found 38 .
3
w
x
w
Ž
.
x
w
xw
Ž
.x
2
3
w
x
In view of the few examples available and the variation of coordination modes, we started a study
w
Ž
.
x
of the bonding between C NPh and early transition metals. The results of this study are disclosed
in this communication.
3
2. Results and discussion
X
Y
Ž
w
Ž
.Ž
.2 x.
As previously reported, N,N ,N -triphenylguanidene C NPh NHPh
may be doubly deproto-
nated using n-BuLi in THF 28–34 . Quick removal of solvent followed by pentane wash gives a
w
x
w
Ž
.
xw
Ž
.3x Ž .
white microcrystalline product of composition Li2 THF C NPh 2 which can be used without
4
further purification. Reaction of 2 in THF with Cp)ZrCl3 results in a color change from colorless to
4
w
x
Similarly, amidinate ligands form a MNCN type metallacycle with a variety of early and late transition metals. See Refs. 27–34 .

(
)
8
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Fig. 1. ORTEP structure of 4 shown at 50% probability.
yellow. After solvent removal, extraction with diethyl ether and cooling to y308C for 12 hours, a
yellow solid is obtained, which, by 1H NMR spectroscopy and elemental analysis, is consistent with a
w
)w
Ž
.
x
xw
Ž
.Ž
.
x
Ž
Ž ..
single product of formula Cp C NPh ZrCl2 Li Et2O THF 3 in Eq. 1 .
3
Ž .
1
The propensity to keep the Et2O and THF suggests a charged zirconium core that keeps Liq as its
countercation. X-ray quality crystals of 3 were not obtainable and the relationship between the Zr core
and Liq remains undetermined.
Addition of one equivalent of LiNPh2 to a THF solution of 3 results in the formation of
1
w
)w
Ž
.
x
Ž
.
xw
Ž
.
2 x
Ž
Ž ..
Cp C NPh ZrCl NPh2 Li THF
4 in Eq. 2 . This reaction is nearly quantitative by H NMR
3
spectroscopy.
Ž .
2

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
9
Table 1
Selected bond lengths A and angles 8 for 4
˚
Ž
.
Ž .
˚
Ž
.
Ž .
Angles 8
Atoms
Distance A
Atoms
Ž .
Zr 1 –N 1
Ž .
Ž .
2.137 2
Ž .
Ž . Ž .
Ž .
91.61 6
Zr 1 –Cl 1
Ž . Ž .
2.4671 6
Ž .
Cl 1 –Zr 1 –N 1
Ž . Ž . Ž .
Ž .
Cl 1 –Zr 1 –N 2
Ž . Ž . Ž .
84.61 5
Ž . Ž .
Ž .
Ž .
90.22 7
Zr 1 –N 3
Ž . Ž .
2.192 2
Ž .
N 1 –Zr 1 –N 3
Ž . Ž .
Ž
Ž
Ž
.
.
.
Ž .
Zr 1 –N 2
Ž .
2.228 2
N 2 –C 23 –N 3
Ž . Ž .
106.6 2
Ž
Ž .
.
Ž .
Ž .
131.5 2
Zr 1 –C 23
2.736 2
N 2 –C 23 –N 4
Ž . Ž .
Ž
.
.
Ž .
1.373 3
Ž .
1.378 3
Ž .
C 23 –N 2
N 3 –C 23 –N 4
Ž . Ž . Ž .
121.9 2
Ž
Ž .
Ž .
112.3 2
C 23 –N 3
O 1 –Li 1 –O 2
Ž
.
Ž .
Ž .
1.320 3
C 23 –N 4
Ž . Ž .
Ž .
Li 1 –N 4
1.979 5
Ž .
Ž . Ž .
Li 1 –O 1
1.190 5
Ž . Ž .
Ž .
Li 1 –O 2
1.874 5
Ž .
Ž
Ž
.
.
Ž .
Li 1 –C 25
2.483 6
Ž .
Ž .
Li 1 –C 36
2.760 5
Crystals of 4 suitable for crystallography were obtained by slowly evaporating a concentrated benzene
solution, and the results of this study are shown in Fig. 1. Bond distances and angles are given in
X
Table 1. As seen in Fig. 1, the C NPh ligand is h2-coordinated forming an a,a -diazametalla-
w
Ž
.
x
w
Ž
.
33x
cycle. The inner carbon of the C NPh
ligand is nearly equidistant to the three nitrogen atoms
C 23 –N 2 1.373 3 A, C 23 –N 3 1.378 3 A, C 23 –N 4 1.320 3 A . However, C 23 –N 4 is
statistically shorter by about 0.05 A. The lithium countercation is coordinated via two THF molecules
˚
˚
˚
Ž . .
Ž Ž
.
Ž .
Ž .
Ž
.
Ž .
Ž .
Ž
.
Ž .
Ž
.
Ž .
˚
Ž .
and N 4 . Additional electron density to the Li, at least in the solid state, is provided by the phenyl
)
Ž .
Ž .
rings on N 3 and N 4 . The geometry at Zr resembles a four-legged piano stool with the Cp ligand
forming the ‘seat’. The Zr–N 2 distance is slightly longer than that of Zr–N 3 perhaps as a result of
Ž .
Ž .
the stronger trans effect of NPh2 relative to Cl.
Ž
.
Reaction of 3 with excess MAO and ethylene results in the formation of polyethylene PE . The
Ž
.
.
activity of the 3rMAO mixture was measured at 26 kg PErZr mol l atm. Under identical
Ž
conditions, Cp2 ZrCl2rMAO gave an activity of 90 kg PErZr mol l atm while 1rMAO gave 15 kg
Ž
.
PErZr mol l atm. Thus, if we assume that MAO serves its standard role of alkylation followed by
w
Ž
.3x
heterolytic ligand extraction, the C NPh ligand leads to neutral catalysts that are more reactive
than their TBM counterparts yet less active than standard cationic metallocenes .
5
w
Ž
.
x
To expand the scope of this investigation, a Group 5 complex containing the C NPh ligand was
3
)
Ž
.
synthesized. Addition of 2 to a THF solution of Cp TaMe2Cl OSO3CF3 results in the formation of
)w
Ž
.
x
Ž
Ž ..
Cp C NPh TaMe2 5 in Eq. 3 .
3
Ž .
3
5
w
x
This also holds true for the related benzamidinate early transition metal complexes. See for example Ref. 39 .

(
)
10
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Fig. 2. ORTEP structure of 5 shown at 50% probability.
This red-orange product is readily crystallized from a concentrated ether solution vapor diffused with
pentane at y358C. The X-ray crystal structure of 5 is shown in Fig. 2. Bond distances and angles are
given in Table 2. The geometry at the Ta in 5 is similar to the Zr environment in 4. The molecule
2
w
Ž
.
x
resembles a four-legged piano stool with the C NPh ligand coordinated in an h fashion giving a
3
a,aX-diazametallocyclobutane. The distances of the nitrogens to the inner core carbon of the
C NPh ligand show significant disparity. The C 31 –N 2 distance 1.268 7 A is consistent with
double bond character whereas the C 31 –N 1 1.398 7 A and C 31 –N 3 1.407 7 A distances
indicate single bond character. The bond angles for N 1 and N 3 Ta 1 –N 1 –C 13 137.9 4 8,
˚
.
w
Ž
.
x
Ž
.
Ž .
Ž .
Ž
Ž .
3
˚
˚
.
.
Ž
.
Ž . Ž
.
Ž
.
Ž . Ž
Ž .
Ž
Ž .
Ž . Ž Ž .
Ž .
Ž .
2
Ž .
Ž .
Ž
.
Ž . .
Ta 1 –N 3 –C 25 139.0 4 8 indicate that these nitrogens are sp hybridized.
Ž
w x
w
x
.
Mixing 5 and MAO at Zr to Al ratios of approximately 500 and 1000 does not result in an
ethylene polymerization catalyst.
3. Conclusion
w
Ž
.
x
In summary, we have shown that C NPh can be used in the synthesis of early transition metal
3
complexes. The electron density within the inner core of the ligand is more delocalized in 4 than in 5.
Table 2
˚
Ž
.
Ž .
Selected bond lengths A and angles 8 for 5
˚
Ž
.
Ž .
Angles 8
Atoms
Distance A
Atoms
Ž . Ž .
Ta 1 –N 3
Ž .
2.058 5
Ž
.
Ž .
.
.
Ž
.
Ž .
85.8 3
Ta 1 –N 1
Ž . Ž .
2.116 5
Ž .
C 11 –Ta 1 –C 12
Ž . Ž .
Ž
Ž
Ž .
N 1 –C 31 –N 2
Ž . Ž .
133.8 5
Ž .
Ž
Ž
.
.
Ž .
Ž .
101.9 5
Ž .
124.3 5
Ta 1 –C 11
Ž .
2.178 7
N 1 –C 31 –N 3
Ž . Ž . Ž .
N 2 –C 31 –N 3
Ž .
2.205 7
Ta 1 –C 12
Ž .
Ž
Ž
Ž
.
.
.
Ž .
Ž . Ž .
Ž
.
.
Ž .
137.9 4
Ž .
139.0 4
N 1 –C 31
1.398 7
Ta 1 –N 1 –C 13
Ž . Ž . Ž
Ta 1 –N 3 –C 25
Ž .
Ž .
N 2 –C 31
1.268 7
Ž .
Ž .
N 3 –C 31
1.407 7

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
11
This difference is probably a result of Liq coordination to the exo-cyclic N atom. It is interesting that
h4-coordination was not observed in either 4 or 5. This coordination mode is observed for the
isoelectronic TBM ligand and allows for donation of up to six p electrons. The structural parameters
of 5 show clear evidence that the two Ta-bound N atoms are sp2 hybridized suggesting that in
w
Ž
.
x
addition to the two Ta–N s bonds, there is an additional p component. The C NPh core can thus
3
donate up to eight electrons to the metal center. A more complete survey of the reactivity patterns of 3
and 5 will be the subject of future studies.
Table 3
Crystal and structure refinement data for 4 and 5
Crystal parameters
4
5
Chemical formula
Formula weight
Crystal system
C49 H56ClN4 LiO4 Zr
866.66
triclinic
C30 H36 N3Ta
619.58
monoclinic
Ž
.
Ž
.
Ž
.
Space group No.
Z
P1 a2
2
C2rc a15
8
a
˚
Ž
.
Ž .
11.7636 1
Ž .
31.2878 4
a A
˚
Ž
Ž
.
.
Ž .
12.4384 1
Ž .
17.9531 1
Ž .
7.9181 1
Ž .
23.003 3
b A
˚
c A
Ž .
Ž .
Ž .
71.238 1
a
b
g
8
86.732 1
Ž .
Ž .
101.687 1
8
Ž .
8
Ž .
89.372 1
3
˚
Ž
.
Ž .
2483.2 4
Ž .
2483.2 4
1.480
0.20=0.40=0.20
y50
Volume A
rcalc mgrm
Crystal dimens. mm
3
Ž
.
1.263
Ž
.
.
0.20=0.25=0.35
y50
Ž
Temperature 8C
Measurement of intensity data and structure refinement
4
5
Diffractometer
Siemens SMART
Siemens SMART
˚
Ž
.
Radiation, l A
Mo, 0.71073
4–56
Mo, 0.71073
3–56
Ž .b
2u range for data collection 8
Limiting indices
y14FhF15
y14FkF16
0FhF40
y10FkF9
y28FlF24
30025
0FlF23
c
Ž .
15510 to 458
Total reflections
Ž
.
Ž
.
Independent reflections
No. of observed data
10983 Rint s0.0255
13565 Rint s0.061
Ž
Ž ..
Ž
Ž ..
10980 I)2s I
4575 I)3s I
316
No. of parameters varied
577
3.19
y1
Ž
.
m mm
3.95
Ž
.
Absorption correction
Range of trans. factors
empirical SADABS
semiempirical
0.5900–0.8840
4.2, 3.9
NA
1.85
0.50600–0.55791
4.41, 13.17
5.65, 14.69
1.085
2
Ž
Ž
.
.
Ž
Ž
.
.
Ž
Ž ..d
R1 Fo , wR2 Fo %, I)2s I
2
R1 Fo , wR2 Fo %, all data
Goodness-of-fit on F2
a It has been noted that the integration program SAINT produces cell constant errors that are unreasonably small, since systematic error is
not included. More reasonable errors might be estimated at 10= the listed values.
b The SMART CCD crystal-to-detector distance is set to 5.094 cm which equates to a maximum 2u angle of 56.528.
cAlthough data are routinely collected to 568, these crystals were weak diffracters and therefore data greater than 458 were omitted from the
refinement.
d
2
1r2
2 .2 xx
2
2
Ž
5
<
<
5.
<
<
w
w
Ž
2 .2 x
w
Ž
w
2Ž
, where ws1r s Fo q aPP qbPP and Ps fP Maximum
.
Ž
.
x
w
Ž
R1 s Ý Fo y Fc rÝ Fo , wR2 s Ý w Fo yFc
rÝ w Fo
2
of 0 or Fo2 q 1yf PFc
.
.
Ž
.
x

(
)
12
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
4. Experimental
4.1. General considerations
All manipulations were carried out using either high-vacuum or glovebox techniques as previously
1
described 40 . H and 13C NMR spectra were recorded on a Bruker AMX-400 spectrometer at 400.1
w
x
and 100.6 MHz, respectively. Toluene, pentane, diethyl ether and tetrahydrofuran were distilled from
)
w
Ž
.
xw
Ž
.
x w
x
Ž
.
benzophenone ketyl prior to use. The preparations of C NPh Li2 THF
27 , Cp Zr CH2 Ph Cl2
3
4
and Cp)ZrCl3 41 are available in the literature.
)([ (
w
x
) ]) ) ( )
(
)(
4.2. Cp C NPh 3 ZrCl2 Li Et2O THF 3
)
Ž
.
A THF solution of 2 1.23 g, 2.78 mmol was added dropwise to a THF solution of Cp ZrCl3
Ž
.
0.925 g, 2.78 mmol . After stirring for 30 min the solvent was replaced with 20 ml of Et2O and the
LiCl removed by filtration leaving a clear bright yellow solution. The volume was reduced by 50%
and the solution cooled at y308C for 12 h. This provided the product as a fluorescent yellow solid
Ž
.
which was isolated by filtration and dried under reduced pressure 1.43 g, 70% . The added THF-d8
Table 4
Crystallographic data for 4
Crystal parameters
Chemical formula
Formula weight
Crystal system
ZrC49 H56ClN4 LiO2
866.66
triclinic
Ž
.
Ž
.
Space group No.
P1 a2
Z
2
˚
Ž
.
Ž .
11.7636 1
a A
˚
Ž
Ž
.
.
Ž .
12.4384 1
Ž .
17.9531 1
b A
˚
c A
Ž .
Ž .
Ž .
71.238 1
a
b
g
8
86.732 1
Ž .
8
Ž .
8
Ž .
89.372 1
3
˚
Ž
.
Ž .
2483.2 4
Volume A
rcalc g cm
Crystal dimens. mm
Temperature 8C
y3
Ž
.
1.263
3
Ž
.
.
0.20=0.25=0.35
y50
Ž
Measurement of intensity data
Diffractometer
Radiation
Siemens SMART
˚
Mo, 0.71073 A
Ž .
2u range 8
3.4–56.0
15510
10983
10980
0.0255
577
No. of data collected
No. of unique data
No. of observed data Fo )4s Fo
Agreement between equivalent data Rint
No. of parameters varied
Ž
Ž
..
Ž
.
y1
Ž
.
m mm
3.19
Ž
.
Absorption correction
empirical SADABS
Range of trans. factors
0.50600–0.55791
0.0441, 0.1317
0.0565, 0.1469
1.085
Ž
.
.
Ž
Ž
. Ž ..
. Ž
Ž
R1 Fo , wR2 Fo , Fo )4s Fo
Ž
.
R1 Fo , wR2 Fo all data
Goodness of fit

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
13
Table 5
4
2
3
˚
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement parameters A =10 for 4. U eq is defined as one third of the trace of
the orthogonalized U tensor
i j
Ž
.
x
y
z
U eq
Ž .
Zr 1
Ž .
Ž .
y2690 1
Ž .
1814 1
Ž .
y3001 1
23 1
Ž .
Ž .
Ž .
y6919 4
Ž .
Ž .
Li 1
y2373 4
2488 3
42 1
Ž .
Ž .
Cl 1
Ž .
Ž .
Ž .
2645 1
y2930 1
y1196 1
39 1
Ž .
Ž .
Ž .
Ž .
Ž .
N 1
y4917 2
y2756 2
2269 1
28 1
Ž .
N 2
Ž .
Ž .
Ž .
2359 1
Ž .
26 1
y1735 2
y3493 2
Ž .
Ž .
Ž .
Ž .
Ž .
N 3
y2929 2
y4452 2
1920 1
26 1
Ž .
N 4
Ž .
Ž .
Ž .
2549 1
Ž .
30 1
y1756 2
y5464 2
Ž .
Ž .
Ž .
Ž .
Ž .
O 1
y1190 2
y8013 2
2173 1
46 1
Ž .
Ž .
O 2
Ž .
Ž .
Ž .
3141 1
y3855 2
y7476 2
51 1
Ž .
Ž .
Ž .
Ž .
Ž .
C 1
y3078 2
y1887 2
443 2
39 1
Ž .
C 2
Ž .
Ž .
Ž .
709 2
Ž .
36 1
y2387 2
y1178 2
Ž .
Ž .
Ž .
Ž .
Ž .
C 3
y1348 2
y1714 2
733 2
41 1
Ž .
C 4
Ž .
Ž .
Ž .
503 2
Ž .
y1399 3
y2766 3
49 1
Ž .
Ž .
Ž .
Ž .
Ž .
C 5
y2469 3
y2879 2
325 2
48 1
Ž .
C 6
Ž .
Ž .
Ž .
160 2
Ž .
y4102 3
y1559 4
78 1
Ž .
Ž .
Ž .
Ž .
Ž .
67 1
C 7
y2664 4
y9 2
850 2
Ž .
C 8
Ž .
Ž .
Ž .
911 2
Ž .
y314 4
y1197 4
85 2
Ž .
Ž .
Ž .
Ž .
Ž .
96 2
C 9
y446 4
y3620 4
406 2
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
y44 2
Ž .
C 10
y2834 5
y3823 3
99 2
Ž
Ž .
Ž .
Ž .
3529 1
Ž .
C 12
y4770 2
y3460 2
34 1
Ž .
Ž
Ž .
Ž .
Ž .
C 13
y5268 3
y3973 2
4267 2
40 1
Ž
Ž .
Ž .
Ž .
4531 2
Ž .
C 14
y6458 3
y4292 2
45 1
Ž .
Ž
Ž .
Ž .
Ž .
C 15
y7147 3
y4104 2
4045 2
44 1
Ž
Ž .
Ž .
Ž .
3301 2
Ž .
C 16
y6663 2
y3602 2
37 1
Ž .
Ž
Ž .
Ž .
Ž .
C 11
y5455 2
y3268 2
3024 1
28 1
Ž
Ž .
Ž .
y2702 2
Ž .
1509 2
Ž .
C 18
y6325 2
41 1
Ž
Ž .
Ž .
y2115 3
Ž .
Ž .
C 19
y7127 3
1211 2
53 1
Ž .
Ž
Ž .
Ž .
Ž .
1363 2
C 20
y7352 3
y1067 3
58 1
Ž
Ž .
y6788 3
Ž .
Ž .
Ž .
C 21
y557 3
1812 2
57 1
Ž
Ž .
y5987 3
Ž .
Ž .
2106 2
Ž .
C 22
y1124 2
44 1
Ž .
Ž
Ž .
Ž .
Ž .
C 17
y5742 2
y2196 2
1956 1
32 1
Ž
Ž .
Ž .
y4528 2
Ž .
2295 1
Ž .
C 23
y2074 2
26 1
Ž
Ž .
Ž .
y6136 2
Ž .
Ž .
C 25
y2537 2
1224 2
35 1
Ž .
Ž
Ž .
Ž .
Ž .
939 2
C 26
y2969 3
y7000 2
47 1
Ž
Ž .
y4174 3
Ž .
Ž .
Ž .
C 27
y7096 3
1040 2
58 1
Ž
Ž .
y4956 3
Ž .
Ž .
1422 2
Ž .
C 28
y6311 3
56 1
Ž .
Ž
Ž .
Ž .
Ž .
C 29
y4543 2
y5457 2
1727 2
39 1
Ž
Ž .
Ž .
y5353 2
Ž .
1636 1
Ž .
C 24
y3328 2
28 1
Ž
Ž .
Ž .
y2587 2
Ž .
Ž .
C 31
y196 2
2728 2
35 1
Ž .
Ž
Ž .
Ž .
Ž .
3272 2
C 32
363 3
y2354 2
43 1
Ž
Ž .
y75 3
Ž .
Ž .
Ž .
C 33
y2795 2
4033 2
45 1
Ž .
Ž
Ž .
Ž .
Ž .
4255 2
C 34
y1094 3
y3442 2
43 1
Ž
Ž .
Ž .
Ž .
Ž .
C 35
y1661 2
y3652 2
3713 2
34 1
Ž
Ž .
Ž .
Ž .
2935 1
Ž .
C 30
y1205 2
y3247 2
27 1
Ž .
Ž
Ž .
Ž .
Ž .
C 37
404 3
y5178 3
2317 2
53 1
Ž
Ž .
1410 4
Ž .
Ž .
2537 4
Ž .
C 38
y5407 3
87 2
Ž
Ž .
Ž .
y6034 4
Ž .
Ž .
C 39
1344 5
3188 4
104 2
Ž .
Ž
Ž .
251 5
Ž .
Ž .
3647 3
C 40
y6458 4
91 2
Ž
Ž .
Ž .
Ž .
Ž .
C 41
y778 4
y6234 3
3443 2
57 1
Ž
Ž .
Ž .
y5585 2
Ž .
2776 2
Ž .
38 1
C 36
y720 3
Ž
Ž .
Ž .
y7882 3
Ž .
Ž .
C 42
y81 3
1541 2
61 1
Ž
Ž .
Ž .
y8365 4
Ž .
1841 3
Ž .
100 2
C 43
857 4
Ž
Ž .
261 4
Ž .
Ž .
Ž .
C 44
y9083 4
2506 3
81 1
Ž .
Ž
Ž .
y1047 3
Ž .
Ž .
2738 2
C 45
y8832 3
57 1

(
)
14
Table 5 continued .
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Ž
.
Ž
.
x
y
z
U eq
Ž
.
.
.
.
Ž .
y4477 3
Ž .
Ž .
3050 2
Ž .
C 46
y8413 3
65 1
Ž
Ž .
Ž .
Ž .
Ž .
C 47
y5793 4
y8149 4
3379 3
97 2
Ž .
Ž
Ž .
Ž .
Ž .
3922 4
C 48
y5834 4
y7310 5
124 2
Ž
Ž .
Ž .
Ž .
Ž .
C 49
y4654 4
y6837 4
3711 3
86 1
Ž .
Ž
.
.
.
.
.
.
Ž .
Ž .
Ž .
y5547 4
C 101
1837 6
y401 6
132 3
Ž
Ž .
1590 4
Ž .
Ž .
y5029 4
Ž .
C 102
384 4
100 2
Ž
Ž .
Ž .
535 4
Ž .
y4588 2
Ž .
78 1
C 103
2284 5
Ž
Ž .
3233 7
Ž .
Ž .
y4649 4
Ž .
C 104
y59 6
131 2
Ž
Ž .
Ž .
Ž .
Ž .
C 105
3510 9
y878 7
y5165 5
171 4
Ž .
Ž
Ž .
2800 8
Ž .
Ž .
C 106
y1039 5
y5624 4
144 3
1
Ž
.
displaced the coordinated THF and Et2O. H NMR C6D6rTHF-d8; 1:1 : d 7.41, 7.08, 6.93, 6.78,
6.58 15H, C6 H5N C , 2.09 s, 15H, C5 C H3 5 13C NMR C6D6rTHF-d8; 1:1 : d 162.4
C6H5N C , 150.0, 149.12, 127.8, 125.8, 124.7, 123.8, 121.9, 120.0 C6H5N C, C5 CH3 5 , 12.5
Ž
w
x
.
Ž
Ž
. .
Ž
.
3
Ž
Ž
w
x
.
Ž
w
x
Ž
. .
3
Ž
.3 .
C5 CH3 5 . Anal. Calcd. for ZrC37H48Cl2LiN3O2: C, 60.38; H, 6.58; N, 5.71;. Found: C, 60.37; H,
6.39; N, 5.64.
Table 6
˚
Ž
.
Ž .
Bond lengths A and angles 8 for 4
Ž . Ž .
Zr 1 –N 1
Ž . Ž .
Zr 1 –N 3
Ž .
2.137 2
Ž .
2.192 2
Ž . Ž .
Zr 1 –N 2
Ž . Ž .
Zr 1 –Cl 1
Ž .
2.228 2
Ž .
2.4671 6
Ž . Ž .
Ž .
2.503 3
Zr 1 –C 4
Ž . Ž .
Ž .
Zr 1 –C 3
Ž . Ž .
2.524 3
Ž .
2.566 3
Zr 1 –C 5
Ž . Ž .
Ž .
Ž .
2.631 2
Ž .
2.736 2
Zr 1 –C 2
2.585 2
Ž . Ž .
Zr 1 –C 1
Ž .
Ž
.
Zr 1 –C 23
Ž . Ž .
Ž .
1.874 5
Li 1 –O 2
Ž . Ž .
Ž .
Li 1 –O 1
Ž . Ž .
1.910 5
Ž .
1.979 5
Li 1 –N 4
Ž .
Ž
Ž
.
.
Ž .
Ž .
2.760 5
Li 1 –C 25
Ž .
2.483 6
Li 1 –C 36
Ž .
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
.
Ž .
Ž .
1.427 3
N 1 –C 11
1.415 3
Ž .
.
.
.
.
.
.
.
.
.
.
.
N 1 –C 17
Ž .
Ž .
N 2 –C 23
1.373 3
Ž .
Ž .
1.416 3
N 2 –C 30
Ž .
Ž .
N 3 –C 23
Ž .
1.378 3
Ž .
1.403 3
N 3 –C 24
Ž .
Ž .
N 4 –C 23
1.320 3
Ž .
Ž .
1.408 3
N 4 –C 36
Ž .
Ž .
O 1 –C 42
Ž .
1.430 4
Ž .
1.443 4
O 1 –C 45
Ž .
Ž .
O 2 –C 49
1.421 4
Ž .
O 2 –C 46
Ž .
1.428 4
Ž . Ž .
Ž . Ž .
C 1 –C 5
Ž .
Ž .
1.412 4
C 1 –C 2
1.406 4
Ž . Ž .
Ž . Ž .
C 2 –C 3
Ž .
Ž .
1.398 4
C 1 –C 6
1.496 4
Ž . Ž .
C 3 –C 4
Ž .
Ž .
1.401 4
C 2 –C 7
Ž . Ž .
1.504 4

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
15
Ž
.
Table 6 continued .
Ž . Ž .
C 4 –C 5
Ž .
1.511 4
Ž .
1.405 5
C 3 –C 8
Ž . Ž .
Ž . Ž .
Ž .
1.512 4
Ž .
1.511 5
C 4 –C 9
Ž .
Ž
.
C 5 –C 10
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
1.385 4
C 12 –C 13
Ž
Ž .
C 12 –C 11
1.403 3
Ž
Ž .
1.380 4
C 13 –C 14
Ž
Ž .
C 14 –C 15
1.379 4
Ž
Ž .
1.387 4
C 15 –C 16
Ž
Ž .
C 16 –C 11
1.405 3
Ž
Ž .
1.390 4
C 18 –C 17
Ž
Ž .
C 18 –C 19
1.405 4
Ž
Ž .
1.353 5
C 19 –C 20
Ž
Ž .
C 20 –C 21
1.379 5
Ž
Ž .
1.388 4
C 21 –C 22
Ž
Ž .
C 22 –C 17
1.384 4
Ž
Ž .
1.384 4
C 25 –C 26
Ž
Ž .
C 25 –C 24
1.408 3
Ž
Ž .
1.376 5
C 26 –C 27
Ž
Ž .
C 27 –C 28
1.385 5
Ž
Ž .
1.383 4
C 28 –C 29
Ž
Ž .
C 29 –C 24
1.392 3
Ž
Ž .
1.386 4
C 31 –C 32
Ž
Ž .
C 31 –C 30
1.387 3
Ž
Ž .
1.378 4
C 32 –C 33
Ž
Ž .
C 33 –C 34
1.386 4
Ž
Ž .
1.383 4
C 34 –C 35
Ž
Ž .
C 35 –C 30
1.391 3
Ž
Ž .
1.386 5
C 37 –C 38
Ž
Ž .
C 37 –C 36
1.396 4
Ž
Ž .
1.348 8
C 38 –C 39
Ž
Ž .
C 39 –C 40
1.376 8
Ž
Ž .
1.395 5
C 40 –C 41
Ž
Ž .
C 41 –C 36
1.389 4
Ž
Ž .
1.484 5
C 42 –C 43
Ž
Ž .
C 43 –C 44
1.438 6
Ž
.
.
.
.
Ž
Ž
Ž
Ž
Ž .
1.493 5
C 44 –C 45
Ž
Ž .
C 46 –C 47
1.509 6
Ž
Ž .
1.458 7
Ž .
1.439 6
C 47 –C 48
Ž
C 48 –C 49
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž .
1.352 7
C 101 –C 102
Ž
Ž
.
C 101 –C 106
1.352 10
Ž
Ž .
1.328 7
Ž .
1.310 7
C 102 –C 103
Ž
C 103 –C 104
Ž
Ž
.
.
C 104 –C 105
1.381 10
Ž
Ž
C 105 –C 106
1.372 11
Ž .
90.22 7
Ž .
Ž . Ž .
N 1 –Zr 1 –N 3
Ž . Ž . Ž .
Ž .
N 1 –Zr 1 –N 2
Ž . Ž . Ž .
126.32 7
Ž .
N 3 –Zr 1 –N 2
Ž . Ž . Ž .
59.90 7
Ž .
N 1 –Zr 1 –Cl 1
Ž . Ž . Ž .
91.61 6
Ž .
N 3 –Zr 1 –Cl 1
Ž . Ž . Ž .
136.18 5
Ž .
N 2 –Zr 1 –Cl 1
Ž . Ž . Ž .
84.61 5
Ž
.
N 1 –Zr 1 –C 4
Ž . Ž . Ž .
137.64 10
Ž .
N 3 –Zr 1 –C 4
Ž . Ž . Ž .
87.74 9
Ž .
88.25 9
Ž .
118.10 8
N 2 –Zr 1 –C 4
Ž . Ž . Ž .
Cl 1 –Zr 1 –C 4

(
)
16
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Ž
.
Table 6 continued .
Ž . Ž . Ž .
Ž .
139.73 8
N 1 –Zr 1 –C 3
Ž . Ž . Ž .
Ž .
N 3 –Zr 1 –C 3
Ž . Ž . Ž .
117.89 9
Ž .
93.63 8
N 2 –Zr 1 –C 3
Ž . Ž . Ž .
Ž .
Cl 1 –Zr 1 –C 3
Ž . Ž . Ž .
86.87 7
Ž
.
C 4 –Zr 1 –C 3
Ž . Ž . Ž .
32.36 10
Ž .
N 1 –Zr 1 –C 5
Ž . Ž . Ž .
105.49 9
Ž .
N 3 –Zr 1 –C 5
Ž . Ž . Ž .
86.53 8
Ž .
N 2 –Zr 1 –C 5
Ž . Ž . Ž .
114.86 9
Ž .
Cl 1 –Zr 1 –C 5
Ž . Ž . Ž .
134.49 7
Ž
.
.
C 4 –Zr 1 –C 5
Ž . Ž . Ž .
32.15 11
Ž
C 3 –Zr 1 –C 5
Ž . Ž . Ž .
52.99 10
Ž .
108.21 8
N 1 –Zr 1 –C 2
Ž . Ž . Ž .
Ž .
137.78 8
Ž .
124.09 8
Ž .
82.32 6
Ž .
52.92 9
N 3 –Zr 1 –C 2
Ž . Ž . Ž .
N 2 –Zr 1 –C 2
Ž . Ž . Ž .
Cl 1 –Zr 1 –C 2
Ž . Ž . Ž .
C 4 –Zr 1 –C 2
Ž . Ž . Ž .
Ž .
C 3 –Zr 1 –C 2
Ž . Ž . Ž .
31.73 8
Ž .
52.41 9
C 5 –Zr 1 –C 2
Ž . Ž . Ž .
Ž .
N 1 –Zr 1 –C 1
Ž . Ž . Ž .
90.97 8
Ž .
114.78 8
N 3 –Zr 1 –C 1
Ž . Ž . Ž .
Ž .
N 2 –Zr 1 –C 1
Ž . Ž . Ž .
140.65 8
Ž .
Cl 1 –Zr 1 –C 1
Ž . Ž . Ž .
108.97 7
Ž .
C 4 –Zr 1 –C 1
Ž . Ž . Ž .
52.57 9
Ž .
C 3 –Zr 1 –C 1
Ž . Ž . Ž .
52.23 8
Ž .
31.50 9
C 5 –Zr 1 –C 1
Ž . Ž . Ž .
Ž .
C 2 –Zr 1 –C 1
Ž . Ž .
31.26 8
Ž
.
.
.
.
.
.
.
.
.
Ž .
N 1 –Zr 1 –C 23
Ž . Ž .
109.55 7
Ž .
Ž
N 3 –Zr 1 –C 23
Ž . Ž .
29.97 7
Ž
Ž .
N 2 –Zr 1 –C 23
Ž . Ž .
29.95 7
Ž
Ž .
110.86 5
Ž .
88.43 8
Ž .
108.51 8
Cl 1 –Zr 1 –C 23
Ž . Ž .
Ž
C 4 –Zr 1 –C 23
Ž . Ž .
Ž
C 3 –Zr 1 –C 23
Ž . Ž .
Ž
Ž .
C 5 –Zr 1 –C 23
Ž . Ž .
102.63 9
Ž
Ž .
139.37 8
Ž .
134.13 8
C 2 –Zr 1 –C 23
Ž . Ž .
Ž
C 1 –Zr 1 –C 23
Ž . Ž . Ž .
Ž .
O 2 –Li 1 –O 1
Ž . Ž . Ž .
112.3 2
Ž .
124.5 3
Ž .
115.9 2
O 2 –Li 1 –N 4
Ž . Ž . Ž .
O 1 –Li 1 –N 4
Ž . Ž .
Ž
.
.
.
.
.
.
Ž .
O 2 –Li 1 –C 25
Ž . Ž .
110.9 2
Ž
Ž .
O 1 –Li 1 –C 25
Ž . Ž .
103.8 2
Ž .
Ž
N 4 –Li 1 –C 25
Ž . Ž .
82.8 2
Ž
Ž .
O 2 –Li 1 –C 36
Ž . Ž .
131.8 3
Ž .
Ž
O 1 –Li 1 –C 36
Ž . Ž .
90.7 2
Ž
Ž
.
N 4 –Li 1 –C 36
29.05 10
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž
.
Ž .
C 25 –Li 1 –C 36
Ž . Ž .
103.1 2
Ž .
114.1 2
Ž
C 11 –N 1 –C 17
Ž . Ž .
Ž
Ž .
C 11 –N 1 –Zr 1
Ž . Ž .
118.0 2
Ž
Ž .
127.2 2
Ž .
121.1 2
C 17 –N 1 –Zr 1
Ž .
Ž
Ž
Ž .
.
.
.
C 23 –N 2 –C 30
Ž
Ž .
Ž .
Ž
.
.
C 23 –N 2 –Zr 1
95.98 13
Ž
Ž .
Ž .
136.3 2
Ž .
122.1 2
C 30 –N 2 –Zr 1
Ž .
Ž
Ž
Ž .
C 23 –N 3 –C 24
Ž
Ž .
Ž .
Ž .
Ž
C 23 –N 3 –Zr 1
97.43 14
Ž
Ž .
Ž
Ž .
139.6 2
Ž .
122.4 2
Ž .
128.6 2
Ž .
107.9 2
C 24 –N 3 –Zr 1
Ž
C 23 –N 4 –C 36
Ž . Ž .
Ž
C 23 –N 4 –Li 1
Ž . Ž .
Ž
.
C 36 –N 4 –Li 1

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
17
Ž
.
Table 6 continued .
Ž
.
.
Ž .
Ž .
Ž
Ž .
.
Ž .
109.0 2
Ž .
124.7 2
C 42 –O 1 –C 45
Ž
C 42 –O 1 –Li 1
Ž
.
.
Ž .
Ž .
Ž .
Ž .
120.7 3
Ž .
109.2 3
C 45 –O 1 –Li 1
Ž
Ž
.
C 49 –O 2 –C 46
Ž
.
.
Ž .
Ž .
Ž .
120.8 3
Ž .
128.5 3
C 49 –O 2 –Li 1
Ž . Ž .
Ž
C 46 –O 2 –Li 1
Ž . Ž . Ž .
Ž . Ž . Ž .
C 2 –C 1 –C 6
Ž .
107.6 2
Ž .
124.9 3
C 2 –C 1 –C 5
Ž . Ž . Ž .
Ž .
126.0 3
C 5 –C 1 –C 6
Ž . Ž . Ž .
Ž
.
.
C 2 –C 1 –Zr 1
Ž . Ž . Ž .
72.54 14
Ž
71.71 14
C 5 –C 1 –Zr 1
Ž . Ž . Ž .
Ž .
C 6 –C 1 –Zr 1
132.1 2
Ž .
Ž . Ž . Ž .
C 3 –C 2 –C 1
108.2 2
Ž . Ž . Ž .
C 3 –C 2 –C 7
Ž .
126.4 3
Ž .
125.1 3
Ž . Ž . Ž .
C 1 –C 2 –C 7
Ž . Ž . Ž .
Ž
.
C 3 –C 2 –Zr 1
Ž . Ž . Ž .
71.76 14
Ž .
C 1 –C 2 –Zr 1
Ž . Ž . Ž .
76.2 2
Ž .
123.2 2
C 7 –C 2 –Zr 1
Ž . Ž . Ž .
Ž . Ž . Ž .
C 2 –C 3 –C 8
Ž .
Ž .
124.7 3
C 2 –C 3 –C 4
108.3 3
Ž . Ž . Ž .
Ž .
Ž .
76.5 2
C 4 –C 3 –C 8
Ž . Ž . Ž .
126.8 3
C 2 –C 3 –Zr 1
Ž . Ž . Ž .
Ž .
C 4 –C 3 –Zr 1
Ž . Ž . Ž .
73.0 2
Ž .
120.7 2
C 8 –C 3 –Zr 1
Ž . Ž . Ž .
Ž . Ž . Ž .
C 5 –C 4 –C 9
Ž .
Ž .
125.0 4
C 5 –C 4 –C 3
108.1 3
Ž . Ž . Ž .
Ž .
Ž .
76.4 2
C 3 –C 4 –C 9
Ž . Ž . Ž .
126.9 4
C 5 –C 4 –Zr 1
Ž . Ž . Ž .
Ž .
C 3 –C 4 –Zr 1
Ž . Ž . Ž .
74.6 2
Ž .
118.2 2
C 9 –C 4 –Zr 1
Ž . Ž . Ž .
Ž .
Ž .
126.8 4
Ž .
124.8 4
C 4 –C 5 –C 1
Ž . Ž .
107.8 3
Ž
.
.
C 4 –C 5 –C 10
Ž . Ž .
Ž
C 1 –C 5 –C 10
Ž . Ž .
Ž .
Ž .
71.5 2
C 4 –C 5 –Zr 1
Ž . Ž . Ž .
Ž .
C 1 –C 5 –Zr 1
Ž . Ž .
76.8 2
Ž
.
Ž .
124.5 2
C 10 –C 5 –Zr 1
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž .
Ž .
120.9 3
C 13 –C 12 –C 11
120.9 2
Ž
C 14 –C 13 –C 12
Ž
Ž .
C 15 –C 14 –C 13
119.0 2
Ž
Ž .
121.1 3
C 14 –C 15 –C 16
Ž
Ž .
C 15 –C 16 –C 11
120.7 3
Ž
Ž .
117.5 2
C 16 –C 11 –C 12
Ž
.
.
Ž
Ž
.
.
Ž .
Ž .
Ž .
119.6 2
C 16 –C 11 –N 1
Ž .
122.9 2
Ž
C 12 –C 11 –N 1
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž .
Ž .
120.8 3
C 17 –C 18 –C 19
119.6 3
Ž
C 20 –C 19 –C 18
Ž
Ž .
C 19 –C 20 –C 21
120.2 3
Ž
Ž .
119.7 3
C 20 –C 21 –C 22
Ž
Ž .
C 17 –C 22 –C 21
121.1 3
Ž
Ž .
118.6 2
C 22 –C 17 –C 18
Ž
.
.
Ž
Ž
.
.
Ž .
Ž .
Ž .
121.7 2
C 22 –C 17 –N 1
Ž .
119.7 2
Ž
C 18 –C 17 –N 1
Ž . Ž .
Ž
Ž
.
.
Ž .
N 4 –C 23 –N 2
Ž . Ž .
131.5 2
Ž .
121.9 2
N 4 –C 23 –N 3
Ž . Ž .
Ž
Ž
.
.
Ž .
N 2 –C 23 –N 3
Ž . Ž .
106.6 2
Ž .
173.2 2
N 4 –C 23 –Zr 1
Ž . Ž .
Ž
.
Ž
.
N 2 –C 23 –Zr 1
54.07 11

(
)
18
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Ž
.
Table 6 continued .
Ž . Ž .
Ž
.
Ž .
52.60 11
Ž .
120.5 3
N 3 –C 23 –Zr 1
Ž
.
Ž
.
Ž
.
C 26 –C 25 –C 24
Ž
.
.
Ž
Ž
.
.
Ž .
Ž .
Ž .
89.7 2
C 26 –C 25 –Li 1
102.1 2
Ž .
Ž
C 24 –C 25 –Li 1
Ž
.
.
.
.
Ž
Ž
Ž
Ž
.
.
.
.
Ž
Ž
Ž
Ž
.
.
.
.
Ž .
C 27 –C 26 –C 25
120.6 3
Ž .
119.4 3
Ž
C 26 –C 27 –C 28
Ž
Ž .
C 27 –C 28 –C 29
120.7 3
Ž
Ž .
120.6 3
Ž .
119.2 2
C 28 –C 29 –C 24
Ž .
Ž
.
Ž
.
C 29 –C 24 –N 3
Ž
.
Ž
.
Ž
.
Ž .
118.2 2
Ž .
122.5 2
Ž .
121.4 2
C 29 –C 24 –C 25
Ž .
Ž
.
Ž
.
N 3 –C 24 –C 25
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
C 32 –C 31 –C 30
Ž
Ž .
C 33 –C 32 –C 31
119.8 3
Ž
Ž .
119.8 2
C 32 –C 33 –C 34
Ž
Ž .
C 35 –C 34 –C 33
120.0 3
Ž
Ž .
121.0 2
Ž .
118.0 2
C 34 –C 35 –C 30
Ž
C 31 –C 30 –C 35
Ž
.
.
Ž
Ž
.
.
Ž .
Ž .
Ž .
122.1 2
C 31 –C 30 –N 2
Ž .
119.9 2
Ž
C 35 –C 30 –N 2
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž .
Ž .
121.6 5
C 38 –C 37 –C 36
120.4 4
Ž
C 39 –C 38 –C 37
Ž
Ž .
C 38 –C 39 –C 40
119.5 4
Ž
Ž .
120.1 4
Ž .
120.8 4
Ž .
117.6 3
C 39 –C 40 –C 41
Ž
C 36 –C 41 –C 40
Ž
C 41 –C 36 –C 37
Ž
.
.
Ž
Ž
.
.
Ž .
Ž .
119.0 3
Ž .
123.1 3
C 41 –C 36 –N 4
Ž .
Ž
C 37 –C 36 –N 4
Ž
.
.
Ž
.
Ž .
Ž .
C 41 –C 36 –Li 1
Ž .
89.3 2
Ž .
133.7 2
Ž
Ž .
C 37 –C 36 –Li 1
Ž . Ž .
Ž
.
.
Ž .
43.0 2
Ž .
106.2 3
N 4 –C 36 –Li 1
Ž . Ž .
O 1 –C 42 –C 43
Ž
Ž
.
.
Ž
Ž
.
.
Ž
Ž
.
.
Ž .
C 44 –C 43 –C 42
107.2 3
Ž
Ž .
C 43 –C 44 –C 45
107.0 3
Ž .
Ž .
Ž
.
.
Ž
Ž
.
.
O 1 –C 45 –C 44
106.8 3
Ž .
Ž
Ž .
105.4 3
O 2 –C 46 –C 47
Ž
.
.
Ž
Ž
.
.
Ž
Ž
.
.
Ž .
C 48 –C 47 –C 46
104.0 4
Ž .
107.9 4
Ž
C 49 –C 48 –C 47
Ž .
Ž
.
Ž
.
Ž .
108.0 4
O 2 –C 49 –C 48
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž .
C 102 –C 101 –C 106
120.0 7
Ž .
120.6 6
Ž
C 103 –C 102 –C 101
Ž
Ž .
C 104 –C 103 –C 102
121.3 5
Ž
Ž .
C 103 –C 104 –C 105
120.0 7
Ž .
Ž
C 106 –C 105 –C 104
119.2 7
Ž .
118.8 6
Ž
C 101 –C 106 –C 105
)([ (
) ])
(
) (
) ( )
4.3. Cp C NPh 3 ZrCl NPh2 Li THF 2 4
Ž
.
Ž
.
To a THF solution of 3 0.084 g, 0.113 mmol , a solution of LiNPh2 0.020 g, 0.113 mmol was
added and the reaction mixture was stirred for 30 min at which time the solvent was replaced with
C6D6 and filtered. This bright yellow solution was used to acquire the 1H and 13C NMR spectroscopy
data. Allowing the solvent to evaporate inside a nitrogen containing glove box overnight gave X-ray
quality crystals which were also used for elemental analysis. A deuterated benzene molecule of
recrystallization was determined by both X-ray and elemental analysis. The added THF-d8 displaced

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
19
Table 7
2
3
) 2
Anisotropic displacement parameters A =10 for 4. The anisotropic displacement factor exponent takes the form: y2p 2 ha U11
˚
Ž
.
wŽ
.
q . . . q2hka) b)U12
x
U11
U22
U33
U23
U13
y7 1
U12
Ž .
Zr 1
Ž .
22 1
37 2
Ž .
49 1
23 1
Ž .
26 1
24 1
Ž .
30 1
42 1
Ž .
44 1
32 1
Ž .
44 2
31 1
Ž .
25 1
35 2
Ž .
30 1
32 1
Ž .
26 1
28 1
Ž .
28 1
39 1
Ž .
45 1
57 2
Ž .
33 1
56 2
Ž .
22 1
51 3
Ž .
40 1
27 1
Ž .
29 1
27 1
Ž .
37 1
52 1
Ž .
54 1
26 1
Ž .
28 1
33 1
Ž .
0 1
Ž .
Ž .
Ž .
Ž .
Ž .
1 1
Ž .
Ž .
1 1
Ž .
Ž .
Ž .
Ž .
Li 1
y1 2
y8 1
y10 2
y3 2
Ž .
Cl 1
Ž .
y17 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
N 1
2 1
y8 1
2 1
Ž .
N 2
Ž .
Ž .
Ž .
Ž .
Ž .
0 1
y1 1
y11 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
N 3
y2 1
y11 1
2 1
Ž .
N 4
Ž .
Ž .
3 1
Ž .
5 1
y1 1
y17 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
O 1
4 1
y10 1
Ž .
O 2
Ž .
Ž .
Ž .
y6 1
y11 1
y3 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
y5 1
C 1
8 1
y8 1
Ž .
C 2
Ž .
7 1
Ž .
Ž .
Ž .
1 1
Ž .
y8 1
Ž .
Ž .
Ž .
Ž .
Ž .
C 3
13 1
Ž .
11 1
y9 1
y7 1
Ž .
C 4
Ž .
49 2
Ž .
54 2
Ž .
26 1
Ž .
Ž .
20 1
8 1
Ž .
Ž .
Ž .
41 2
Ž .
Ž .
149 4
Ž .
Ž .
45 2
Ž .
Ž .
39 2
Ž .
y7 1
Ž .
C 5
73 2
45 2
20 1
3 1
y10 1
Ž .
C 6
Ž .
Ž .
y16 2
y20 2
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
8 2
C 7
108 3
34 2
47 2
9 1
y13 2
Ž .
C 8
Ž .
C 9
Ž .
62 2
Ž .
91 3
Ž .
135 4
Ž .
101 3
Ž .
64 2
Ž .
55 2
Ž .
47 2
Ž .
25 2
Ž .
Ž .
y34 2
y57 2
Ž .
Ž .
64 3
28 2
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
196 6
Ž .
69 3
Ž .
32 2
Ž .
Ž .
Ž .
Ž .
4 1
C 10
y2 2
y35 3
y43 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
C 12
29 1
41 1
28 1
1 1
y6 1
Ž
Ž .
44 2
Ž .
46 2
Ž .
29 1
Ž .
6 1
Ž .
y11 1
Ž .
C 13
7 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y6 1
Ž .
4 1
C 14
49 2
46 2
33 1
11 1
Ž
Ž .
35 1
Ž .
45 2
Ž .
44 2
Ž .
7 1
Ž .
y5 1
Ž .
C 15
y5 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y11 1
Ž .
y4 1
C 16
30 1
42 1
38 1
6 1
Ž
Ž .
27 1
Ž .
28 1
Ž .
27 1
Ž .
Ž .
y6 1
Ž .
4 1
C 11
y1 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y14 1
Ž .
C 18
36 1
51 2
36 1
4 1
y2 1
Ž
Ž .
33 2
Ž .
90 3
Ž .
40 2
Ž .
4 2
Ž .
y17 1
Ž .
0 2
C 19
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y16 1
Ž .
C 20
39 2
79 2
55 2
17 2
15 2
Ž
Ž .
51 2
Ž .
55 2
Ž .
63 2
Ž .
6 2
Ž .
y17 2
Ž .
22 2
C 21
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y15 1
Ž .
C 22
41 2
45 2
45 2
1 1
10 1
Ž
Ž .
24 1
Ž .
41 1
Ž .
28 1
Ž .
4 1
Ž .
y7 1
Ž .
4 1
C 17
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y7 1
Ž .
C 23
24 1
28 1
25 1
y2 1
2 1
Ž
Ž .
38 1
Ž .
35 1
Ž .
34 1
Ž .
y9 1
Ž .
y12 1
Ž .
5 1
C 25
Ž
Ž .
Ž .
Ž .
Ž .
y16 1
Ž .
y27 2
Ž .
C 26
70 2
35 2
45 2
9 1
Ž
Ž .
79 2
Ž .
40 2
Ž .
74 2
Ž .
y15 2
Ž .
y49 2
Ž .
y4 2
C 27
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y44 2
Ž .
y3 1
C 28
51 2
52 2
82 2
y14 2
Ž
Ž .
35 1
Ž .
37 1
Ž .
52 2
Ž .
Ž .
y23 1
Ž .
1 1
C 29
y7 1
Ž
Ž .
Ž .
Ž .
Ž .
y1 1
Ž .
y14 1
Ž .
C 24
32 1
27 1
27 1
0 1
Ž
Ž .
33 1
Ž .
37 1
Ž .
38 1
Ž .
3 1
Ž .
y14 1
Ž .
y7 1
C 31
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y24 1
Ž .
y9 1
C 32
37 1
46 2
53 2
y2 1
Ž
Ž .
51 2
Ž .
53 2
Ž .
43 2
Ž .
Ž .
y29 1
Ž .
4 1
C 33
y13 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y17 1
Ž .
C 34
51 2
51 2
30 1
y3 1
1 1
Ž
Ž .
33 1
Ž .
37 1
Ž .
32 1
Ž .
Ž .
Ž .
y1 1
C 35
1 1
y9 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
2 1
C 30
26 1
27 1
29 1
y4 1
y12 1
Ž
Ž .
39 2
Ž .
44 2
Ž .
82 2
Ž .
y13 2
Ž .
y28 2
Ž .
C 37
6 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y65 3
Ž .
20 2
C 38
51 2
66 2
169 5
y41 3
Ž
Ž .
100 4
Ž .
87 3
Ž .
175 6
Ž .
Ž .
y110 4
Ž .
C 39
y49 4
44 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y98 4
Ž .
51 3
C 40
148 5
70 3
100 4
y31 3
Ž
Ž .
84 2
Ž .
47 2
Ž .
54 2
Ž .
Ž .
y41 2
Ž .
C 41
y12 2
23 2
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y29 1
Ž .
13 1
C 36
45 2
29 1
50 2
y13 1
Ž
Ž .
55 2
Ž .
58 2
Ž .
57 2
Ž .
1 2
Ž .
y1 2
Ž .
C 42
12 2
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y10 3
Ž .
15 2
C 43
50 2
93 3
136 5
44 3
Ž
Ž .
74 3
Ž .
64 2
Ž .
84 3
Ž .
37 2
Ž .
84 3
Ž .
68 2
Ž .
6 2
Ž .
11 2
Ž .
y28 2
Ž .
C 44
31 2
Ž
Ž .
y18 2
Ž .
0 1
C 45

(
)
20
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Ž
.
Table 7 continued .
U11
U22
U33
U23
U13
U12
Ž
.
.
.
.
Ž .
69 2
Ž .
54 2
Ž .
66 2
Ž .
y1 2
Ž .
y14 2
Ž .
y17 2
C 46
Ž
Ž .
Ž .
Ž .
Ž .
5 3
Ž .
Ž .
y34 3
C 47
58 3
115 4
111 4
y19 3
Ž
Ž .
56 3
Ž .
110 4
Ž .
173 6
Ž .
Ž .
Ž .
7 3
C 48
y36 4
15 3
Ž
Ž .
Ž .
Ž .
Ž .
y32 2
Ž .
8 2
Ž .
C 49
77 3
86 3
74 3
3 2
Ž
.
.
.
.
.
.
Ž .
105 4
Ž .
136 5
Ž .
148 6
Ž .
Ž .
Ž .
y45 4
C 101
y65 5
y20 4
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
y6 2
C 102
65 3
96 4
131 5
y49 3
y11 3
Ž
Ž .
97 3
Ž .
65 3
Ž .
57 2
Ž .
Ž .
Ž .
y4 2
C 103
y13 2
y1 2
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
56 5
C 104
168 7
Ž
145 6
86 4
1 4
y52 4
Ž
.
Ž .
135 7
Ž .
62 3
Ž .
128 7
Ž .
109 5
Ž .
10 5
Ž .
y37 3
Ž .
y22 6
Ž .
C 105
221 10
Ž .
112 7
Ž
Ž .
Ž .
y10 4
C 106
201 9
38 5
the coordinated THFs. 1H NMR d C6D6rTHF-d8; 1:1 7.24–6.26 m, 25H, phenyls , 1.55
Ž
.
Ž
.
13
Ž
Ž
. .
Ž
.
Ž
w
x
.
C5 C H3 5
.
C NMR C6D6rTHF-d8; 1:1 : d 163.9 C6H6N C ,153.8, 152.7, 150.1, 128.7,
127.8, 127.5, 124.0, 122.5, 120.9, 118.6, 116.03, C6H5N C, C5 CH3 5
C5 CH3 5. Anal. Calcd for ZrC49H56ClLiN4O2C6D6: C, 69.47; H, 6.59; N, 5.89; Found: C, 68.84;
3
Ž
w
x
Ž
.
Ž
.
.
,
C6H5 2 N , 11.5
3
Ž
Ž
.
H, 6.50; N, 5.94.
Table 8
Crystallographic data for 5
Crystal parameters
Chemical formula
Formula weight
Crystal system
TaC31H36 N3
619.58
monoclinic
Ž
.
Ž
.
Space group No.
Z
C2rc a9
8
˚
Ž
.
Ž .
31.2878 4
a A
˚
Ž
Ž
.
.
Ž .
7.9181 1
Ž .
23.003 3
b A
˚
c A
Ž .
Ž .
Ž .
2483.2 4
b
8 .
101.687 1
3
˚
Ž
.
Volume A
rcalc g cm
Crystal dimens. mm
Temperature 8C
y3
Ž
.
1.480
3
Ž
.
.
0.20=0.40=0.20
y50
Ž
Measurement of intensity data
Diffractometer
Radiation
Siemens SMART
˚
Mo, 0.71073 A
Ž .
2u range, 8
3.4–56.0
30025
13565
No. of data collected
No. of unique data
Ž
Ž
..
Ž
No. of observed data Fo )3s Fo
4575
0.0415
.
Agreement between equivalent data Rint
No. of parameters varied
316
39.5
y1
Ž
.
m mm
Absorption correction
Range of trans. factors
semiempirical
0.5900–0.8840
0.042, 0.039
1.85
Ž
.
Ž
. Ž
Ž
..
R1 Fo , wR2 Fo , Fo )3s Fo
Goodness of fit

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
21
)[ (
4.4. Cp C NPh 3 TaMe2
) ]
( )
5
Ž
.
Ž
.
A THF solution of 2 0.835 g, 1.88 mmol was added to a benzene:THF 9:1 solution of
)
Ž
. Ž
.
Cp TaMe2Cl OSO3CF3 1.0 g, 1.88 mmol . The reaction was stirred for 45 min at which point the
solvent was replaced with diethyl etherrtoluene 9:1 . The resulting mixture was filtered and the
solvent removed to give a red-orange solid. The solid was then washed with pentane and placed under
Ž
.
1
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
vacuum to give 1.02 g 86% of product. H NMR d C6D6 6.99 b, 8H , 6.94 t, 2H , 6.84 d, 2H ,
6.81 t, 2H , 6.61 t, 1H C6 H5N C ,1.60 s, 15H, C5 C H3 5 , 0.39 s, 6H, Ta Me2 . 13C NMR
Ž
.
Ž
. Ž
w
x
.
Ž
Ž
. .
Ž
.
3
Ž
.
Ž
w
x
.
C6D6 147.6 C6H5N C , 153.0, 149.4, 127.9, 127.8, 127.0, 126.8, 124.0, 123.7, 123.2, 123.0
120.9, 120.1 C6H5N C, C5 CH3 5 , 69.0 Ta CH3 2, 11.2 C5 CH3 5
3
Ž
w
x
Ž
. .
Ž
.
Ž
Ž
. .
.
3
4.5. Ethylene polymerization
Ž
.
Ž
.
Compound 3 0.020 g was activated with methylalumoxane MAO, 6.4 wt% Al and stirred for 10
min. The reaction flask was then evacuated and 2 atm of ethylene were introduced. The reaction is
Table 9
Positional parameters and BisorBeq for 5
Atom
x
y
z
Beq
Ž .
N 1
Ž .
0.088312 8
Ž .
0.1122 2
Ž .
0.20691 3
Ž .
0.1406 6
Ž .
0.44096 1
Ž .
0.5308 2
Ž .
2.521 5
Ž .
2.8 1
Ta 1
Ž .
Ž .
N 3
Ž .
0.1638 2
Ž .
0.1324 2
Ž .
y0.0953 6
Ž .
0.5523 2
Ž .
0.4572 2
Ž .
2.7 1
Ž .
2.4 1
N 2
Ž .
Ž .
0.0114 6
Ž .
C 2
Ž .
0.1341 2
Ž .
0.0916 2
Ž .
Ž .
0.5153 7
Ž .
0.4423 3
Ž .
0.4324 3
Ž .
2.7 1
Ž .
3.2 2
C 1
Ž .
0.4469 7
Ž .
C 4
Ž .
0.0683 2
Ž .
0.0976 3
Ž .
Ž .
0.3592 9
Ž .
0.3767 3
Ž .
0.3507 3
Ž .
3.8 2
Ž .
4.0 2
C 3
Ž .
0.4572 8
Ž .
Ž .
0.1380 2
Ž .
Ž .
0.4815 8
Ž .
0.6368 8
Ž .
0.3907 3
Ž .
3.3 2
C 5
0.3521 8
Ž .
Ž .
Ž .
Ž .
C 6
Ž .
0.1713 2
0.4927 3
3.8 2
Ž .
0.0752 2
Ž .
0.4732 4
Ž .
4.8 2
C 7
Ž .
C 9
Ž .
Ž .
0.0874 4
Ž .
0.509 1
Ž .
0.287 1
Ž .
Ž .
0.2887 3
Ž .
Ž .
7.1 3
C 8
Ž .
0.0237 3
0.3481 4
6.5 3
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
0.0329 2
Ž .
0.2832 9
Ž .
Ž .
0.4798 3
Ž .
Ž .
4.0 2
C 10
0.1794 3
0.3780 4
4.7 2
Ž
Ž .
C 11
0.2777 9
Ž
Ž .
Ž .
0.0605 8
Ž .
Ž .
C 12
0.0408 2
0.3765 3
3.7 2
Ž
Ž .
0.0998 2
Ž .
Ž .
0.5865 3
Ž .
3.2 2
C 13
0.1624 8
Ž
Ž .
Ž
.
.
Ž .
Ž .
C 14
0.0824 2
0.0325 10
0.6141 3
4.3 2
Ž
Ž .
0.0711 3
Ž .
0.061 1
Ž .
0.216 2
Ž .
0.6687 4
Ž .
6.2 3
C 15
Ž
Ž .
Ž .
Ž .
C 16
0.0766 3
0.6945 4
7.9 3
Ž
Ž .
0.0928 3
Ž .
Ž .
0.6668 4
Ž .
7.0 3
C 17
0.346 1
Ž
Ž .
Ž .
Ž .
Ž .
C 18
0.1051 3
0.3212 9
Ž .
0.6124 3
4.7 2
Ž
Ž .
0.1765 2
Ž .
0.6145 2
Ž .
2.5 1
C 19
y0.0810 8
Ž
Ž .
Ž .
Ž .
Ž .
C 20
0.1744 2
y0.2232 8
0.6491 3
3.2 1
Ž
Ž .
0.1891 2
Ž
Ž .
0.7105 3
Ž .
4.1 2
C 21
y0.2149 10
Ž
Ž .
Ž .
Ž .
Ž .
C 22
0.2059 3
y0.067 1
0.7372 3
4.4 2
Ž
Ž .
0.2089 2
Ž .
Ž .
0.7026 3
Ž .
4.2 2
C 23
0.0740 9
Ž .
0.0673 8
Ž
Ž .
Ž .
Ž .
C 24
0.1947 2
0.6419 3
3.3 2
Ž
Ž .
0.1603 2
Ž .
Ž .
0.4265 2
Ž .
2.4 1
C 25
y0.0832 7
Ž
Ž .
Ž .
Ž .
Ž .
C 26
0.2048 2
y0.1001 7
0.4477 3
2.8 1
Ž
Ž .
0.2301 2
Ž .
y0.1879 8
Ž .
0.4142 3
Ž .
3.2 1
C 27
Ž
Ž .
Ž .
y0.2574 7
Ž .
Ž .
C 28
0.2105 2
0.3600 3
3.4 2
Ž
Ž .
0.1664 2
Ž .
y0.2398 8
Ž .
0.3392 3
Ž .
3.2 2
C 29
Ž
Ž .
Ž .
Ž .
Ž .
C 30
0.1413 2
y0.1538 8
Ž .
0.3721 3
2.8 1
Ž
Ž .
0.1393 2
Ž .
0.5195 3
Ž .
2.4 1
C 31
0.0093 7

(
)
22
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
quenched with 100 ml of a 10% HCl methanolic solution. After stirring this mixture for 6 h, the solid
Ž
.
polyethylene PE, Tm s1258C is filtered, washed four times with methanol, and dried to constant
Ž
.
weight 2.95 g .
4.6. Structure determination of 4 and 5
Slow evaporation of a benzene solution for 4 and an ether solution for 5 afforded crystals that were
suitable for X-ray diffraction. Fragments of both 4 and 5 were cut and mounted on glass fibers under
Paratone-8277 and placed on the X-ray diffractometer in a cold nitrogen stream supplied by a
Siemens LT-2A low temperature device. The X-ray intensity data were collected on a standard
Siemens SMART-CCD Area Detector System equipped with a normal focus molybdenum-target
Ž
.
X-ray tube operated at 1.5 kW 50 kV, 30 mA . A total of 1.3 hemispheres of data were collected
using a narrow frame method with scan widths of 0.38 in v, and exposure times of 10 srframe.
˚
˚
Frames were integrated to 0.75 A for 4 and 0.90 A for 5 with the Siemens SAINT program yielding a
total of 15510 reflections for 4 and 30025 reflections for 5. The unit cell parameters were based upon
the least-squares refinement of three dimensional centroids of 10980 reflections and 4575 reflections
at y508C for 4 and 5, respectively. The space groups were assigned on the basis of systematic
Ž
w x.
absences by using the XPREP program SHELXTL 5.04 42 . The structure of 4 was solved by direct
Ž
.
methods SHELXTL and the structure of 5 was determined by heavy-atom Patterson methods
TEXSAN 43 . Both structures were refined by full-matrix least-squares on F . All non-hydrogen
atoms for both structures were refined with anisotropic thermal parameters. H atoms were included in
2
Ž
w x.
Table 10
Intramolecular distances involving the nonhydrogen atoms of 5
Atom
Ž .
Atom
Ž .
Distance
Ž .
Atom
Ž .
Atom
Distance
Ž .
Ž .
1.51 1
Ž .
1.488 9
Ž .
1.376 9
Ž .
1.387 9
Ž .
Ta 1
N 1
2.116 5
C 4
C 5
Ž .
1.41 1
Ž .
Ž .
Ž .
Ž .
Ta 1
Ž .
N 3
Ž .
2.058 5
Ž .
C 4
Ž .
C 9
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ta 1
C 1
2.377 6
C 5
C 10
Ž .
Ž .
Ž .
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
Ta 1
Ž .
C 2
Ž .
2.454 6
Ž .
C 13
C 14
Ž
Ž
Ta 1
C 3
2.476 6
C 13
C 18
Ž .
Ž .
Ž .
Ž
Ž
Ž .
Ta 1
C 4
Ž .
2.469 6
C 14
C 15
1.39 1
Ž .
Ž .
Ž
Ž
Ž .
1.36 1
Ž .
1.36 1
Ta 1
Ž .
C 5
2.410 6
Ž .
C 15
C 16
Ž
.
.
.
.
.
.
.
.
Ž
Ž
Ta 1
C 11
2.178 7
C 16
C 17
Ž .
Ž
Ž .
Ž
Ž
Ž .
Ta 1
C 12
2.205 7
C 17
C 18
1.39 1
Ž .
Ž
Ž .
Ž
Ž
Ž .
1.389 8
Ž .
1.398 8
N 1
Ž .
C 13
1.425 7
Ž .
C 19
C 20
Ž
Ž
Ž
N 1
C 31
1.398 7
C 19
C 24
Ž .
Ž
Ž .
Ž
Ž
Ž .
N 2
C 19
1.409 7
C 20
C 21
1.394 9
Ž .
N 2
Ž
Ž .
1.268 7
Ž
Ž
C 22
Ž .
1.38 1
C 31
C 21
Ž .
Ž
Ž .
Ž
Ž
Ž .
N 3
C 25
1.437 7
C 22
C 23
1.386 9
Ž .
Ž
Ž .
Ž
Ž
Ž .
1.378 9
Ž .
1.386 8
Ž .
1.390 8
Ž .
1.397 8
N 3
Ž .
C 31
Ž .
1.407 7
Ž .
C 23
C 24
Ž
Ž
C 1
C 2
1.412 8
C 25
C 26
Ž .
Ž .
Ž .
Ž
Ž
C 1
Ž .
C 5
Ž .
1.429 8
Ž .
C 25
C 30
Ž
Ž
C 1
C 6
1.493 9
C 26
C 27
Ž .
Ž .
Ž .
Ž
Ž
Ž .
C 2
C 3
1.417 9
C 27
C 28
1.387 9
Ž .
C 2
Ž .
C 7
Ž .
1.505 9
Ž .
1.421 9
Ž .
1.48 1
Ž
Ž
Ž .
1.373 9
Ž .
1.375 8
C 28
C 29
Ž .
Ž .
Ž
Ž
C 3
Ž .
C 4
Ž .
C 29
C 30
C 3
C 8
Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
23
Table 11
Intramolecular bond angles involving the nonhydrogen atoms of 5
Atom Atom Atom Angle
Ž . Ž . Ž . Ž .
Atom
Ž .
Atom
Ž .
Atom
Angle
Ž .
Ž .
56.0 2
Ž .
85.0 3
Ž .
88.0 2
Ž .
33.5 2
Ž .
N 1 Ta 1 N 3 62.9 2
C 3
Ta 1
C 4
Ž .
33.4 2
Ž . Ž . Ž . Ž .
Ž .
Ž .
N 1 Ta 1 C 1 95.3 2
C 3
Ž .
Ta 1
Ž .
C 5
Ž . Ž . Ž . Ž .
Ž
.
.
N 1 Ta 1 C 2 108.2 2
C 3
Ta 1
C 11
Ž . Ž . Ž . Ž .
Ž .
Ž .
Ž
N 1 Ta 1 C 3 141.1 2
C 3
Ž .
Ta 1
Ž .
C 12
Ž .
Ž . Ž . Ž . Ž .
N 1 Ta 1 C 4 149.7 2
C 4
Ta 1
C 5
Ž . Ž . Ž . Ž .
Ž .
C 4
Ž .
Ta 1
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
82.5 3
N 1 Ta 1 C 5 116.8 2
C 4
Ž .
Ta 1
Ž .
C 11
117.3 3
Ž .
Ž . Ž . Ž .
Ž
.
.
Ž
N 1 Ta 1 79.4 2
C 11
C 12
Ž . Ž . Ž .
Ž
Ž .
Ž .
Ž
Ž .
N 1 Ta 1 125.7 2
C 12
C 5
Ž .
Ta 1
C 11
135.9 2
Ž . Ž . Ž .
Ž .
Ž .
Ta 1
Ž
C 12
Ž .
109.9 2
N 3 Ta 1 102.6 2
C 1
C 5
Ž . Ž . Ž .
Ž .
Ž
.
Ž .
Ž
Ž .
N 3 Ta 1 136.5 2
C 2
C 11
Ž .
Ta 1
C 12
85.8 3
Ž . Ž . Ž .
Ž .
Ž .
Ž
Ž .
N 3 Ta 1 142.1 2
C 3
Ta 1
Ž .
N 1
Ž .
C 13
137.9 4
Ž .
Ž . Ž . Ž .
Ž .
Ž
N 3 Ta 1 109.3 2
C 4
Ta 1
N 1
C 31
96.4 3
Ž . Ž . Ž .
Ž .
Ž
.
.
Ž .
Ž
Ž .
N 3 Ta 1 88.3 2
C 5
C 13
N 1
C 31
122.9 5
Ž . Ž . Ž .
Ž
.
Ž
Ž .
N 2
Ž
C 31
Ž .
124.3 5
N 3 Ta 1 132.8 2
C 11
C 19
Ž .
Ž . Ž . Ž .
Ž
.
Ž .
Ž
Ž .
N 3 Ta 1 93.6 2
C 12
Ta 1
N 3
C 25
139.0 4
Ž . Ž . Ž .
Ž .
Ž .
Ta 1
Ž .
Ž
Ž .
98.8 3
Ž .
120.8 5
C 1 Ta 1 33.9 2
C 2
N 3
Ž .
C 31
Ž . Ž . Ž .
Ž .
Ž
.
Ž
C 1 Ta 1 56.4 2
C 3
C 25
N 3
C 31
Ž . Ž . Ž .
Ž .
Ž .
Ta 1
Ž .
Ž .
C 1
Ž .
C 5
Ž .
Ž .
73.9 3
C 1 Ta 1 56.4 2
C 4
Ta 1
Ž .
C 1
C 2
Ž .
76.0 4
Ž . Ž . Ž .
Ž .
C 1 Ta 1 34.7 2
C 5
Ž . Ž . Ž .
Ž
.
Ž .
C 2
Ž .
Ž .
C 1
Ž .
C 5
Ž .
Ž .
107.7 6
C 1 Ta 1 108.5 2
C 11
Ta 1
Ž .
C 1
C 6
Ž .
122.0 4
Ž . Ž . Ž .
Ž
.
C 1 Ta 1 138.7 2
C 12
Ž . Ž . Ž .
Ž .
Ž .
C 5
Ž .
C 1
Ž .
C 6
Ž .
128.0 6
Ž .
123.9 6
C 2 Ta 1 33.4 2
C 3
C 2
Ž .
C 1
Ž .
C 6
Ž .
Ž . Ž . Ž .
Ž .
C 2 Ta 1 55.4 2
C 4
Ž . Ž . Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
C 2 Ta 1 56.3 2
C 5
Ta 1
Ž .
C 2
Ž .
C 1
Ž .
70.1 3
Ž .
74.2 4
Ž . Ž . Ž .
Ž
.
.
C 2 Ta 1 80.0 2
C 11
Ta 1
Ž .
C 2
Ž .
C 3
Ž .
Ž . Ž . Ž .
Ž
Ž .
124.1 4
Ž .
120.2 8
C 2 Ta 1 120.2 2
C 12
Ta 1
C 2
C 7
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
C 1 C 2 108.5 6
C 3
C 15
C 16
C 16
C 17
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
C 1 C 2 125.0 6
C 7
C 17
C 18
120.8 9
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
C 3 C 2 126.5 7
C 7
C 13
Ž .
C 18
C 17
118.6 8
Ž .
Ž . Ž . Ž .
Ž .
Ž
Ž
Ta 1 C 3 72.4 4
C 2
N 2
Ž .
C 19
C 20
118.7 5
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
Ta 1 C 3 73.0 4
C 4
N 2
C 19
C 24
122.0 5
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž .
119.0 6
Ž .
119.9 6
Ta 1 C 3 126.3 5
C 8
C 20
C 19
C 20
C 21
C 22
C 19
C 19
C 24
Ž . Ž . Ž .
Ž .
Ž
Ž
C 2 C 3 107.5 6
C 4
C 20
C 21
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
C 2 C 3 125.3 7
C 8
C 21
C 22
120.7 6
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
C 4 C 3 126.7 7
C 8
C 22
C 23
119.6 6
Ž .
Ž . Ž . Ž .
Ž .
Ž
Ž
Ta 1 C 4 73.6 4
C 3
C 23
C 24
120.3 7
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
Ta 1 C 4 70.9 4
C 5
C 24
C 23
120.5 6
Ž . Ž . Ž .
Ž .
Ž .
Ž
Ž
Ž .
122.9 5
Ž .
117.5 5
Ta 1 C 4 124.9 5
C 9
N 3
Ž .
C 25
C 26
Ž . Ž . Ž .
Ž .
Ž
Ž
C 3 C 4 108.5 6
C 5
N 3
C 25
C 30
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž
Ž
Ž
Ž
.
.
.
.
.
.
Ž
Ž
Ž .
C 3 C 4 124.9 8
C 9
C 26
C 25
C 26
C 27
C 25
C 30
119.5 5
Ž .
Ž . Ž . Ž .
Ž .
Ž
Ž
C 5 C 4 126.4 7
C 9
C 26
C 27
119.6 5
Ž .
Ž . Ž . Ž .
Ž .
Ž
Ž
Ta 1 C 5 71.4 3
C 1
C 27
C 28
119.9 6
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
120.2 6
Ž .
120.3 6
Ta 1 C 5 75.6 4
C 4
C 28
C 29
Ž . Ž . Ž .
Ž
.
Ž
Ž
Ta 1 C 5 126.3 4
C 10
C 28
C 29
C 30
Ž . Ž . Ž .
Ž .
Ž
Ž
Ž .
C 1 C 5 107.8 6
C 4
C 25
Ž .
C 30
C 29
Ž .
120.5 6
Ž . Ž . Ž .
Ž
.
.
.
.
.
Ž
Ž .
133.8 5
C 1 C 5 125.5 7
C 10
N 1
C 31
N 2
Ž . Ž . Ž .
Ž
Ž .
Ž
Ž .
Ž .
C 4 C 5 126.0 7
C 10
N 1
Ž .
C 14
C 31
N 3
Ž .
101.9 5
Ž .
Ž
.
.
.
Ž
Ž .
Ž
Ž .
N 1 122.0 6
C 13
C 14
N 2
C 31
N 3
124.3 5
Ž .
Ž .
Ž
Ž
Ž .
Ž
Ž
.
.
Ž
Ž
.
.
N 1
C 13
C 18
117.7 6
C 13
C 18
120.3 6
Ž .
120.7 9
Ž
.
Ž
Ž
Ž .
119.4 8
Ž
Ž
C 13
C 14
C 15
C 14
C 15
C 16
Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

(
)
24
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
idealized positions for both structures. Data collection and refinement parameters for 4 and 5 are
given in Table 3. Additional information is given in Appendices A and B.
Acknowledgements
The authors are grateful to Exxon Corporation for financial support and to Dr. Rene Lachicotte for
assistance with the crystallographic studies.
Table 12
Anisotropic displacement parameters for 5
Atom
U11
U22
U33
0.0376 1
U12
0.0011 1
U13
0.00546 9
U23
0.0019 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ta 1
Ž .
0.0280 1
0.043 3
Ž .
0.041 3
0.029 3
Ž .
0.036 4
0.046 4
0.0297 1
0.030 3
Ž .
0.033 3
0.032 3
Ž .
0.026 3
0.021 3
Ž .
Ž .
Ž .
N 1
0.036 3
0.008 2
0.014 3
y0.001 2
Ž .
Ž .
0.027 3
Ž .
0.004 2
Ž .
0.006 2
Ž .
N 2
Ž .
y0.001 2
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
y0.004 2
N 3
0.031 3
0.000 2
0.005 2
Ž .
Ž .
0.041 4
Ž .
0.056 4
Ž .
y0.001 3
Ž .
0.012 3
Ž .
0.012 4
Ž .
0.002 3
C 1
Ž .
Ž .
Ž .
Ž .
0.004 3
Ž .
0.004 3
C 2
Ž .
C 4
Ž .
0.044 4
Ž .
0.069 5
Ž .
0.042 4
Ž .
0.044 4
Ž .
0.053 4
Ž .
0.040 4
Ž .
Ž .
0.005 4
Ž .
y0.004 4
Ž .
0.015 3
Ž .
0.012 3
C 3
Ž .
0.000 3
Ž .
0.017 4
Ž .
Ž .
0.048 4
Ž .
0.030 3
Ž .
0.055 4
Ž .
Ž .
Ž .
0.005 4
Ž .
0.009 3
C 5
y0.001 3
0.028 4
Ž .
Ž .
Ž .
Ž .
Ž .
y0.010 3
Ž .
C 6
Ž .
0.042 4
0.039 4
0.061 5
0.000 3
Ž .
0.059 5
Ž .
0.030 4
Ž .
0.105 6
Ž .
0.008 4
Ž .
Ž .
y0.006 4
C 7
0.043 5
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
y0.008 5
Ž .
0.034 5
C 8
Ž .
0.066 6
0.079 6
0.092 7
0.014 5
Ž .
0.130 9
Ž .
0.070 5
Ž .
0.109 7
Ž .
0.047 4
Ž .
0.029 4
Ž .
0.076 5
Ž .
y0.019 7
Ž .
0.008 5
Ž .
C 9
0.005 5
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
0.003 4
Ž .
0.047 5
Ž .
0.009 4
C 10
Ž
Ž .
0.031 4
Ž .
0.054 4
Ž .
0.071 5
Ž .
Ž .
0.005 3
Ž .
0.015 3
Ž .
Ž .
0.003 3
C 11
0.004 3
0.015 4
Ž
Ž .
Ž .
Ž .
Ž .
C 12
0.026 4
0.037 4
0.070 5
y0.012 3
Ž
Ž .
0.031 3
Ž .
0.056 5
Ž .
0.038 4
Ž .
Ž .
0.010 3
Ž .
C 13
0.007 3
y0.004 3
Ž
Ž .
Ž .
Ž .
Ž .
y0.001 4
Ž .
Ž .
0.009 4
C 14
0.039 4
0.081 6
0.044 4
0.007 3
Ž
Ž .
0.035 5
Ž
.
Ž .
0.051 5
Ž .
0.009 5
Ž .
0.009 4
Ž .
C 15
0.150 10
Ž .
0.20 1
0.025 6
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
0.007 7
C 16
0.059 6
0.039 5
0.047 8
0.016 4
Ž
Ž .
0.088 7
Ž .
Ž .
0.053 6
Ž .
0.047 6
Ž .
0.006 5
Ž .
C 17
0.122 9
Ž .
y0.039 6
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y0.022 4
C 18
0.070 6
0.060 5
0.049 4
0.013 4
0.012 4
Ž
Ž .
0.029 3
Ž .
Ž .
0.027 3
Ž .
0.005 3
Ž .
0.005 3
Ž .
y0.002 3
C 19
0.041 4
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
0.000 3
C 20
0.041 4
0.044 4
Ž .
0.036 3
y0.005 3
0.007 3
Ž
Ž .
0.055 5
Ž .
0.041 4
Ž .
0.006 4
Ž .
0.018 3
Ž .
C 21
0.062 5
0.012 4
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
y0.006 4
C 22
0.061 5
0.074 6
0.031 4
0.010 4
0.009 4
Ž
Ž .
0.048 5
Ž .
Ž .
0.045 4
Ž .
0.002 4
Ž .
0.000 4
Ž .
y0.015 4
C 23
0.063 5
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
0.002 3
C 24
0.038 4
0.046 4
0.041 4
0.003 3
0.008 3
Ž
Ž .
0.037 4
Ž .
0.023 3
Ž .
0.039 4
Ž .
0.030 3
Ž .
0.002 3
Ž .
0.006 3
Ž .
C 25
0.006 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
0.001 3
C 26
0.032 3
0.032 3
0.005 3
0.001 3
Ž
Ž .
0.037 4
Ž .
Ž .
0.036 3
Ž .
0.008 3
Ž .
0.010 3
Ž .
C 27
0.051 4
Ž .
0.004 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
y0.003 3
C 28
0.054 5
0.040 4
0.040 4
0.004 3
0.019 3
Ž
Ž .
0.043 4
Ž .
Ž .
0.034 3
Ž .
0.002 3
Ž .
0.006 3
Ž .
y0.011 3
C 29
0.045 4
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
y0.001 3
C 30
0.030 3
0.042 4
Ž .
0.032 3
y0.002 3
0.002 3
Ž
Ž .
0.030 3
Ž .
0.035 3
Ž .
Ž .
0.010 3
Ž .
0.000 3
C 31
0.028 3
y0.005 3
) 2
U
h2 q b) 2U22 k2 q c) 2U33 l2 q 2 a) b)U12 hk q 2 a) c)U13 hl q
11
Ž
2 Ž
a
The general temperature factor expression: exp y2p
2b) c)U23 kl
..
.

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
25
Appendix A. X-ray report for ZrC49H56ClN4LiO4
A.1. X-ray data collection
A yellow fragment crystal of approximate dimensions of 0.20=0.25= 0.35 mm was selected for
X-ray analysis. The crystal was mounted on a glass fiber with epoxy under nitrogen and immediately
placed in a cold nitrogen stream at y508C on the X-ray diffractometer. The X-ray intensity data were
collected on a standard Siemens SMART CCD Area Detector System equipped with a normal focus
Ž
.
molybdenum-target X-ray tube operated at 1.5 kW 50 kV, 30 mA . A total of 1321 frames of data
were collected using a narrow frame method with scan widths of 0.38 v and exposure times of 10
Ž
.
srframe using a crystal-to-detector distance of 5.094 cm. maximum 2u angle of 56.528 . The total
data collection time was approximately 8 h. Frames were integrated with the Siemens SAINT
Ž
.
program to yield a total of 15510 reflections, of which 10983 were independent Rint s2.55% and
˚
Ž .
Ž
.
Ž
.
10980 were above 4s F . The unit cell parameters at y508C of as11.7636 1 A, bs12.4384
˚
˚
Ž .
Ž .
Ž .
Ž .
Ž .
1 A, and cs17.9531 1 A, as86.732 1 , bs71.238 1 , gs89.372 1 , were based upon the
least-squares refinement of three dimensional centroids of 10980 reflections. The space group was
Ž
.
assigned as P1 a2 the basis of systematic absences and intensity statistics using XPREP, and the
crystal solved and refined using direct methods included in the SHELXTL 5.04 package. For a Z
value of 2 there is one independent molecule within the asymmeric unit. In the final model,
2
Ž
.
non-hydrogen atoms were refined anisotropically on F , with hydrogens included in idealized
locations. The structure was refined to R1 s0.0441. wR2 s0.1317. Fractional coordinates and
Ž
.
thermal parameters are given in the supplementary material Tables 4–7 .

(
)
26
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
Appendix B. X-ray report for TaC31H36N3
B.1. X-ray data collection
A parallelpiped red crystal of approximate dimensions of 0.20=0.40 =0.20 mm was selected for
X-ray analysis. The crystal was mounted under nitrogen and immediately placed in a cold nitrogen
stream at y508C on the X-ray diffractometer. The X-ray intensity data were collected on a standard
Siemens SMART CCD Area Detector System equipped with a normal focus molybdenum-target
Ž
.
X-ray tube operated at 1.5 kW 50 kV, 30 mA . A total of 1321 frames of data were collected using a
narrow frame method with scan widths of 0.38 v and exposure times of 10 srframe using a
Ž
.
crystal-to-detector distance of 5.094 cm. maximum 2u angle of 56.528 . The total data collection
time was approximately 8 h. Frames were integrated with the Siemens SAINT program to yield a total
Ž
.
Ž .
of 30025 reflections, of which 13565 were independent Rint s4.15% and 4575 were above 3s F .
˚
˚
˚
Ž .
Ž
.
Ž .
Ž .
The unit cell parameters at y508C of as31.2878 4 A, bs7.9181 1 A, and cs23.003 3 A,
bs101.687 1 , were based upon the least-squares refinement of three dimensional centroids of 4575
Ž .
reflections.
B.2. Data reduction
w
x
The data were integrated with the SAINT program using an algorithm proposed by Kabsch 47 .
SAINT was used to perform the integration of intensity of reflections and scaling, absorption and time
decay correction and statistical analysis of the data. The data were corrected for Lorentz and
Ž
polarization effects. Of the 30025 reflections which were collected, 13565 were unique Rint
.
s0.0415 ; equivalent reflections were merged. The minimum and maximum transmission factors
were 0.5900 and 0.8840. The linear absorption coefficient, m, for Mo-K a radiation is 39.5 cmy
.
1
XPREP was used for space group and empirical absorption corrections.
B.3. Structure solution and refinement
Ž
w x.
The structure was solved by heavy-atom Patterson methods SAPI91 44 and expanded using
Ž
w x.
Fourier techniques DIRDIF92 45 . The non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were included in idealized positions. The final cycle of full-matrix least-square refinement
6
Ž
Ž ..
was based on 4575 observed reflections I)3.00s I and 316 variable parameters and converged
Ž
.
largest parameter shift was 0.03 times its esd with unweighted and weighted agreement factors of:
2
Ý Fo y Fc rÝwFo2 s0.039
5
<
<
5 <
<
RsÝ Fo y Fc Ý Fo s0.042,
Rw s
(
7
The standard deviation of an observation of unit weight was 1.54. The weighting scheme was based
Ž
.
on counting statistics and included a factor ps0.010 to downweight the intense reflections. All
w
x
calculations were performed using the teXsan 46 crystallographic software package of Molecular
Ž
.
Structure Corporation Tables 8–12 .
6
2
2
Ž<
<
<
<.2
Ž
2Ž ..
Ž
2 . Ž 2Ž 2 ..
Ž
.
Ž
2Ž
,
s 2 Fo s S Cq R B q
.
Least-squares: Function minimized: Sw Fo y Fc
,
where ws1r s Fo s 4Fo r s Fo
2
Ž
2 .2 . Ž
pFo
.
r Lp , SsScan rate, Cstotal integrated peak count, RsRatio of scan time to background counting time, Bstotal background
count, Lp sLorentz-polarization factor, ps p-factor.
Standard deviation of an observation of unit weight: Sw F y F 2r N y N , where N snumber of observations, N snumber
7
<
<
<
<
c
(
Ž
.
.
Ž
o
o
v
o
v
of variables.

(
)
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
27
References
w x
Ž .
M. Bochmann, J. Chem. Soc., Dalton Trans. 1996 255.
1
w x
2
Ž .
H.H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, R.M. Waymouth, Angew. Chem. Int. Ed. Engl. 34 1995 1143.
¨
w x
Ž .
G. Fink, R. Muhaupt, H.A. Brintzinger Eds. , Ziegler Catalysts, Springer, Berlin, 1995.
¨
3
w x
Ž
. Ž
.
4
A.M. Thayer, Chem. Eng. News 73 37 1995 15.
w x
Ž .
5
C. Schaverien, J. Adv. Organomet. Chem. 36 1994 283.
w x
Ž .
R.F. Jordan, Adv. Organomet. Chem. 32 1991 325.
6
w x
Ž .
7
T.J. Marks, Acc. Chem. Res. 25 1992 57.
w x
Ž .
P.J. Shapiro, E. Bunel, W.P. Schaefer, J.E. Bercaw, Organometallics 9 1990 867.
J.D. Scollard, D.H. McConville, J.J. Vittal, Organometallics 14 1995 5478.
8
w x
Ž .
9
w
w
w
w
w
w
w
w
w
w
w
w
w
w
w
w
w
w
w
x
10 S.-Y. Lai, J.R. Wilson, G.W. Knight, J.C. Stevens, P.-W. Chum, U.S. Patent 5272236, 1993.
x
Ž
.
11 J.D. Scollard, D.H. McConville, J. Am. Chem. Soc. 118 1996 10008.
x
Ž
.
12 D.J. Crowther, N.C. Baenziger, R.F. Jordan, J. Am. Chem. Soc. 113 1991 1455.
x
Ž
.
13 G.C. Bazan, W.P. Schaefer, J.E. Bercaw, Organometallics 12 1993 2126.
x
Ž
.
14 R. Uhrhammer, D.J. Crowther, J.D. Olson, D.C. Swenson, R.F. Jordan, Organometallics 11 1992 3098.
x
Ž
.
15 D.J. Crowther, D.C. Swenson, R.F. Jordan, J. Am. Chem. Soc. 117 1995 10403.
x
Ž
.
16 R.W. Quan, G.C. Bazan, A.F. Kiely, W.P. Schaeffer, J.E. Bercaw, J. Am. Chem. Soc. 116 1994 4489.
x
Ž
.
17 L. Jia, H. Zhang, N.S. Hosmane, Organometallics 11 1992 2957.
x
Ž
.
18 K.L. Houseknecht, K.E. Stockman, M. Sabat, M.G. Finn, R.N. Grimes, J. Am. Chem. Soc. 117 1995 1163.
x
Ž
Ž
.
19 K. Mashima, S. Fujikawa, A.J. Nakamura, J. Am. Chem. Soc. 115 1993 10990.
x
.
20 G.C. Bazan, S.J. Donnelly, G. Rodriguez, J. Am. Chem. Soc. 117 1995 2671.
x
Ž
.
21 G.C. Bazan, G. Rodriguez, Polyhedron 14 1995 93–102.
x
Ž
.
22 K. Mashima, S. Fujikawa, H. Urata, E. Tanaka, A. Nakamura, J. Chem. Soc. Chem. Commun. 1994 1623.
x
Ž
.
23 G.C. Bazan, G. Rodriguez, B.P. Cleary, J. Am. Chem. Soc. 116 1994 2177.
x
Ž
Ž
.
.
24 G. Rodriguez, G.C. Bazan, J. Am. Chem. Soc. 119 1997 343.
x
25 G. Rodriguez, G.C. Bazan, J. Am. Chem. Soc. 117 1995 10155.
x
Ž
.
26 N.J. Bremer, A.B. Cutcliffe, M.F. Farona, W.G. Kofron, J. Chem. Soc. A 1971 3264.
x
Ž
.
27 M.B. Dinger, W. Henderson, Chem. Commun. 1996 211.
x
Ž
.
28 J.C. Flores, J.C.W. Chien, M.D. Rausch, Organometallics 14 1995 1827.

(
)
28
G. Rodriguez et al.rJournal of Molecular Catalysis A: Chemical 128 1998 5–28
w
w
w
w
x
Ž
.
29 K. Dehnicke, C. Ergezinger, E. Hartmann, A. Zinn, K. Hosler, J. Organomet. Chem. 352 1988 C1.
¨
x
Ž
.
30 F. Schrumpf, H.W. Roesky, T. Subrahmanyan, M. Noltemeyer, Z. Anorg. Allg. Chem. 583 1990 124.
x
Ž
.
31 D.Y. Dawson, J. Arnold, Organometallics 16 1997 1111.
x
Ž
.
32 R. Gomez, R. Duchateau, A. Chernega, A. Meetsma, F.T. Edelmann, J.H. Teuben, M.L.H. Green, J. Chem. Soc. Dalton Trans. 1995
´
217.
w
w
w
w
w
w
w
w
x
Ž
.
.
33 R. Gomez, M.L.H. Green, J. Haggitt, J. Chem. Soc. Chem. Commun. 1994 2607.
x
´
Ž
34 P. Berno, S. Hao, R. Minhas, S. Gambarotta, J. Am. Chem. Soc. 116 1994 7417.
x
Ž
.
35 P.J. Bailey, A.J. Blake, M. Kzysczuk, S. Parsons, D.J. Reed, J. Chem. Soc. Chem. Commun. 1995 1647.
x
Ž
.
36 J. Klein, A. J.Mekik, J. Chem. Soc. Chem. Commun. 1973 275.
x
Ž
.
37 P.J. Gund, J. Chem. Educ. 49 1972 100.
x
Ž
.
38 D. Wilhem, H. Dietrich, T. Clark, W. Mahdi, A.J. Kos, P. von R. Schleyer, J. Am. Chem. Soc. 106 1984 7279.
x
Ž
Ž
.
39 D. Herskovics-Korine, M.S. Eisen, J. Organomet. Chem. 503 1995 307.
x
.
40 B.J. Burger, J.E. Bercaw, in: A.L. Wayda, M.Y. Darensbourg Eds. , Experimental Organometallic Chemistry, ACS Symposium Series
353, Am. Chem. Soc. Washington, DC, 1987.
w
w
w
w
w
x
Ž
.
41 P.T. Wolczanski, J.E. Bercaw, Organometallics 1 1982 793.
x
42 Siemens Analytical X-ray Systems, Inc., Madison, WI 53719-1173.
x
43 Crystal Structure Analysis Package, Molecular Structure Corporation, 1985, 1992.
x
44 H.-F. Fan, 1991. Structure Analysis Programs with Intelligent Control, Rigaku Corporation, Tokyo, Japan.
x
45 P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, S. Garcia-Granda, R.O. Gould, J.M.M. Smits, C. Smykalla, The DIRDIF
program system, Techn. Rep. Crystallogr. Lab. Univ. Nijmegen, The Netherlands, 1992.
w
w
x
46 teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation, 1985 and 1992.
x
Ž
.
47 Kabsch, J. Appl. Crystallogr. 21 1988 916–924.