Photochemical C-Cl bond activation of trichloroarenes by the rhenium complex (η5-C5Me5)Re(CO) 3. X-ray structure of trans-(η5-C5 Me5)Re(CO)2(2-methoxy-4,5-dichlorophen

Article abstract of DOI:10.1016/j.jorganchem.2003.08.042

Photochemical reaction of (η⁵-C₅ Me₅)Re(CO)₃, with 2,4,5-trichloroanisole and 3,4,5-trichlorotrifluoromethylbenzene yields (η⁵-C ₅Me₅)Re(CO)₂(C₆H₂

Full text of DOI:10.1016/j.jorganchem.2003.08.042

Journal of Organometallic Chemistry 688 (2003) 168Á173
/
www.elsevier.com/locate/jorganchem
Photochemical Cꢀ
/
Cl bond activation of trichloroarenes by the
rhenium complex (h5-C5Me5)Re(CO)3. X-ray structure of trans-
(h5-C5Me5)Re(CO)2(2-methoxy-4,5-dichlorophenyl)chloride
Alvaro Aballay a, Fernando Godoy a, Gonzalo E. Buono-Core a, A. Hugo Klahn a,*,
Beatriz Oelckers a, Mar´ıa Teresa Garland b, Juan Carlos Munoz b
˜
a Instituto de Qu´ımica, Pontificia Universidad Cato´lica de Valpara´ıso, Casilla 4059, Valpara´ıso, Chile
b Facultad de Ciencias F´ısicas y Matema´ticas, Universidad de Chile, Casilla 653, Santiago, Chile
Received 10 July 2003; received in revised form 19 August 2003; accepted 19 August 2003
Abstract
Photochemical reaction of (h5-C5Me5)Re(CO)3, with 2,4,5-trichloroanisole and 3,4,5-trichlorotrifluoromethylbenzene yields (h5-
C5Me5)Re(CO)2(C6H2Cl2(MeO))Cl (1) and (h5-C5Me5)Re(CO)2(C6H2Cl2(CF3))Cl, (2) formed by insertion of the fragment (h5-
C5Me5)Re(CO)2 into the Cꢀ
respect to the methoxy group as revealed by the X-ray structure of 1. In the case of the reaction with C6H2Cl3(CF3), H-NMR
spectroscopy indicates that only the CꢀCl bond meta respect to CF3 group is cleaved. Complex 1 was isolated as the trans isomer
/
Cl bond of the chloroarenes. The Cꢀ
/
Cl bond activation of trichloroanisole occurs at the chlorine ortho
1
/
while 2 was obtained as an isomeric mixture (trans-2 and cis-2). The stereochemistry of these complexes has been assigned by IR and
13C-NMR spectroscopies and supported by X-ray crystallography for 1.
# 2003 Elsevier B.V. All rights reserved.
Keywords: CꢀCl bond activation; Chloroarenes; Pentamethylcyclopentadienyl; Rhenium
/
1. Introduction
know, reports from our laboratory [3,4] and a paper by
Sutton and Leiva [5] are the only previous publications
related to this work. With regard to photochemical
reactions, we and others have demonstrated that cyclo-
Chloroarenes are of particular interest because of
their negative environmental and health impact [1].
Environmental concerns have driven several research
groups to examine practical and effective processes for
the transformation of highly toxic chloroarenes into
arenes by using transition metal complexes under
stoichiometric and catalytic conditions [2]. Unfortu-
nately, the utilization of rhenium complexes into degra-
dation reactions of these persistent environmental
pollutants has received little attention. As far as we
pentadienylrheniumtricarbonyl
complexes
(h5-
C5R5)Re(CO)3 (RꢀH and Me) serve as useful precur-
/
sors to produce complexes of the type (h5-
C5R5)Re(CO)2L, when they are UV-irradiated in the
presence of THF [6], PR3 [7], alkenes [8], etc. These
complexes are also appropriate photochemical precur-
sors for studying the coordination [9], Cꢀ
bond activation of fluorinated benzenes [10Á
Cl bond activation of chlorobenzenes [3,4]. As part of
our continuing investigation on the Cꢀhalogen bond
/
F and Cꢀ
/
H
/
12] and Cꢀ
/
/
activation by cyclopentadienyl rhenium carbonyl com-
plexes, in this paper we wish to report the photochemical
reaction of (h5-C5Me5)Re(CO)3 in the presence of 2,4,5-
* Corresponding author. Tel.: ꢁ
422.
E-mail address: hklahn@ucv.cl (A.H. Klahn).
/
56-32-273-174; fax: ꢁ56-32-273-
/
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.08.042

A. Aballay et al. / Journal of Organometallic Chemistry 688 (2003) 168Á
/173
169
trichloroanisole and 3,4,5-trichlorotrifluoromethyl ben-
zene, with the aim to focus on the electronic or steric
effects of the methoxy and trifluoromethyl groups on
the Cꢀ/Cl bond activation of the trichlorobenzene ring.
2. Results and discussion
Hexane solutions of 2,4,5-trichloroanisole and 3,4,5-
trichlorotrifluoromethylbenzene, in the presence of (h5-
C5Me5)Re(CO)3, were UV-irradiated (lꢀ350 nm) at
/
room temperature for 11 and 4 h, respectively. In both
cases, the reactions produced one major dicarbonyl
product in low conversion yield (Scheme 1), while
most of the starting tricarbonyl complex remained
unreacted. Longer irradiation times did not increase
the yield of the products; instead, significant amounts of
the dichloro complex (h5-C5Me5)Re(CO)2Cl2 [13] and
decomposition products were formed.
Fig. 1. Perspective view (ORTEP) of trans-(h5-C5Me5)Re(CO)2(C6H2-
Cl2OMe)Cl (1) showing the atom numbering scheme. Atoms are
represented by thermal ellipsoids at the 50% probability level.
[3,4,13,14]. The appearance of a single resonance for the
equivalent CO groups in the 13C-NMR spectra at d
196.0, is a further evidence for the trans orientation of
the carbonyl ligands in this type of compounds.
Furthermore, the X-ray structure of complex 1 (Fig. 1)
confirms the geometry of the isomer and adds to the list
of determined structures of related cyclopentadienyl
complexes containing the aryl-Re-halogen moiety.
The insertion product (h5-C5Me5)Re(CO)2(C6H2Cl2-
(MeO))Cl (1) was isolated as air stable orange micro-
crystals after column chromatography on Florisil and
crystallization from dichloromethaneÁhexane. Complex
/
1 is stable both as a solid and in solution of polar and
non-polar organic solvents with regards to the conver-
sion to the cis isomer. No isomerization was observed
even in boiling benzene or acetonitrile, though the
complex does not survive for long at these temperatures.
The trans stereochemistry of this compound was
assigned on the basis of the IR and 13C-NMR spectra.
In the former technique, the spectrum exhibited only
two n(CO) absorptions at 2040 and 1956 cmꢂ1 (CH2Cl2
solution), being the lower wavenumber band much more
intense. Similar patterns of intensities have been ob-
served in several other dicarbonyl rhenium complexes
possessing a four-legged piano-stool type of structure
These
include
trans-(h5-C5Me5)Re(CO)2(2,3,4,5-
C6HCl5)Cl [3], trans-(h5-C5Me5)Re(CO)2(C6H5)I [15],
trans-(h5-C5Me4CH2Br)Re(CO)2(C6F5)Br [16] and
trans-(h5-C5H5)Re(CO)2(C6HF4)Br [17]. Selected bond
lengths and angles are presented in Table 1. The Reꢀ
/
˚
˚
Cl bond (2.478 A)
C(aryl) bond (2.188 A) and Reꢀ
/
compare well with those determined for trans-(h5-
C5Me5)Re(CO)2(2,3,4,5-C6HCl5)Cl [3] (2.197 and
˚
2.488 A, respectively). The interbond angle sub-
tended by the two CO groupsat Re (98.98) is also close
to the angles in similar trans complexes.
Scheme 1. Products from the irradiation of (h5-C5Me5)Re(CO)3 with chloroarenes.

170
A. Aballay et al. / Journal of Organometallic Chemistry 688 (2003) 168Á173
/
Table 1
Formally, the reactions described above can be
viewed as an insertion of the photogenerated fragment
5
˚
Selected bond lengths (A) and angles (8) for trans-(h -C5Me5)R-
e(CO)2-(C6H2Cl2OMe)Cl (1)
[(h5-C5Me5)Re(CO)2] into a Cꢀ
nated arene molecules, in a similar fashion to the
/Cl bond of the chlori-
Bond lengths
photochemical reactions of (h5-C5Me5)Re(CO)3 with
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
C18ꢀ
C19ꢀ
C12ꢀ
C17ꢀ
/
C1
2.283(4)
2.251(3)
2.300(3)
2.358(3)
2.284(4)
2.188(3)
1.969(4)
1.916(4)
2.4784(9)
1.131(4)
1.150(4)
1.368(4)
1.406(5)
/C2
several partially fluorinated [10Á12] and chlorinated
/
/C3
benzenes [3,4], reported previously from our group.
/C4
Neither coordination nor Cꢀ
/
H bond activation pro-
/C5
ducts of the chlorinated arenes were observed in these
reactions. These results are in good agreement with the
/
C11
C18
C19
Cl(3)
/
/
lower Cꢀ
/
Cl bond strength when compared to that of the
/
CꢀH bond [18].
/
/
O2
O3
O1
O1
An interesting feature associated with the trichloroar-
enes involved in this work is the possibility they offer to
address electronic and/or steric effects of the substituent
on the aromatic ring (OMe or CF3), with respect to the
/
/
/
Bond angles
selectivity of the Cꢀ
/
Cl bond activation. For 2,4,5-
C18ꢀ
C11ꢀ
C11ꢀ
C11ꢀ
C18ꢀ
C19ꢀ
O2ÁC18ꢀ
O3ÁC19ꢀ
C12ꢀO1ꢀ
/
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
Reꢀ
/
C19
Cl(3)
C18
98.91(16)
143.2(2)
79.70(14)
80.59(13)
74.98(11)
77.47(11)
175.6(3)
176.9(4)
119.3(3)
/
/
trichloroanisole, the X-ray structure of complex 1 (Fig.
1) reveals that the activation occurs in the position ortho
with respect to the OMe group. Taking into account the
/
/
/
/
C19
/
/
Cl(3)
Cl(3)
model proposed for the Cꢀ
/
H and Cꢀ/F bonds activation
/
/
of arenes or fluorinated arenes by transition metal
complexes [19], and also the experimental evidence for
the coordination of chlorobenzenes to rhenium in the
complexes (h5-C5Me5)Re(CO)2(5,6-h2-1,2,4-C6H3Cl3)
and (h5-C5Me5)Re(CO)2(5,6-h2-1,2,3,4-C6H2Cl4) [20],
we have also considered an intermediate with the
chloroarene coordinated in an h2-fashion, prior to the
/
/
Re1
Re1
C17
/
/
/
/
In contrast, the complex (h5-C5Me5)Re(CO)2(C6-
H2Cl2(CF3))Cl (2) could be separated into the trans
and cis isomeric forms, by column chromatography.
Each isomer was characterized by IR and 1H-NMR
spectroscopies. The IR spectrum of trans-2 exhibited
similar pattern of the n(CO) absorption bands (2047 and
1965 cmꢂ1 in CH2Cl2 solution) to those observed for
complex 1, whereas cis-2 showed an intensity pattern
indicative of a lateral orientation of the two CO groups,
that is, the lower wavenumber band is the less intense of
the pair [3,13,14]. The 1H-NMR spectra can also be used
to distinguish the two isomers of 2; the methyl reso-
nances for the (h5-C5Me5) ligand of trans-2, observed at
d 1.75, occur at higher field of that found at d 2.03 for
cis-2, whereas the resonances for the aromatic protons
of trans-2 are shifted to lower field when compared with
those observed for cis-2. Unfortunately, after an over-
night scanning the 13C-NMR spectra of either isomer in
CDCl3, showed resonances for the isomeric mixture
(trans-2:cis-2 ratio of about 0.8) due to the isomeriza-
insertion of the metal fragment into the Cꢀ
/Cl bond.
Since the activation occurs at the chlorine ortho with
respect to the OMe, then two possibilities for the
coordination of the unsaturated fragment [(h5-
C5Me5)Re(CO)2] to 2,4,5-trichloroanisole can be envi-
saged: coordination through the CClꢁ
/
C(OMe) or CClꢁ
/
CH bonds of the molecule. The former can be discarded
by considering both experimental results and recent
theoretical studies which have demonstrated that the
same rhenium fragment coordinate to the less substi-
tuted double bond of partially fluorinated [21] and
chlorinated [20] benzenes. In the second intermediate,
the fragment should coordinate the CClꢁ
the 2,3-position of the arene. However, the binding at
this position has similar steric environment to the other
/CH bond at
two distinct CClꢁ
arene (at 3,4- and 4,5-positions). At this stage we do not
have a conclusive answer for the activation of the CꢀCl
/
CH bonds present in the chlorinated
/
tion trans-2l
/
cis-2 process. A similar isomerization
bond ortho to the bulky methoxy group, but we suspect
that the electron-donor capability of this group plays a
still undetermined role.
The same model can be assumed to account for the
observed insertion product of 3,4,5-trifluromethylben-
zene, but in this case, the CF3 group seems to play a
minor role on the selectivity of activation. The 1H-NMR
spectrum of 2 shows that the CꢀCl bond meta with
respect to the CF3 group has been cleaved, since each
isomer exhibited two resonances for the aromatic
process was observed for the cis- and trans-(h5-
C5Me5)Re(CO)2(2,3,4,5-C6HCl4)Cl [3]. Nevertheless, in
both cases the spectrum showed three resonances at d
192.6, 202.6 and 205.1, assigned to the carbonyls of the
two products. By comparison with carbonyl chemical
shifts found in similar compounds reported from our
laboratory [3,4], the higher field resonance is assigned to
trans-2 and the lower field resonances to the two
inequivalent CO ligands of the complex cis-2.
/

A. Aballay et al. / Journal of Organometallic Chemistry 688 (2003) 168Á
/173
171
protons (vide infra). The activation of one of the
chlorine atoms located at the meta position appears to
follow the same pattern of substitution observed pre-
viously in the reaction of several polychlorinated
benzenes with transition metal complexes, under ther-
mal [22] or photochemical [3] conditions, wherein most
Mass spectra were obtained at the Laboratorio de
Servicios Anal´ıticos, Universidad Cato´lica de Valpar-
a´ıso, and the Chemistry Department at University of
York. Elemental analyses were obtained at the Centro
de Instrumentacio´n, Pontificia Universidad Cato´lica de
Chile, Santiago, Chile.
of the cases, the Cꢀ
/
Cl bond activation occurs at the less
hindered position.
3.1. trans-(h5-C5Me5)Re(CO)2(C6H2(OMe)Cl2)Cl
(1)
As we pointed out above, complex 2 was obtained as
an isomeric mixture, but complex 1 was isolated as a
single isomer, so an obvious question arises: why the
(h5-C5Me5)Re(CO)3 (100 mg, 0.247 mmol) is dis-
solved in 20 ml of a saturated solution of 2,4,5-
trichloranisole, in hexanes, in a Pyrex tube (25 cm, 1.5
cm external diameter). The solution is irradiated at 350
nm for 11 h. The solution turned yellow, and red crystals
are formed on the walls of the tube. Solvent was
transferred under vacuum and the yellow residue and
the crystals were chromatographed on Florisil. Elution
difference? The cis l
/
trans isomerization is quite a
common process observed both in solution [23] and in
confined environments [24] in complexes of the type
CpML2L2. According to the results found previously in
our laboratory on the insertion products of several
partially chlorinated benzenes, of the general formula
(h5-C5Me5)Re(CO)2(C6HnCl5ꢂn)Cl (nꢀ
trans to cis isomerization only occurs for complexes
with nꢀ1 and 2 and it is a solvent-dependent process
/1, 2 and 3), the
with hexanesÁCH2Cl2 (10:1) moved a mixture of un-
/
/
changed (h5-C5Me5)Re(CO)3 and 2,4,5-trichloroanisole.
Dichloromethane moved orange trans-(h5-C5Me5)Re-
(CO)2(C6H2(OCH3)Cl2)Cl (1) which was obtained as
orange crystals by layering a concentrated CH2Cl2
solution of the orange solid with hexanes (yield 55 mg,
0.093 mmol, 38% conversion).
(trans isomers are favored in nonpolar organic solvents,
whereas the cis forms are the most stable species in polar
solvents) [3,4]. By considering now the reluctance of 1 to
interconvert to the cis isomer and the fact that complex
2, which possesses the electron withdrawing CF3 sub-
stituent on the dichloroaryl ligand, behaves similarly to
IR (CH2Cl2, n(CO)/cmꢂ1): 2040s and 1956vs; 1H-
NMR (CDCl3) d 1.70 (s, 15H), 3.80 (s, 3H), 6.84 (s, 1H),
their tetra (nꢀ
/
1) and trichloroaryl (nꢀ2) analogues, we
/
suggest that the electronic effects on the aryl ligand also
play an important role in the thermal isomerization of
this type of compound.
Clearly much work is required to establish unequi-
vocally the above statement as well as the factors
7.68 (s, 1H); 13C{1H}-NMR (CDCl3) d 10.82 (C5
57.00 (OCH3), 105.06 (C5Me5); 112.27 (C6H3(CH3)Cl),
/Me/5),
¯
¯
¯
¯
119.41 (C6H3(CH3)Cl), 125.35 (C6H3(CH3)Cl), 131.39
¯
(C6H3(CH3)Cl), 147.81 (C6H3(CH3)Cl), 164.35 (C6H3-
¯
¯
¯
(CH3)Cl), 196.50 (CO); mass spectrum (based on
187Re/35Cl) m/z 588 [M]ꢁ, 560 [MꢂCO]ꢁ, 532 [Mꢂ
2CO]ꢁ, 356 [Mꢂ C6H2(OCH3)Cl2]ꢁ (Found: C,
2COꢂ
influencing the selectivity of Cꢀ
/
Cl bond activation of
/
/
chloroarenes by the photogenerated rhenium fragment
[(h5-C5Me5)Re(CO)2]. Studies on a more complete series
of complexes possessing electron-donating and electron-
withdrawing substituents on the chlorophenyl ligands
are currently underway to further evaluate these issues.
/
/
38.51; H, 2.99. Calc. for C19H20Cl3O3Re: C,38.77; H,
3.39%).
3.2. (h5-C5Me5)Re(CO)2(C6H3(CF3)Cl2)Cl (2)
Four Pyrex tubes containing (h5-C5Me5)Re(CO)3
(100 mg, 0.247 mmol) dissolved in a mixture of 3,4,5-
trichlorotrifluoromethylbenzene (1 ml) and hexanes (19
ml) each one, were irradiated at 350 nm for 4 h. The
resulting yellow solutions are mixed and the solvent was
pumped off. The brown oily residue was chromato-
graphed on a silica gel column. Elution with hexanes
moved a mixture of unreacted (h5-C5Me5)Re(CO)3 and
3. Experimental
All reactions were carried out under nitrogen using
standard Schlenk techniques. (h5-C5Me5)Re(CO)3 was
prepared according to a procedure described in the
literature [25]. 2,4,5-Trichlorophenol, and 3,4,5-trichlor-
otrifluoromethylbenzene from Aldrich were used as
received. 2,4,5-Trichloroanisole was prepared in 85%
yield from the corresponding phenol by a Williamson
synthesis. Solutions were irradiated using a Rayonet
RPR 100 photoreactor. Infrared spectra were recorded
3,4,5-trichlorotrifluoromethylbenzene.
HexanesÁ
/
CH2Cl2 (10:1) moved orange trans-(h5-C5Me5)Re-
(CO)2(C6H3(CF3)Cl2)Cl (trans-2) (10 mg, 0.016 mmol).
HexanesÁ
CH2Cl2 (5:1) moved red cis-(h5-C5Me5)R-
e(CO)2(C6H3(CF3)Cl2)Cl (cis-2) (12 mg, 0.019 mmol).
/
in solution (CaF2 cell) on a PerkinÁ
/
Elmer FT-1605
spectrophotometer, 1H- and 13C-NMR spectra on
Bruker ADVANCE 400. 1H-NMR chemical shifts
were referenced using the chemicals shifts of residual
solvent resonances, 13C chemical shifts to solvent peaks.
3.2.1. trans-2
IR (CH2Cl2, n(CO)/cmꢂ1): 2048s and 1967vs; 1H-
NMR (CDCl3) d 1.75 (s, 15H), 7.53 (d, 1H, Jꢀ1.6 Hz),
/

172
A. Aballay et al. / Journal of Organometallic Chemistry 688 (2003) 168Á173
/
7.93 (d, 1H, Jꢀ
/
1.6 Hz); 13CÁ
9.60 (C5Me/5), 192.60 (CO), aromatic carbons cannot be
/
{1H}-NMR (CDCl3) d
given in Table 2. A red crystal of 1 was glued to a glass
fiber and mounted on Bruker SMART APEX diffract-
ometer, equipped with a CCD area detector. Data was
/
assigned due to the isomerizaton to the cis isomer. Mass
spectrum (based on 187Re/35Cl) m/z: 626 [M]ꢁ, 598
collected using graphite-monochromated MoÁ
/
Ka radia-
0.71073 A). Cell constants for 1 were obtained
from the least-squares refinement of three-dimensional
centroids of 995 reflections in the range 5.0452u 5
CO]ꢁ, 570 [Mꢂ
/
2CO]ꢁ, 356 [Mꢂ
/
2COꢂ
/
tion (lꢀ
/
˚
[Mꢂ
/
C6H2(CF3)Cl2]ꢁ (Found: C, 36.36; H, 2.54. Calc. for
C19H17Cl3F3O2Re: C, 36.42; H, 2.71%).
/
/
55.40. Data were measured through the use of CCD
recording of v rotation frames (0.38 each). All data were
corrected for Lorentz and polarization effects. Absorp-
tion corrections were applied using the SADABS routine
[26]. Both data were integrated with the Bruker SAINT-
PLUS program [27].
The structure was solved by Patterson, completed by
difference Fourier techniques and refined by full-matrix
least-squares on F2
(SHELXL-97) [28] with initial iso-
tropic, but subsequent anisotropic thermal parameters.
Hydrogens in 1 were included in calculated positions
and refined riding on carbon atoms with free isotropic
displacement parameters. Atomic scattering factors
were used as implemented in the program [28].
3.2.2. cis-2
1
IR (CH2Cl2, n(CO)/cmꢂ1): 2027vs and 1956vs; H-
NMR (CDCl3) d 2.03 (s, 15H), 7.16 (d, 1H, Jꢀ
7.40 (d, 1H, Jꢀ
1.5 Hz); 13CÁ{1H}-NMR (CDCl3) d
10.30 (C5Me/5), 202.60 (CO), 205.10 (CO), aromatic
/
1.5 Hz),
/
/
/
carbons cannot be assigned due to the isomerizaton to
the trans isomer. Mass spectrum (based on 187Re/35Cl)
m/z: 626 [M]ꢁ, 598 [Mꢂ
/
CO]ꢁ, 570 [Mꢂ2CO]ꢁ, 356
/
[Mꢂ
/
2COꢂ
C6H2(CF3)Cl2]ꢁ (Found: C, 36.06; H,
2.64. Calc. for C19H17Cl3F3O2Re: C, 36.42; H, 2.71%).
/
3.3. Crystal structure determination
X-ray quality crystals of 1 were obtained by recrys-
tallization from hexanes solutions by slow cooling to ꢂ
10 8C. A summary of crystal data, data collection, and
refinement parameters for the structural analyses is
/
4. Supplementary material
Crystallographic data for complex 1 have been
deposited with the Cambridge Crystallographic Data
Center, CCDC no. 214452. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
Table 2
Crystal data and structure refinement for trans-(h5-C5Me5)Re(CO)2-
(C6H2Cl2(OCH3))Cl (1)
Empirical formula
Formula weight
Temperature
C19H20Cl3O3Re
588.90
(Fax: ꢁ44-1223-336033; e-mail: deposit@ccdc.cam.a-
c.uk or www: http://www.ccdc.cam.ac.uk).
/
297(2) K
0.71073 A
Monoclinic, P2(1)/c
˚
Wavelength
Crystal system, space group
Unit cell dimensions
Acknowledgements
˚
a (A)
15.4018(11)
9.9530(7)
14.9010(11)
90
˚
b (A)
This work was supported by FONDECYT-Chile,
through an operating grant to A.H.K. 1020655 and
Direccio´n de Investigacio´n, Pontificia Universidad Ca-
to´lica de Valpara´ıso (Project 125.745/02). M.T.G. ac-
knowledges FONDAP 11980002. We also wish to thank
Fundacion Andes for financial support for X-ray
diffractometer (Convenio C-13575) and NMR spectro-
meter (Convenio C-13672). J.C.M. is a grateful recipient
of a scholarship from the Deutscher Akademischer
Austauschdienst. The donation of NH4ReO4 by MO-
LYMET-Chile is greatly appreciated.
˚
c (A)
a (8)
b (8)
115.8070(10)
90
g (8)
3
V (A )
˚
2056.4(3)
4
1.902
Z
Dcalc (g cmꢂ3
)
Absorption coefficient (mmꢂ1
F(000)
)
6.314
1136
Crystal size (mm)
u range for data collection (8)
Limiting indices
0.32ꢃ
2.52Á27.94
205h 5
195l 519
/
0.22ꢃ
/
0.10
/
ꢂ
/
/
/
20, ꢂ
/
125
/
k 5
/
12, ꢂ
/
/
/
Reflections collected/unique
14653/4606 [Rint
99.9%
ꢀ/0.0249]
Completeness to uꢀ 26.00
/
References
Max/min transmission
Refinement method
1.0, 0.694538
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
4606/0/241
1.036
[1] O. Hutzinger, S. Safe, V. Zitko, The Chemistry of PCBs, CRC
Press, Cleveland, OH, 1974.
Final R indices [I ꢀ
R indices (all data)
Largest difference peak and hole 0.787 and ꢂ
/
2s(I)]
R1ꢀ
/
0.0252, wR2ꢀ
0.0314, wR2ꢀ
0.536
/
0.0559
0.0584
[2] (a) V.V. Grushin, H. Alper, Chem. Rev. 94 (1994) 1047;
(b) M. Cucullu, S.P. Nolan, T.R. Belderrain, R.H. Grubbs,
Organometallics 18 (1999) 1299;
R1ꢀ
/
/
/
ꢂ3
˚
(e A
)
(c) M. Portnoy, D. Mieltein, Organometallics 12 (1993) 1665.

A. Aballay et al. / Journal of Organometallic Chemistry 688 (2003) 168Á
/173
173
[3] A.H. Klahn, A. Toro, B. Oelckers, G. Buono-Core, V. Manri-
quez, O. Wittke, Organometallics 19 (2000) 2580.
[4] H. Klahn, M. Carreno, F. Godoy, B. Oelckers, A. Pizarro, A.
˜
[16] A.H. Klahn, B. Oelckers, F. Godoy, M.T. Garland, A. Vega,
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3079.
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[5] D. Sutton, C. Leiva, Organometallics 17 (1998) 4568.
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Soc. 113 (1991) 8165.
[17] M.T. Garland, R.F. Baggio, A.H. Klahn, B. Oelckers, Acta
Crystallogr. C55 (1999) 61.
[18] CRC Handbook of Chemistry and Physics, 67th ed., CRC Press,
Boca Raton, FL, 1986, p. F-186.
[7] A.H. Klahn, C. Leiva, K. Mossert, X. Zhang, Polyhedron 10
(1991) 1873.
[19] S.T. Belt, M. Heliwell, W.D. Jones, M.G. Patridge, R.N. Perutz,
J. Am. Chem. Soc. 115 (1993) 1429.
[8] J.M. Zhuang, D. Sutton, Organometallics 10 (1991) 1516.
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Patridge, R.N. Perutz, J. Chem. Soc. Dalton Trans. (1997) 1269.
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Chem. Soc. Dalton Trans. (2003) in press.
[21] A. Aballay, A.H. Klahn, B. Oelckers, unpublished results.
[22] M. Esteruelas, J. Herrero, F.M. Lopez, M. Martin, L. Oro,
Organometallics 18 (1999) 1110.
[11] F. Godoy, C.L. Higgitt, A.H. Klahn, B. Oelckers, S. Parsons,
R.N. Perutz, J. Chem. Soc. Dalton Trans. (1998) 2039.
[12] J. Carbo´, O. Eisenstein, C.L. Higgitt, A.H. Klahn, F. Maseras, B.
Oelckers, R.N. Perutz, J. Chem. Soc. Dalton Trans. (2001) 1452.
[13] F.W.B. Einstein, A.H. Klahn, D. Sutton, K.G. Tyers, Organo-
metallics 5 (1986) 53.
[23] J.W. Faller, A.S. Anderson, J. Am. Chem. Soc. 92 (1970) 5852.
[24] N.J. Coville, D.C. Levendis, Eur. J. Inorg. Chem. (2002) 3067.
[25] A.T. Patton, C.E. Strouse, C.B. Knobler, J.A. Gladysz, J. Am.
Chem. Soc. 105 (1983) 5804.
[26] R.H. Blessing, Acta Crystallogr. A51 (1995) 33.
[27] SAINTꢁ, version 6.01, Bruker AXS, Madison, WI, 2000 and
/
[14] R.B. King, R.H. Reimann, Inorg. Chem. 15 (1976) 183.
[15] C. Leiva, A.H. Klahn, F. Godoy, A. Toro, V. Manriquez, O.
Wittke, D. Sutton, Organometallics 18 (1999) 339.
SAINT, version 4.0.
[28] G.M. Sheldrick, SHELXL-97 Program for Crystal Structure
Refinement, University of Gottingen, Gottingen, Germany, 1997.
¨
¨