Synthesis and structural characterization of sulfonates, phosphinates and carboxylates of organometallic group 4 metal fluorides

Article abstract of DOI:10.1016/S0022-328X(96)06818-0

Reaction of [Cp*TiF₃] (Cp* = (η⁵-C₅Me₅)) with Me₃SiOSO₂-p-C₆H₄CH₃, Me₃SiOPOPh₂ and 1,2-(Me₃SiOCO)₂C₆H₄ yields the dinuclear complexes [{Cp*TiF(μ-F)(μ-OSO₂-p-C₆H₄CH ₃)}₂] (1), [{Cp*TiF(μ-F)(μ-OPOPh₂)}₂] (2) and [(Cp*TiF(μ-F)(μ-OCO-o-C₆H₄CO ₂SiMe₃)}₂] (3). The molecular structures of 1 and 2 have been determined by single-crystal X-ray analysis. In complexes 1-3, the two titanium atoms are connected by bridging fluorine atoms as well as bridging sulfonate, phosphinate and carboxylate groups respectively. Each titanium atom is also bonded to a terminal fluorine atom. Reaction of [Cp₂*ZrF₂] with 1,2-(Me₃SiOCO)₂C₆H₄ leads to the mononuclear pentacoordinate 18-electron species [Cp₂*ZrF(μ-OCO-o-C₆H₄CO ₂SiMe₃)] (4) and its structure was determined by X-ray crystallographic methods.

Full text of DOI:10.1016/S0022-328X(96)06818-0

Ž
.
Journal of Organometallic Chemistry 550 1998 1–6
Synthesis and structural characterization of sulfonates, phosphinates and
1
carboxylates of organometallic Group 4 metal fluorides
Syed A.A. Shah, Hendrik Dorn, Judith Gindl, Mathias Noltemeyer, Hans-Georg Schmidt,
)
Herbert W. Roesky
Institut fur Anorganische Chemie der UniÕersitat Gottingen, Tammannstrasse 4, D-37077 Gottingen, Germany
¨
¨
¨
¨
Abstract
)
)
5
w
x Ž
Ž
..
Ž
.
2
Ž
Reaction of Cp TiF3 Cp s h -C5Me5 with Me3SiOSO2-p-C6H4CH3, Me3SiOPOPh2 and 1,2- Me3SiOCO C6H4 yields the
)
)
)
wÄ
Ž
.Ž
.4 x Ž . wÄ
Ž
.Ž
.4 x Ž .
wÄ
.Ž
dinuclear complexes Cp TiF m-F m-OSO2-p-C6H4CH3
1 , Cp TiF m-F m-OPOPh2
2 and Cp TiF m-F m-OCO-o-
2
2
.4 x Ž .
C6H4CO2SiMe3
3 . The molecular structures of 1 and 2 have been determined by single-crystal X-ray analysis. In complexes 1–3,
2
the two titanium atoms are connected by bridging fluorine atoms as well as bridging sulfonate, phosphinate and carboxylate groups
)
w
x
Ž
.
respectively. Each titanium atom is also bonded to a terminal fluorine atom. Reaction of Cp2 ZrF2 with 1,2- Me3SiOCO C6H4 leads to
the mononuclear pentacoordinate 18-electron species Cp2 ZrF m-OCO-o-C6H4CO2SiMe3
X-ray crystallographic methods. q 1998 Elsevier Science S.A.
2
)
w
Ž
.x Ž .
4 and its structure was determined by
Keywords: Group 4; Halides; Transition metals; Titanium; Zirconium
1. Introduction
formation of trimethylsilyl fluoride as by-product
w
x
7,8,10 . By using trimethysilyl esters of sulfonic and
phosphinic acids in combination with an organometallic
Contrary to the large amount of information regard-
ing organometallic Group 4 chlorides, relatively little is
known about the corresponding fluorides. The main
reasons for this have been the comparative difficulty in
preparing the fluoride compounds or separating them
from the fluorinating reagent 1–3 . We have recently
reported on the use of trimethyltin fluoride as a fluori-
nating agent in the preparation of a wide range of
cyclopentadienyl-substituted Group 4 fluorides from the
)
)
5
w
x
Ž
Ž
Group 4 metal fluoride, such as Cp TiF3 Cp s h -
..
C5Me5 , it may be possible to generate discrete ionic
)
w
xq w
xy
species of the form Cp TiF2
RSO3
or
)
w
xqw
xy
Cp TiF2 R2 PO2 , with the elimination of Me3SiF.
A similar Group 4 ionic species with a sulfonate count-
erion was found when using the trifluoromethanesul-
w
x
w
Ž
.
3x2qw yx2
Ž
CF3SO3 Cps
fonate ligand, i.e. Cp2 Zr H2O
5
Ž
.. w x
h -C5H5 11 . Cationic organometallic species have
been intensively researched, especially with regard to
w x
corresponding chloro complexes 4 , and thus, detailed
investigations into the chemistry of organometallic
w
x
Ziegler–Natta polymerization catalysis 12 . It has been
established that the active species found in the
w
x
Group 4 fluorides have now been undertaken 5–10 .
The unique reactivity and coordination behaviour of
these fluorides allow many interesting and previously
unobtainable compounds to be isolated. In many of
these cases, the driving force in the reactions is the
w
x
Ž
Cp2 ZrX 2 rMAO X s Cl or Me; MAO s
.
methylalumoxane catalytic system is the cation
w
xq
w
x
Cp2 ZrMe
Here we describe the reactions of organometallic
13,14 .
Group 4 fluorides with trimethylsilyl esters of sulfonic,
phosphinic and carboxylic acids, and report on molecu-
lar structures which gives an insight on the coordination
behaviour of the fluoride as well as the ancillary lig-
ands.
)
Corresponding author.
1 Dedicated to Professor Ken Wade on the occasion of his 65th
birthday and in recognition of his outstanding contributions to inor-
ganic and organometallic chemistry.
0022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

(
)
2
S.A.A. Shah et al.rJournal of Organometallic Chemistry 550 1998 1–6
2. Results and discussion
2.1. Synthesis and characterization of complexes 1–4
Scheme 2.
Recent studies from our laboratory have shown that
)
)
5
the retention of one trimethylsilyl ester group in the
complex, with a singlet for SiMe3 appearing at 0.53 ppm.
w
x
Ž
Ž
..
Cp TiF3 Cp s h -C5Me5 reacts with trimethyl-
silyl esters of carboxylic acids to form dinuclear com-
)
)
w
x
Ž
.
Reaction of Cp2 ZrF2 with 1,2- Me3SiOCO C6 H4
w
Ä
Ž
.
4
x w
x
plexes of the type Cp TiF2 OCOR
15 . Com-
2
2
could, in theory, yield a polynuclear dicarboxylate com-
plexes 1–3 are prepared in essentially the same way, i.e.
)
Ž
plex, where the carboxylate groups would act as 2q
w
x
via reaction of Cp TiF3 and a trimethylsilyl ester of
.
1 -dentate ligands, such that each zirconium atom has
Ž
.
the relevant acid Scheme 1 .
Since there is no reaction when Cp TiF3 is re-
)
w
x
three ligating oxygen atoms 16,17 . However, this is
not the case. Instead, only one carboxylate group
chelates to the zirconium centre leaving a terminal
fluorine atom still bonded to zirconium Scheme 2 . The
probable reason for this is the steric crowding around
the central zirconium atom. Since the carboxylate groups
are in mutual ortho positions, it would be necessary for
two bulky Cp2) Zr units to be very close to one another
to facilitate 2 q 1 -dentate dicarboxylate ligation.
Therefore, only one trimethylsilyl ester group may react
with the fluorine attached to zirconium to form the
chelating carboxylate, while the second fluorine remains
unreacted.
w
x
)
w
x
placed by Cp TiCl3 it may be surmised that the
formation of Me3SiF acts as a driving force in these
reactions.
Ž
.
All compounds were obtained as crystalline materials
and were fully characterized by their spectral data and
by elemental analyses. Both 1H and 19 F NMR spectra of
Ž
.
complexes 1–3 in CDCl3 show the presence of iso-
mers in solution. For example, two sets of Cp) reso-
Ž
.
Ž
nances 2.22 and 2.25 ppm for 1, 2.14 and 2.15 ppm for
2 and 2.16 and 2.17 ppm for 3 , and of p-methyl groups
in the case of 1 2.23 and 2.28 ppm , in 3:1 relative
.
Ž
.
1
intensity are evident in the respective H NMR spectra.
The complex 19 F NMR spectra of 1–3 show bridging
and terminal fluorine atoms. The multiplets of the ter-
minal fluorine atoms appear at 212.5 ppm for 1,
170.3 ppm for 2 and 174.1 ppm for 3. For the bridging
fluorine atoms, multiplets are observed at y15.9 and
In terms of reactivity, complex 4 proved to be rela-
tively inert and stable towards air and water. Similar
poor reactivity was observed for other Group 4 dicar-
boxylates with a formal 18-electron configuration
w
x
17,18 , due to the increased difficulty in nucleophilic
substitutions at the metal centre.
Ž
.
.
y18.5 ppm compound 1 , y29.5 and y35.1 ppm
Ž
Ž
.
compound 2 and y4.8 and y10.5 ppm compound 3 ,
2.2. Molecular structures of 1, 2 and 4
indicating that they are magnetically non-equivalent.
Further signals in the 19 F NMR spectra, probably due to
isomerization processes, could not be assigned clearly.
A 31 P NMR spectrum of 2 was also obtained, showing a
doublet at 35.1 ppm and a multiplet at 31.9 ppm.
The molecular structures of 1 and 2 were determined
by X-ray crystallography and are depicted in Figs. 1 and
2, together with the atom-labelling scheme. Selected
bond distances and angles are listed in Table 1. Com-
pounds 1 and 2 have no ionic character, but both are
1
Complex 4 was characterized by infrared and H and
19 F NMR spectroscopy as well as mass spectrometry
EI . There is a singlet at 34.3 ppm in the 19 F NMR
Ž
.
1
spectrum of 4, while the H NMR spectrum indicated
Fig. 1. Molecular structure of compound 1. Hydrogen atoms are
Scheme 1.
omitted for clarity.

(
)
S.A.A. Shah et al.rJournal of Organometallic Chemistry 550 1998 1–6
3
Fig. 3. Molecular structure of compound 4. Hydrogen atoms are
omitted for clarity.
Fig. 2. Molecular structure of compound 2. Hydrogen atoms are
omitted for clarity.
the bridging Ti–F distances in 2 is surprising but a
)
w
Ä
Ž
.
4
2 x
similar arrangement exists in Cp TiF2 detphmal
Ž
.
detphmalsdiethylphenylmalonate where the bridging
covalent dinuclear complexes with the titanium atoms
˚
Ž . w x
Ž .
Ž
Ti–F distances are 1.940 2 and 2.170 3 A 2 . The
Ti–F distances for the terminal fluorine atoms in 1 and
2 are similar 1.827 4 A in 1 and 1.848 2 A in 2 and
these are in the usual range found for Cp)Ti-fluoride
bridged by fluorine atoms as well as sulfonate in the
.
Ž
.
case of 1 and phosphinate groups in 2 . However, both
compounds differ in their exact geometry. While the
Cp) ligands in 1 adopt a mutual cis arrangement, the
opposite is found in 2. This trans arrangement in 2 is
similar to that found in previously studied organotita-
˚
˚
Ž
Ž .
Ž .
.
w
x
complexes 2,15,19 .
Relatively little structural information is known re-
garding early transition metal sulfonates or phosphinates
and, to the best of our knowledge, compounds 1 and 2
represent the first structurally characterized organotita-
w
x
nium fluoro-carboxylates 15 . Curiously, 1 is more
symmetrical than 2. For instance, within the central
Ti2 F2 rhomboid of 1 all Ti–F distances are almost
˚
Ž
Ž
Ž . Ž .
Ž .
Ž . Ž .
nium sulfonate other than trifluoromethanesulfonate
identical Ti 1 –F 1 2.022 3 A and Ti 1 –F 3
˚
Ž .
.
compounds — for known structurally characterized
2.042 3 A as are the angles at the fluorine atoms
w
x.
Ž
Ž . Ž .
Ž
.
Ž .
Ž . Ž .
Ž
.
organotitanium trifluoromethanesulfonates see Ref. 20
and phosphinate respectively. The sulfonato groups in 1
Ti 1 –F 1 –Ti 1a 109.6 2 8 and Ti 1 –F 2 –Ti 1a
Ž . .
108.0 2 8 . In 2, however, there is a lesser degree of
are tetrahedral with typical S–O and S–C bond dis-
symmetry indicated by the differences in bond lengths
˚
w
x
Ž
.
Ž
Ž .
Ž
.
Ž .
tances 21 . As expected, the S–O bonded distances are
within the Ti2 F2 rhomboid Ti 1 –F 2a 1.961 2 A and
˚
Ž
.
Ž . Ž .
Ž .
.
longer than the S–O free ones. Similarly, the phosphi-
nato groups in 2 are also tetrahedral and the P–O and
P–C bond distances are in close agreement with those
Ti 1 –F 2 2.227 2 A . The large difference between
Table 1
w
x
of other diphenylphosphinate complexes 22 .
˚
Ž .
Ž
.
Bond distances A and angles deg for 1 and 2
The molecular structure of 4 is shown in Fig. 3 and
selected bond distances and angles are collated in Table
2. The central zirconium atom is pentacoordinate, being
1
2
Ž . Ž .
Ti 1 –F 1
Ž .
Ž .
Ž . Ž .
Ž .
1.848 2
2.022 3 Ti 1 –F 1
Ž . Ž .
Ž . Ž .
Ž .
2.227 2
Ti 1 –F 2
1.827 4 Ti 1 –F 2
Ž . Ž .
Ž . Ž .
Ž
.
Ž .
1.961 2
Ti 1 –F 3
2.042 3 Ti 1 –F 2a
Ž . Ž .
Ž . Ž . Ž .
Ž .
2.040 2
Ti 1 –O 1
2.070 5 Ti 1 –O 1
Table 2
Ž . Ž .
Ž . Ž . Ž .
Ž .
2.036 2
Ti 1 –O 2
2.094 5 Ti 1 –O 2
Ž . Ž .
˚
Ž .
Ž
.
Bond distances A and angles deg for 4
Ž . Ž .
S 1 –O 1
S 1 –O 2a
Ž
.
Ž .
1.801 4
1.484 5 P 1 –C 11
Ž . Ž . Ž .
Ž .
Ž
.
Ž .
1.509 3
Ž . Ž .
Zr 1 –O 1
Ž .
Ž .
2.316 4
1.478 5 P 1 –O 1
Zr 1 –F 1
Ž . Ž .
1.976 4
2.278 5
Ž . Ž .
Ž .
Ž .
Ž .
Ž
.
Ž .
1.516 3
S 1 –O 3
1.429 5 P 1 –O 2a
Ž . Ž .
Ž . Ž .
Ž .
S 1 –C 6
1.762 7
Zr 1 –O 2
Ž .
O 2 –C 11
Ž
.
.
Ž .
1.260 9
O 1 –C 11
Ž . Ž .
Ti 1 –F 3 –Ti 1a 108.2 2
Ž
.
Ž .
Ž .
Ž . Ž .
Ž
.
Ž .
108.97 8
Ti 1 –F 1 –Ti 1a 109.6 2
Ti 1 –F 2 –Ti 1a
Ž .
Ž
Ž .
1.281 8
Ž . Ž .
Ž
.
Ž . Ž .
Ž
.
Ž
.
Ti 1 –F 2a –Ti 1a 109.41 8
Ž . Ž .
Ž .
Si 1 –O 4
1.700 6
Ž . Ž . Ž . Ž .
Ž . Ž . Ž .
Ž .
Ž
F 3 –Ti 1 –F 1 71.2 2
F 2 –Ti 1 –F 2a
71.03 8
Ž .
Ž
.
Ž
.
O 4 –C 18
1.325 10
Ž . Ž . Ž . Ž .
Ž .
Ž .
Ž
.
.
Ž .
F 2 –Ti 1 –O 1 92.9 2
F 2 –Ti 1a –F 2a
70.59 8
90.46 10
92.13 10
155.13 10
Ž . Ž . Ž . Ž .
Ž . Ž .
Ž
.
.
.
.
Ž .
Ž . Ž .
Ž .
134.4 2
F 2 –Ti 1 –O 2
89.7 2
154.8 2
112.0 3
108.5 3
F 1 –Ti 1 –O 1
F 1 –Zr 1 –O 1
Ž . Ž . Ž .
77.4 2
Ž .
Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž
Ž .
O 1 –Ti 1 –O 2
Ž . Ž . Ž .
F 1 –Ti 1 –O 2
F 1 –Zr 1 –O 2
Ž .
Ž . Ž . Ž .
Ž
Ž . Ž . Ž .
Ž .
O 3 –S 1 –O 1
O 1 –Ti 1 –O 2
O 1 –Zr 1 –O 2
57.0 2
Ž . Ž . Ž .
Ž .
Ž . Ž .
Ž
.
Ž
Ž . Ž .
Ž
.
Ž .
O 3 –S 1 –C 6
O 1 –P 1 –O 2a
116.07 13
O 1 –C 11 –O 2
Ž . Ž .
119.2 6
Ž . Ž .
Ž
.
Ž .
Ž
.
Ž .
Ž
.
Ž .
Ž
.
.
Ž .
O 1 –S 1 –O 2a
111.5 3
C 11 –P 1 –C 21
105.2 2
C 11 –O 1 –Zr 1
92.9 4
Ž . Ž .
Ž
.
Ž .
Ž
Ž . Ž .
Ž .
O 1 –P 1 –C 11
111.0 2
C 11 –O 2 –Zr 1
90.6 4

(
)
4
S.A.A. Shah et al.rJournal of Organometallic Chemistry 550 1998 1–6
Ž
.
surrounded by two pentamethylcyclopentadienyl lig-
ands, a fluorine atom and two oxygen atoms of the
20 ml . The mixture was stirred for 24 h, after which
time all the volatiles were removed in vacuo and the
Ž
.
Ž
.
aromatic carboxylate ligand OCO-o-C6 H4CO2 SiMe3 .
The carboxylate group bonds to the zirconium atom in a
chelating fashion. The Zr–O distances in 4 are not equal
residue extracted with dichloromethane 30 ml . After
concentrating to ca. 15 ml and cooling to y25 8C, red
Ž
.
crystals of 1 were obtained 0.81 g, 83% ; m.p. 214 8C.
˚
˚
.
Ž
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Zr 1 –O 1 2.278 5 A and Zr 1 –O 2 2.316 4 A and
Anal. Found: C, 51.5; H, 5.5; F, 10.2. Calc.: C, 52.0; H,
5.7; F, 9.7. IR KBr, Nujol : 1499 m , 1266 s , 1143
Ž . Ž . Ž . Ž . Ž .
Ž
.
Ž .
Ž .
this is consistent with many other organozirconium
w
x
Ž
.
carboxylate complexes 16,17,23–25 . Similarly, the in-
ternal angles within the four-membered ring formed by
the chelation of the carboxylate ligand to zirconium are
m , 1125 s , 1106 vs , 1005 s , 813 m , 807 m ,
684 m , 617 m , 448
m
cmy1. MS: mrz 525
Ž .
Ž .
Ž .
)
Ž
.
Ž
MyCp yFyCH3 yC6 H4CH3, 2 , 372 Mr2yF,
)
)
w
x
.
Ž
.
Ž
Ž
.
also in agreement with related complexes 16,17,23–25 .
In pentacoordinate chloro-carboxylate complexes of
zirconium, the steric crowding of the coordination envi-
ronment around the central zirconium atom leads to
1 , 256 Mr2yCp , 1 , 221 Cp TiF2 , 10 , 135
1
)
Ž
.
.
.
Cp , 100% . H NMR 200 MHz, CDCl3 : d 2.22,
3
)
Ž
Ž
.
Ž
2.25 s, Cp , 2.23, 2.28 s, CH3 , 7.02 d, JHH s8 Hz,
3
.
Ž
.
Ž
m-C6 H4 , 7.09 d, JHH s8 Hz, m-C6 H4 , 7.56 d,
3
3
w
x
.
Ž
.
subsequent elongation of the Zr–Cl bond lengths 24,25 .
However, in the case of 4, the Zr–F distance
JHH s8 Hz, o-C6 H4 , 7.61 d, JHH s8 Hz, o-C6 H4
ppm. 19 F NMR 188 MHz, CDCl3 : d y41.7 t, JFF
s
2
Ž
.
Ž
2
˚
Ž . .
Ž
.
Ž
.
1.976 4 A is in close agreement with those found in
˚
Ž . .
tetracoordinate complexes such as Cp2 ZrF2 1.98 1 A
26 or C5Me4 Et ZrClF 2.002 3 A 7 . The rest of
the molecule shows no significant variation from ex-
pected parameters.
24 Hz, bridging F , y40.8 t, JFF s24 Hz, bridging F ,
2
2
w
x
Ž
Ž
.
Ž
y27.9 m, bridging F , y18.5 dt, JFF s98 Hz, JFF
2
2
˚
. w x
w
x
w
Ž
.
x
Ž
Ž .
.
Ž
s35 Hz, bridging F , y15.9 dt, JFF s98 Hz, JFF
s
s
2
2
2
.
Ž
35 Hz, bridging F , 212.5 dd, JFF s98 Hz, JFF
2
2
.
Ž
35 Hz, term. F , 214.3 dd, JFF s98 Hz, JFF s35 Hz,
2
.
Ž
.
Ž
term. F , 215.8 d, JFF s24 Hz, term. F , 217.2 d,
2
.
JFF s24 Hz, term. F ppm.
3. Experimental details
)
[{
(
)(
)} ]
3.2.2. Preparation of Cp TiF m-F m-OPOPh2
2
( )
3.1. General comments
2
2 was prepared in an analogous manner to that
)
w
x
Ž
.
All reactions were performed under an atmosphere of
dry nitrogen by employing either Schlenk line tech-
niques or an inert atmosphere glove-box. Solvents were
freshly distilled from sodium and degassed prior to use.
CDCl3 and C6 D6 were trap-to-trap distilled from cal-
described for 1 using Cp TiF3 0.70 g, 2.90 mmol
Ž
.
and Me3SiOPOPh2 0.86 g, 2.90 mmol . The crude
product was recrystallized from dichloromethane to yield
1.02 g 80% of red crystals of 2; m.p. 236 8C. Anal.
Ž
.
Found: C, 60.0; H, 5.5; F, 9.1. Calc.: C, 60.3; H, 5.8; F,
)
)
w
x
w x
w
x
w x
4 ,
Ž
.
.
.
Ž .
Ž .
Ž .
Ž .
cium dihydride. Cp TiF3
4 , Cp2 ZrF
8.7. IR KBr, Nujol : 1437 s , 1262 m , 1168 m ,
w
x
w 2
x
Ž
Ž
Ž .
Ž
.
Me3SiOPOPh2 27 , Me SiOSO2C6 H4CH3 28 and
1146 vs , 1128 vs , 1069 m , 1041 vs , 1020 vs ,
Ž . Ž . Ž . Ž . Ž . Ž .
Ž
.
w3
x
1,2- Me3SiOCO C6 H4 28 were prepared according
996 s , 804 m , 749 m , 733 s , 695 m , 629 m ,
2
y1
Ž .
Ž .
Ž .
Ž
to published methods. NMR spectra were recorded on a
602 s , 489 m , 448 m cm . MS: mrz 857 MyF,
Bruker AM 250 spectrometer. H, 19 F and 31 P NMR
1
)
.
Ž
.
Ž
.
22 , 741 MyCp , 15 , 659 MyOPOPh2 , 9 , 419
1
)
Ž
.
Ž
.
Ž
data are listed in parts per million downfield from
SiMe4, CFCl3 and 85% H3PO4 respectively. IR spectra
were recorded on a Perkin–Elmer Bio-Rad Digilab
Mr2yF, 100 , 135 Cp , 38% . H NMR 200 MHz,
CDCl3 : d 2.14, 2.15 s, Cp , 7.43 m, Ph ppm. 19 F
)
.
Ž
.
Ž
.
Ž
.
Ž
.
NMR 188 MHz, CDCl3 : d y35.1 m, bridging F ,
2
Ž
Ž
.
FTS-7 spectrophotometer Kel-F mulls between NaCl
y29.5 dt, JFF s114 Hz, Js35 Hz, bridging F , 6.3
2
plates in the range of 4000 to 1350 cmy1 or Nujol mulls
Ž
.
Ž
.
Ž
m, bridging F , 148.4 m, term. F , 170.3 dd, JFF
s
31
89 Hz, 2JFF s35 Hz, term. F ppm. P NMR 100 MHz,
.
.
Ž
between KBr plates . Mass spectra were obtained on
.
Ž
.
Ž .
Finnigan MAT System 8230 or Varian MAT CH 5
DMErCDCl3 : d 35.1 d, JPF s33 Hz , 32.9 m ppm.
Ž
.
mass spectrometers. Melting points uncorrected were
)
[
{
(
)(
measured using Buchi 510 and HWS-SG 3000 appara-
3.2.3. Preparation of
] ( )
Cp TiF m-F m-OCO-o-
¨
)}
tus. Elemental analyses were performed by the Beller
C6 H4CO2 SiMe3
3
2
Ž
.
laboratory Gottingen, Germany or in our institute.
3 was prepared in an analogous manner to that
¨
)
w
x
Ž
.
described for 1 using Cp TiF3 1.00 g, 4.16 mmol
Ž
.
Ž
.
3.2. Synthesis
and 1,2- Me3SiOCO C6 H4 1.29 g, 4.15 mmol . The
2
crude product was recrystallized from dichloromethane
to yield 2.78 g 73% of red crystals of 3; m.p. 182 8C.
)
[
{
(
)(
Ž
.
3.2.1. Preparation of
] ( )
Cp TiF m-F m-OSO2-p-
)}
C6 H4CH3
1
Anal. Found: C, 54.9; H, 6.1; F, 8.1. Calc.: C, 55.0; H,
2
)
w
x
Ž
.
Ž
.
Ž .
Ž .
To a stirred solution of Cp TiF3 0.60 g, 2.50 mmol
6.2; F, 8.3. IR NaCl, Kel-F : 1733 m , 1688 s , 1598
Ž
.
Ž . Ž . Ž . Ž . Ž . Ž .
in toluene 50 ml was added
a
solution of
m , 1582 s , 1551 s , 1486 m , 1401 s , 1377 m
cmy1. MS: mrz 872 MyCO2 , 2 , 761 My
Ž
.
Ž
.
Ž
Me3SiOSO2C6 H4CH3 0.61 g, 2.50 mmol in toluene

(
)
S.A.A. Shah et al.rJournal of Organometallic Chemistry 550 1998 1–6
5
Table 3
Crystal data for 1, 2 and 4
Compound
1 Ø 2 dioxane
2 Ø 2CH2Cl2
4
Formula
Molecular weight
Crystal size mm
Crystal system
C42 H62 F4O10S2Ti2
962.84
0.40=0.40=0.20
Monoclinic
C46 H54Cl4 F4O4 P2Ti2
1046.43
0.70=0.50=0.30
Monoclinic
C31H43FO4SiZr
617.96
0.50=0.50=0.30
Orthorhombic
P212121
3
Ž
.
Space group
P2rn
11.552 1
P21rc
˚
Ž .
a A
Ž .
Ž .
Ž .
9.789 2
17.100 2
˚
Ž .
b A
Ž .
15.321 2
Ž .
17.229 2
Ž .
9.947 2
˚
Ž .
Ž .
Ž .
Ž .
31.262 5
c A
12.777 1
90
16.441 3
90
Ž
.
.
.
a deg
90
90
90
Ž
Ž
.
Ž .
96.063 10
90
Ž .
4817 1
b deg
Ž
97.030 10
90
g
deg
3
˚
Ž
.
Ž .
2244 4
Ž .
3044 1
V A
Z
2
4
4
y3
Ž
.
Dcalcd g cm
m mm
F 000
u range deg
1.425
0.520
1012
3.5–25
3217
2954
1.443
0.677
2160
3.5–25
6183
6173
1.348
0.440
1296
3.5–25
5337
5241
5228r0r356
1.063
y1
Ž
Ž
.
.
Ž
.
Reflections collected
Independent reflections
Datarrestraintsrparameters
Goodness-of-fit on F2
2951r0r265
1.108
6173r0r569
1.016
w
Ž .x
R1 I)2s I
0.0843
0.0931
0.2285
0.0445
0.0556
0.1167
0.0558
0.0656
0.1646
Ž
.
R1 all data
Ž
.
wR2 all data
y
y3
˚
A
Ž
.
Largest difference peak and hole e
1.646 and y0.875
0.827 and y0.569
0.476 and y0.528
)
.
Ž
.
Ž
COOSiMe3, 5 , 737 MyCp yCO2 , 9 , 645 My
lattice molecules were found per molecular unit of 1.
Crystals of 2 were grown from dichloromethane and
two molecules of CH2Cl2 were found per molecular
unit of 2. Crystals of 4 were grown from hexane.
Relevant crystallographic data of 1, 2 and 4 are given in
Table 3. The intensities for the structures were collected
on a Stoe–Siemens AED four-circle diffractometer us-
)
)
.
Ž
Cp yCOOSiMe3 yF, 100 , 497 My2Cp ySiMe3
1
)
.
Ž
.
Ž
.
y4F, 95 135 Cp , 5% . H NMR 200 MHz, CDCl3 :
)
Ž
.
Ž
.
Ž
Ž
d 0.20, 0.24 s, SiMe3 , 2.16, 2.17 s, Cp , 7.18 m,
19
.
Ž
.
m-C6 H4 , 7.48 m, o-C6 H4 ppm. F NMR 188 MHz,
.
Ž
.
Ž
CDCl3 : d y10.5 m, bridging F , y4.8 m, bridging
.
Ž
.
Ž
.
F , 174.1 m, term. F , 176.8 m, term. F ppm.
Ž
ing graphite monochromated Mo Ka radiation ls
)
˚
.
[
(
3.2.4. Preparation of
] ( )
Cp2 ZrF m-OCO-o-
0.71073 A at 153 K for 1 and at 213 K for 2 and 4. All
)
}
C6 H4CO2 SiMe3
4
structures were solved by direct methods with SHELXS-90
2
)
2
w
x
Ž
a
.
w x
29 and refined by full-matrix least squares on F
To a solution of Cp2 ZrF2 0.75 g, 1.88 mmol in
hexane 30 ml was added
Ž
.
w x
solution of 1,2-
using SHELXL-93 30 . The hydrogen atoms were located
geometrically and refined using a riding model. Absorp-
tion corrections, by azimuthal scans, were applied using
Ž
Ž
.
Ž
.
Me3SiOCO C6 H4 0.58 g, 1.87 mmol in hexane
20 ml . After stirring for 24 h, the solution was concen-
trated to half its original volume whereby colourless
crystals of 4 formed 0.78 g, 79% ; m.p. 221 8C. Anal.
2
.
ŽSHELXTL 31 . Tables of frac-
w x.
a semiempirical method
Ž
.
tional coordinates and equivalent isotropic displacement
parameters, hydrogen atom coordinates, anisotropic dis-
placement parameters and a complete list of bond lengths
and angles have been deposited at the Cambridge Crys-
tallographic Data Centre.
Found: C, 60.1; H, 6.8; F, 2.9. Calc.: C, 60.3; H, 7.0; F,
Ž
.
Ž .
Ž .
.
Ž .
3.1. IR NaCl, Kel-F : 1719 s , 1496 s , 1430 s ,
y1
Ž .
Ž
Ž
.
1379 s cm . MS: mrz 602 MyMe, 4 , 481 My
)
)
)
.
Ž
.
Ž
Cp , 7 , 378 Cp2 ZrF, 12 , 263 Cp ZrF2 , 100 , 135
1
)
Ž
.
Ž
.
Ž
Cp , 20% . H NMR 200 MHz, C6 D6 : d 0.53 s,
)
.
Ž
.
Ž
.
9H, SiMe3 , 1.85 s, 30H, Cp , 7.02 m, 2H, m-C6 H4 ,
7.17 m, 2H, o-C6 H4 ppm. 19 F NMR 188 MHz,
Ž
.
.
Ž
Acknowledgements
Ž .
C6 D6 : d 34.3 s ppm.
3.3. X-ray crystallography
Suitable crystals of
We thank the Deutsche Forschungsgemeinschaft and
the BMBF for generous support of this work. S.A.A.S.
is grateful to the Alexander von Humboldt Foundation
for a postdoctoral fellowship.
1
were grown from a
dichloromethane and dioxane mixture and two dioxane

(
)
6
S.A.A. Shah et al.rJournal of Organometallic Chemistry 550 1998 1–6
w
w
w
w
x
17 U. Niemann, J. Diebold, C. Troll, U. Rief, H.-H. Brintzinger, J.
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