Synthesis, reactivity and molecular structure of phosphino tetramethyl cyclopentadienyl complex (η5: η1-C 5Me4CH2PPh2)Re(CO)2

Article abstract of DOI:10.1039/b820751h

The fulvene complex (η⁶-C₅Me₄CH ₂)Re(C₆F₅)(CO)₂ reacts at the exocyclic methylene carbon with potassium diphenylphosphide to yield the anionic species [(η⁵-C₅

Full text of DOI:10.1039/b820751h

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Synthesis, reactivity and molecular structure of phosphino tetramethyl
cyclopentadienyl complex (g5: g1-C5Me4CH2PPh2)Re(CO)2†
Fernando Godoy,*a A. Hugo Klahn,*a Beatriz Oelckers,a Mar´ıa Teresa Garland,b Andres Iba´n˜ezb and
Robin N. Perutzc
Received 20th November 2008, Accepted 4th February 2009
First published as an Advance Article on the web 2nd March 2009
DOI: 10.1039/b820751h
6
The fulvene complex (h -C5Me4CH2)Re(C6F5)(CO)2 reacts at the exocyclic methylene carbon with
5
potassium diphenylphosphide to yield the anionic species [(h -C5Me4CH2PPh2)Re(C6F5)(CO)2]- (1).
◦
5
Protonation of 1 with HCl at 0 C produces the hydride complex trans-(h -C5Me4CH2PPh2)-
Re(C6F5)(H)(CO)2 (2). Thermolysis of a hexanes solution of 2, under nitrogen atmosphere, produces
5
1
the chelated complex (h :h -C5Me4CH2PPh2)Re(CO)2 (3) in good yield. The thermolysis under a CO
atmosphere affords a mixture of the complexes (h :h -C5Me4CH2PPh2)Re(CO)2 (3) and
(h -C5Me4CH2PPh2)Re(CO)3 (4a). The reaction of 3 with two electron donor ligands yields
5
1
5
5
t
(h -C5Me4CH2PPh2)Re(CO)2(L) (4a, L = CO; 4b, L = PMe3; 4c, L = BuNC). Complex 3 also reacts
with I2, HBF4 and MeOTf to yield the cationic compounds trans-[(h :h -C5Me4CH2PPh2)Re(R)(CO)2]+
(5a, R = I; 5b, R = H; 5c, R = Me). Upon treatment with chloroform, the hydride complex 5b converts
to the corresponding chloro derivative 5d. The trans stereochemistry for complexes 5 have been
assigned on basis of n(CO) IR intensities and 13C-NMR chemical shifts. The reaction of the cationic
5
1
5
1
complexes (5a, 5c) with KI and Me3NO·2H2O yields the neutral species cis-(h :h -C5Me4CH2PPh2)-
Re(I)(R)(CO) (6a, R = I, 6b, R = Me). The molecular structure of 3 and 6a have been determined by
X-ray crystallography.
5
tion reactions.8 A related chelating derivative (h -C5H4PPh2)Re-
Introduction
(NO)(R)(PPh3) (R PPh2,CH2PPh2) was described by
Gladysz and used to prepare heterobimetallic rhenium/rhodium
complexes.9
=
In recent years, hetero-bidentate ligands containing a cyclopenta-
dienyl linked to a heteroatom functionality1 or an alkene2 group
have received considerable attention mainly because they are
envisaged as convenient entries to mono and bimetallic complexes
(homo or hetero). These ligands belong to the group of hemilabile
ligands,3 where the side-chain functionality can either act as
donor or as a spectator ligand. The bifunctional character of
the hemilabile ligands provides interesting perspectives in terms
of stabilization of reactive species, small molecule activation and
homogeneous catalysis.4
Nevertheless, few half sandwich compounds of this type are
known for group 7 metals.5 For instance, Wang has reported
the synthesis and reactivity of the complex (h :h -C5H4(CH2)2-
NHMe)Re(CO)2 and Gladysz has prepared diphenylphosphino
cyclopentadienyl complexes (h -C5H4PPh2)Re(CO)3.7 Other het-
As far as we are aware heterodifunctional phosphinotetra-
methylcyclopentadienyl-rhenium complexes remain unreported
in literature. Nevertheless some procedures have been published
for the preparation of the heterodifunctional phosphinotetram-
ethylcyclopentadienyl ligands.10 One of these approaches involve
the modification of some of the classical methods used for
the preparation of pentamethylcyclopentadienyl ligand.11 An-
other method used either tetramethylspiro[2.4]hepta-2,6-diene
(C5Me4(CH2)2)12 or 1,2,3,4-tetramethylfulvene (C5Me4CH2).10,13 in
reaction with KPR2 (R = Ph, Me), producing the potassium salt,
5
1
5
which can be easily used to prepare complexes of the type (h -
6
C5Me4(CH2)nPPh2)MLx (n = 1,2).10
5
We have previously demonstrated that tetramethylfulvene
6
erodifunctional ligand that contain a phosphine and amino
groups connected directly or by a short chain to the cyclopen-
tadienyl ring bound to Re(CO)3 fragment, have been devel-
oped by Bolm. This Josiphos type of ligand coordinated to
palladium was used as catalyst in asymmetric allylic alkyla-
complexes (h -C5Me4CH2)Re(R)(CO)2 (R = C6F5, I) can be
used as good precursors in the syntheses of a series of func-
tionalized tetramethylcyclopentadienyl rhenium complexes. For
instance, the fulvene complexes react with allylmagnesium
5
chloride or 2-thienyllithium to yield the anionic species [(h -
-
=
C5Me4CH2L)Re(R)(CO)2] (L = CH2CH CH2; 2-C4H3S). Proto-
aInstituto de Qu´ımica, Universidad Cato´lica de Valpara´ıso, Casilla,
4059, Valpara´ıso, Chile. E-mail: fernando.godoy@usach.cl, hklahn@ucv.cl;
Tel: (56)-(02)-7181034, (56)-(32)-2273174
nation with HCl afforded the trans hydride complexes, which under
thermolysis conditions (hexanes solution under an N2 atmosphere
◦
5
x
at 40 C) yielded the compounds (h :h -C5Me4CH2L)Re(CO)2
(x = 2 and 1 respectively).14
bFacultad de Ciencias F´ısicas y Matema´ticas, Universidad de Chile, Casilla,
653, Santiago, Chile
In continuation of our studies on new functionally substi-
tuted tetramethylcyclopentadienyl rhenium compounds, we now
report the synthesis and characterization of the chelated complex
cDepartment of Chemistry, University of York, York, UK, YO10 5DD
† CCDC reference numbers 703987 and 703988. For crystallographic data
in CIF or other electronic format see DOI: 10.1039/b820751h
3044 | Dalton Trans., 2009, 3044–3051
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1
(h :h -C5Me4CH2PPh2)Re(CO)2. Also described are reactions of
this compound, with two electron donor ligands leading to a series
of a three legged piano stool type of complexes of a formula
and in solution, prevented us from obtaining the mass spectrum
and elemental analysis.
Thermal reactions of trans-(g5-C5Me4CH2PPh2)-
Re(C6F5)(H)(CO)2 (2)
5
(h -C5Me4CH2PPh2)Re(L)(CO)2.(L = CO, PMe3, tBuNC) and the
reactions with iodine, HBF4 and MeOTf to yield the new chelated
cationic complexes trans-[(h :h -C5Me4CH2PPh2)Re(R)(CO)2]+
5
1
The hydride complex 2, underwent reductive elimination of
pentafluorobenzene very easily. However, the nature of the
organometallic products depended on whether CO or N2 was
used for the reaction (Scheme 2): under nitrogen only the chelated
(R = I, H, Me).
Results and discussion
5
1
complex (h :h -C5Me4CH2PPh2)Re(CO)2 (3) was obtained in 70%
Reactions of the fulvene complex (g6-C5Me4CH2)(C6F5)Re(CO)2
yield, whereas thermal reaction under a CO atmosphere afforded
5
a mixture of 3 and the tricarbonyl (h -C5Me4CH2PPh2)Re(CO)3
Addition of a small excess of potassium diphenylphosphide
to a solution of the fulvene precursor produced the anionic
complex [(h -C5Me4CH2PPh2)Re(C6F5)(CO)2]- (1) (Scheme 1).
The anion 1 was not isolated and it was identified only by IR
spectroscopy in solution. The two prominent absorption bands
(n(CO)), observed at 1862 and 1774 cm-1 in THF, are comparable
to those reported for analogous anionic rhenium complexes.14,15
Complex 1 was reacted in situ with HCl at 0 ◦C to give the
4a, in a 2 : 1 ratio. Prolonged heating of the mixture resulted
exclusively in the formation of the complex 4a. In both cases, the
presence of C6F5H was confirmed by GC-MS.
5
Complex 3 was isolated as air stable, pale yellow crystals, soluble
in most of organic solvents; its solutions are stable for weeks if
kept under nitrogen. Infrared data of 3 showed two strong CO
absorptions at almost the same frequency to those observed for the
5
complex (h -C5Me5)Re(PPh3)(CO)2.17 The presence of two distinct
5
hydride complex trans-(h -C5Me4CH2PPh2)Re(C6F5)(H)(CO)2 (2)
methyl resonances observed in the 1H NMR spectrum of complex
3 and one doublet for methylene group (JPH = 35 Hz) agree
well with the symmetric nature of the complex that results from
(Scheme 1). This compound showed characteristic CO absorption
bands at 2022 and 1945 cm-1 in THF solution, similar to those
observed in other hydride fluoroaryl complexes possessing the
two CO ligands in a diagonal or trans orientation.16 The 1H-
NMR spectrum of 2 in d6-benzene showed a broad low frequency
resonance (d: -8.82) for the hydride proton, probably broadened
5
1
coordination of the C5Me4CH2PPh2 ligand to rhenium in an h :h
fashion. In addition, to the expected resonances for the carbon
nuclei of the chelated ligand, the 13C NMR spectrum of 3 also
showed a high frequency doublet (d: 207.2; JPC = 7.7 Hz) for the
by long range couplings to fluorine nuclei, as observed for the
related complexes trans-(h -C5Me5)Re(ArylF)(H)(CO)2 (ArylF
1
two equivalent CO groups. The 31P{ H} NMR spectrum, exhibited
5
=
a single resonance at d: -105.9 for the coordinated phosphorus of
the phosphine side arm. Further confirmation of the structure of
complex 3 was obtained from a X-ray diffraction study (vide infra).
C6F5, 2,3,5,6-C6HF4).16 The presence of the (diphenylphosphine-
methyl)-tetramethylcyclopentadienyl ligand (C5Me4CH2PPh2) in
complex 2, was unequivocally established by 1H, 13C and 31P-NMR
spectroscopy. In addition, the presence of the pentafluorophenyl
group was confirmed by 19F NMR spectroscopy.15,16 The trans
stereochemistry was confirmed by the presence of a single
resonance for the CO groups in the 13C-NMR spectrum. The
extreme air sensitivity of the hydride complex 2 both as a solid
Reaction of the complex (g5:g1-C5Me4CH2PPh2)Re(CO)2 (3) with
two electron donor ligands
In an effort to explore the reactivity of the phosphine functional-
ized tetramethylcyclopentadienyl ligand coordinated to rhenium,
Scheme 1 Godoy et al. “Synthesis, Reactivity and Molecular Structure of Phosphino....”
Scheme 2 Godoy et al. “Synthesis, Reactivity and Molecular Structure of Phosphino....”
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t
5
complex 3 was reacted with CO, PMe3 and BuNC. In all cases,
phosphine ligand in the complex [(h -C5Me4CH2PMe2)]2Fe, which
displacement of the coordinated phosphine of the side arm was
observed, producing the three-legged piano-stool complexes, (h -
was confirmed by X-Ray diffraction.10
5
Oxidative addition reactions to (g5:g1-C5Me4CH2PPh2)Re(CO)2
(3). While the reaction of 3 with two electron donor ligands pro-
duced Re(I) complexes possessing a three-legged piano-stool type
of structure, reaction of this complex with I2, HBF4 and MeOTf
yielded Re(III) cationic complexes trans-[(h :h -C5Me4CH2PPh2)-
Re(R)(CO)2]+ (5a, R = I; 5b, R = H; 5c, R = Me) (Scheme 4).
As cationic species, these complexes are insoluble in non polar
solvents but dissolve in CHCl3, CH2Cl2 and THF, in which they
are stable with respect to thermal isomerization. The presence
of the (diphenylphosphinomethyl)-tetramethylcyclopentadienyl
C5Me4CH2PPh2)Re(L)(CO)2 (4a, L = CO; 4b, L = PMe3; 4c,
t
L = BuNC) in almost quantitative yields (Scheme 3). The IR
spectra of the complexes 4a and 4b showed CO absorptions
bands at the same wave number as those observed for the
5
1
18
19
complexes Cp*Re(CO)3 and Cp*Re(PMe3)(CO)2 respectively.
Evidence for the non-coordinated diphenylphosphine side arm
of the cyclopentadienyl ligand could be easily inferred from the
31P{ H} NMR spectrum of the complexes 4a–c, since a single
1
resonance was observed at about d -14 in all cases. A similar
low frequency shift of the intermolecular coordinated and non-
coordinated phosphine group has been also previously observed
5
1
ligand coordinated to the rhenium in an h :h -fashion was
unequivocally established by 1H and 13C NMR spectroscopy.
5
5
1
in the complexes (h -C5H4SiMe2P(p-tolyl)2)2ZrMe2 and (h :h -
C5H4SiMe2P(p-tolyl)2)2ZrMe.20 In addition, the 31P{ H} NMR
1
spectrum of 4b also showed a resonance for the PMe3 ligand at d
-28.4 which agrees well with that reported for Cp*Re(PMe3)(CO)2
(d -27.0).19
Scheme 4 Godoy et al. “Synthesis, Reactivity and Molecular Structure
of chelated complex....”
Like many other hydrido rhenium complex,23 5b transforms to
5
1
the chloro derivative trans-[(h :h -C5Me4CH2PPh2)Re(Cl)(CO)2]+
(5d) when dissolved in chlorinated solvents. After 16 h in CDCl3
the hydride complex transforms completely into 5d. An example
of this type of chlorination has been reported by Jones et al.;24
Scheme 3 Godoy et al. “Synthesis, Reactivity and Molecular Structure
of Phosphino....”
t
The presence of the BuCN ligand coordinated to rhenium
-1
5
1
∫
in complex 4c was confirmed by IR (n(C N) at 2132 cm
addition of CCl4 to (h :h -C5H4SiMe2CH2PPh2)Rh(H)(C6F5) led
5 1
(s)), H and 13C-NMR spectroscopy (see Experimental section).
to the complex (h :h -C5H4SiMe2CH2PPh2)Rh(Cl)(C6F5).
The IR spectra of compounds 5a–d showed only two n(CO)
absorptions. Furthermore, the relative intensity of these absorp-
tions are typical for a trans arrangement of the two CO groups
i.e. the higher wavenumber absorption being much less intense of
the pair. As expected, the two n(CO) absorptions band are shifted
to much higher frequency when compared to those observed for
3 as a result of reduction of the electron density at the Re(III) in
complexes 5a–d.
1
The spectroscopic parameters are in good agreement with those
reported for the complex CpRe(CNtBu)(CO)2.21
The lability of the phosphine ligand in compound 3 is not
surprising, it has been previously observed in other Cp–phosphine
metal complexes.22 This can be associated to the ring strain, which
can be evidenced by the structural studies of 3; the angle between
the methylene carbon, the phosphorus atom and the rhenium atom
is smaller than 109.5◦, i.e. a tetrahedral angle. As C(10) appears
to be displaced from the plane defined by C(1) to C(5), upon
ring-opening C(10) remains in the plane defined by C(1) to C(5)
yielding complexes 4a–c.
1
The 31P{ H} NMR spectra of 5a–d also confirmed the co-
ordination of the diphenylphosphine group to rhenium, since
a single resonance is observed at about d -150. The low
frequency shift of about 50 ppm when compared with the
Re(I) starting material, agrees well with those observed for
When exposed to air, solutions of compounds 4a–c suffered
partial oxidation of the phosphine group to yield the complexes
5
t
5
1
5
1
(h -C5Me4CH2P(O)Ph2)Re(L)(CO)2 (L = CO, PMe3, BuNC).
the complexes (h :h -C5Me4SiMe2CH2PPh2)Rh(C2H4) and (h :h -
Oxidation is indicated by an high frequency shift of the 31P{ H}
C5Me4SiMe2CH2PPh2)RhI2.25
1
~
NMR resonance (Dd ~ 42) as well as by mass spectra of the
final products. We did not make further efforts to isolate and
characterize these oxidation products. This kind of oxidation
reaction was also observed in the molecule (C5Me4HPPh2); in
The presence of a doublet at d ~ 195 (JPC 16 Hz) for the
=
CO groups observed in the 13C{ H} NMR spectra of 5a–d is
1
further evidence for a trans stereochemistry exhibited for these
compounds.
1
1
both cases, the 31P{ H} NMR spectrum showed a single resonance
The H-NMR spectrum of the hydride complex (5b) showed
shifted high frequency (Dd ~ 42) with respect to the unoxidised
phosphorus atoms. Green et al. reported the oxidation of the
a doublet at d -6.56 (JHP = 20.8 Hz) which confirmed the
coordination of the diphenylphosphine ligand to the rhenium
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5
1
fragment. This chemical shift is very close to those reported for
spectroscopies. In addition the molecular structure of cis-(h :h -
C5Me4CH2PPh2)ReI2(CO) (6a) was determined by X-ray crys-
tallography. Similar decarbonylation reactions, have been ob-
served previously in our laboratory in the cationic complexes
[(h :h -C5Me4CH2 CH2CH CH2)Re(H)(CO)2] (d: -6.64)14 and
other rhenium hydride complexes.23 It is important to note that
the values of the coupling constant JPH can also be used to support
the trans stereochemistry previously proposed. For example, Faller
and Anderson reported the synthesis and characterization of a
5
2
+
=
[Cp*ReI(CO)2(L)]+ I3 (L = CO, P(OMe)3, P(OPh)3, PMe3,
-
PMe2Ph) which yield the neutral complexes Cp*ReI2(L)(CO).28
Complex 6a showed a single n(CO) absorption band at 1906
cm-1 and a single resonance (d 217; JPC = 17 Hz) for the CO
group in the 13C NMR spectrum, both parameters are almost
identical to those recorded for the monocarbonyl diiodo complex
cis-Cp*ReI2(PMe2Ph)(CO).28
5
series of hydride complexes, (h -C5H5)Mo(PR3)(H)(CO)2 (R =
Me, n-Bu, Ph), the 1H-NMR spectra of the trans complexes
~
exhibit one resonance at ~ -6.2 ppm (JHP 22 Hz), while the cis
=
26
~
isomers showed a coupling significantly larger (JHP 60 Hz).
=
A similar coupling constant was found in the complex trans-
[(Cp)Re(PPh3)(H)(CO)2]+, where the JHP is 2.5–3 times smaller
than in the corresponding cis isomer.27
X-Ray structure of
3 and 6a. The molecular struc-
5
1
5
1
tures of (h :h -C5Me4CH2PPh2)Re(CO)2 (3) and (h :h -
C5Me4CH2PPh2)Re(I)2(CO) (6a) are shown in Fig. 1 and 2,
respectively. Table 1 collects the most relevant bond distances
With the aim of having a more complete understanding of the
effect of the oxidation state of rhenium on the coordination of
the lateral phosphine ligand, we carried out the reaction of the
5
1
cationic complexes trans-[(h :h -C5Me4CH2PPh2)Re(R)(CO)2]+
(5a, R = I and 5c, R = Me) with KI in the presence of
the decarbonylation agent Me3NO·2H2O in CH2Cl2 at room
temperature. In both cases, the neutral chelated complexes cis-
5
1
(h :h -C5Me4CH2PPh2)Re(I)(R)(CO) (6a, R = I and 6b, R =
Me) were obtained, as shown in Scheme 5. The products
were isolated as a single isomers, as red–brown and orange
microcrystals respectively, and characterized by IR and NMR
5
1
Scheme 5 Godoy et al. “Synthesis, Reactivity and Molecular Structure
Fig. 1 Molecular structure of (h :h -C5Me4CH2PPh2)Re(CO)2 (3) drawn
of Phosphino....
with 50% probability displacement ellipsoids. Hydrogen atoms omitted.
5
1
Fig. 2 Molecular structure of (h :h -C5Me4CH2PPh2)Re(I)2(CO) (6a) drawn with 50% probability displacement ellipsoids. Hydrogen atoms omitted.
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◦
˚
Table 1 Selected bond lengths (A) and angles ( ) for complexes 3 and 6a
Experimental
3
6a
General
Re(1)–P(1)
Re(1)–C(1)
Re(1)–C(23)
Re(1)–C(24)
Re(1)–I(1)
2.320 (8)
2.259 (3)
1.896 (3)
1.905 (3)
2.436(3)
2.257(9)
1.865(10)
All reactions were carried out under nitrogen using standard
Schlenk techniques. All solvents were purified and dried by
conventional methods, and distilled under nitrogen prior to use.
Potassium diphenylphosphide and hydrogen chlorine in ether were
obtained from Aldrich. Infrared spectra were recorded in solution
—
—
—
2.7868(9)
2.7855(8)
1.940 (3)
1.080(9)
Re(2)–I(2)
Re(1)–Ga
1.929 (3)
1.156 (4)
1.151 (4)
1.525 (4)
1.856 (3)
89.08 (14)
91.16 (10)
97.78 (19)
127.8 (2)
—
1
(CaF2 cell) on a Perkin-Elmer FT-1605 spectrophotometer. H,
C(23)–O(1)
C(24)–O(2)
C(1)–C(10)
C(10)–P(1)
C(23)–Re(1)–C(24)
Re(1)–P(1)–C(10)
C(1)–C(10)–P(1)
Re(1)–C(5)–C(9)
I(1)–Re(1)–I(2)
13C, 19F and 31P NMR spectra were recorded on a Bruker AC
400 instrument. All 1H NMR chemical shifts are referenced
using the chemical shifts of residual solvent resonance. 13C NMR
chemical shifts were referenced to solvent peaks. 19F NMR spectra
—
1.524(14)
1.832(10)
—
91.9(3)
95.6(6)
128.5(7)
81.69(3)
1
were referenced to internal C6F6 at d -162.9 and 31P{ H} NMR
chemical shifts were referenced to external H3PO4 (85%) at d 0.0.
Mass spectra (VG Autospec) were obtained at the Chemistry
Department of the University of York, England. Elemental anal-
yses were obtained at the Centro de Instrumentacio´n, Pontificia
Universidad Cato´lica de Chile, Santiago, Chile.
a G = Centroid (C5Me4CH2PPh2)
and angles. Complex 3 exhibits a three-legged piano-stool type of
structure, where the two basal positions are occupied by carbonyls
groups and the third is used for the phosphorus atom of the
cyclopentadienyl diphenylphosphine moiety, whereas complex 6a
exhibits a four-legged piano-stool structure with a CO, two iodines
and the phosphorus occupying the basal positions.
Syntheses
6
The fulvene complex (h -C5Me4CH2)Re(CO)2(C6F5) was prepared
5
from (h -C5Me5)Re(CO)3 according to the procedure described in
literature.15b
Trans-(g5-C5Me4CH2PPh2)Re(C6F5)(H)(CO)2 (2). To a solu-
tion of (h -C5Me4CH2)Re(C6F5)(CO)2 (100 mg, 0.184 mmol) in
˚
The Re–CO bond distances (1.896(3) and 1.905(3) A) of
5
6
3 are in a good agreement with those reported for [(h -
THF (15 mL) stirred at 0 ◦C was added 0.40 mL (0.200 mmol) of
KPPh2 (0.5 M in THF). The reaction mixture turned pale yellow
immediately and the IR spectrum only showed CO absorptions
at 1862 and 1774 cm-1. Then the HCl solution in diethyl ether
(0.3 mL, 0.300 mmol) was added. The IR spectrum of the solution
showed the complete disappearance of the anionic species and
new CO absorptions at 2015, 1942 cm-1. The solvent was removed
under vacuum. Hexanes (3 ¥ 10 mL) was added to the residue, and
the mixture filtered. The solvent was pumped off to afford 2 as a
pale yellow solid. IR [hexane, n(CO), cm-1]: 2024 (s), 1959 (vs).
1H NMR (C6D6) d: -8.82 (Re-H), 1.40 (s, 6H, C5Me4), 1.42 (s,
6H, C5Me4), 4.95 (d, JPH 9.9 Hz, 2H, CH2), 7.65 (m, 10 H, PPh2).
+
-
29
˚
C5Me4CH2PMe3)Re(CO)2(PMe3)] I (1.877 and 1.912 A). The
˚
C(10)–P(1) and C(1)–C(10) distances (1.856(3) and 1.525(4) A)
5
1
are comparable to those of the complexes [(h :h -C5H4CMe2P(p-
tolyl2)2Zr(X)]+ (X = Me, Cl).20
˚
In relation of the Re-P length (2.320(8) A) of 3 is shorter than
˚
the Re(III) complex 6a (2.436(3) A), and is very close to other
phosphine complexes of rhenium(I).14,28
The Re–I(1) and Re–I(2) distances in 6a are 2.7855(8) and
˚
2.7868(9) A, respectively, indicating that they are unaffected by the
ligand trans to them. The I(1)–Re–I(2) angle is 81.69(3)◦, which
clearly establishes the cis orientation of these ligands. This value
5
is in good agreement with those reported for the complex cis-(h -
C5Me5)Re(I)2(CO)2.29
1
13C{ H} NMR (C6D6) d : 10.7 (s, C5Me4), 10.8 (s, C5Me4), 26.6 (d,
J
PC 18 Hz, CH2), 97.5 (s, C5Me4), 98.6 (s, C5Me4), 99.6 (s, C5Me4);
128.5 (d, JPC 11 Hz, Cmeta Ph), 130.1 (d, JPC 2 Hz, Cpara, Ph), 132.2
(d, JPC 13 Hz, Cortho, Ph), 134.6 (d, JPC 47 Hz, Cipso, Ph), 195.4 (s,
Conclusion
1
CO). 31P{ H} NMR d: -16.2. 19F (C6D6) d: -102.9 (d, JFF 22.9 Hz,
6
The fulvene complex (h -C5Me4CH2)Re(C6F5)(CO)2 acts as a
good precursor for the synthesis of several functionalized tetram-
2Fortho), -157.6 (t, JFF = 22.9 Fpara), -162.4 (t, JFF = 22.9 Fmeta).
ethylcyclopentadienyl rhenium complexes. Reaction with KPPh2
followed by HCl yields trans-(h -C5Me4CH2PPh2)Re(C6F5)-
(g5:g1-C5Me4CH2PPh2)Re(CO)2 (3). The hexanes solution
containing the hydride complex 2 (prepared from fulvene complex,
100 mg, 0.184 mmol), was heated under N2 at 40 ◦C for 3 h.
The solution turned pale yellow and yellow solid was formed. An
IR spectrum recorded at this time showed two strong absorption
bands at 1926 and 1866 cm-1 (hexanes). The reaction mixture was
concentrated under vacuum, and the solid was chromatographed
through a short Florisil column. Elution with hexanes–CH2Cl2
(1 : 1) moved a light yellow band from which complex 3 was
isolated in 70% as yellow solid (72 mg, 0.128 mmol). IR [CH2Cl2,
5
(H)(CO)2. Reductive elimination of C6F5H yields the chelated
5
1
species (h :h -C5Me4CH2PPh2)Re(CO)2 containing an intra-
molecularly coordinated diphenylphosphine fragment. The PPh2
group is easily displaced by two electron donor ligands such as
CO, PMe3 and tBuNC. The phosphorus atom of the side chain of
the functionalized tetramethylcyclopentadienyl system, is partially
oxidized when the unchelated species are exposed to air. Reaction
with I2, HBF4 and MeOTf yielded Re(III) cationic species with
a trans stereochemistry, in which the PPh2 sidearm remained
coordinated. A CO group could be abstracted from the cationic
species with Me3NO in the presence of KI.
1
n(CO), cm-1]: 1920 (vs), 1855 (vs). H-NMR (C6D6) d: 2.16 (s,
6H, C5Me4), 2.28 (s, 6H, C5Me4), 4.06 (d, JPH 8.8 Hz, 2H,CH2),
1
7.42 (m, 6H, PPh2), 7.66 (m, 4H, PPh2). 13C{ H} NMR (CDCl3)
3048 | Dalton Trans., 2009, 3044–3051
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d : 11.2 (s, C5Me4), 11.9 (s, C5Me4), 24.5 (d, JPC 35 Hz, CH2), 80.2
(d, JPC 3 Hz, C5Me4), 91.4 (d, JPC 2 Hz, C5Me4), 98.5 (d, JPC 3 Hz,
C5Me4), 128.5 (d, JPC 11 Hz, Cmeta Ph), 130.1 (d, JPC 2, Cpara, Ph),
132.2 (d, JPC 13 Hz, Cortho, Ph), 134.6 (d, JPC 47 Hz, Cipso, Ph), 207.2
0.055 mmol, d = 0.795 g/mL, 97%). After 5 min at room
temperature, the 1H NMR spectrum of the reaction mixture
showed the complete disappearance of 3 and the presence of 4c.
The reaction mixture was filtered through Celite, the solvent was
1
(d, JPC 8 Hz, CO). 31P{ H} NMR (CDCl3) d: -105.9 (s, PPh2).
pumped off and 4c was isolated as a white solid. Yield 32 mg
-1
Mass spectrum (low energy) (IE, based on 187Re) m/z : 562 [M+],
532 [M+ - CO -2H], 506 [M+ - 2CO].
(0.049 mmol, 91%). IR [hexanes, cm ] n(C N): 2132 (s); n(CO):
∫
1928 (s) 1889 (vs). 1H NMR (C6D6) d: 1.12 (s, 9H, CNtBu), 1.95 (s,
6H, C5Me4), 2.04 (s, 6H, C5Me4), 3.44 (s, 2H, CH2), 7.14 (m, 6H,
(a) From complex 2
Ph), 7.49 (m, 4H, Ph). 13C{ H}-NMR (C6D6) d: 10.6 (s, CNtBu),
1
(g5-C5Me4CH2PPh2)Re(CO)3 (4a). The hexanes solution con-
taining the hydride complex 2 (prepared from 1, 100 mg,
0.184 mmol), was bubbled with CO and then heated at 40 ◦C for
3 h. An IR spectrum recorded at this time showed two strong ab-
sorption bands at 2026 and 1966 cm-1, and also minor absorptions
at 2013 and 1923 cm-1. The reaction mixture was concentrated
under vacuum to ca. 3 mL, and then it was filtered through a
short Florisil column (3 cm) under a N2 atmosphere. Elution
11.0 (s, C5Me4), 11.1 (s, C5Me4), 27.3 (d, JPC = 18 Hz, CH2), 95.3
(d, JPC = 19 Hz, C5Me4), 96.7 (s, C5Me4), 97.9 (d, JPC = 2 Hz,
C5Me4), 128.5 (d, JPC = 7 Hz, Ph), 133.5 (d, JPC = 19 Hz, Ph),
138.57 (d, JPC = 17 Hz, Ph), 202.7 (s, CO). 31P{ H} NMR d: -13.9
1
(s, PPh2). MS (EI, based on 187Re) m/z : 654 [M+], 617 [M+ - CO],
562 [M+ - CNtBu].
Note: No satisfactory elemental analysis of the complexes 4,
was obtained because of partial oxidation of the lateral phosphine
group.
5
with hexanes removed the complex (h -C5Me4CH2PPh2)Re(CO)3
(4a), which was obtained as a white solid after evaporation of the
solvent. Recrystallisation from hexanes yielded 4a as solid as with
(26 mg, 0.044 mmol, 24% yield) elution with hexanes : CH2Cl2
(1:4) removed the chelated complex 3 (42 mg, 0.075 mmol, 41%
trans-[(g5:g1-C5Me4CH2PPh2)Re(I)(CO)2]+ I- (5a). To a solu-
tion of 3 (80 mg, 0.143 mmol) in 15 mL of CH2Cl2 was added I2
(36 mg, 0.143 mmol). An IR spectrum showed the disappearance
of CO absorptions due to the starting complex, and the emergence
of new absorption bands at 2046 and 1986 cm-1. The solvent was
removed under vacuum, and the residue was kept under vacuum. It
was dissolved in the minimum amount of CH2Cl2, and crystallized
by diffusion of a hexanes layer. 5a was isolated as brownish-red
crystals in 63% yield. (73 mg, 0.089 mmol). IR [CH2Cl2, n(CO),
cm-1]: 2046 (s) 1986 (vs). 1H-NMR (CDCl3) d: 2.39 (s, 6H, C5Me4),
2.41 (s, 6H, C5Me4), 5.10 (d, JPH = 9.5 Hz, 2H, CH2), 7.74 (m,
5
yield). (h -C5Me4CH2PPh2)Re(CO)3 (4a). IR [hexanes, n(CO),
cm-1]: 2013 (s) 1923 (s); 1H NMR (CDCl3) d: 1.81 (s, 6H, C5Me4),
2.14 (s, 6H, C5Me4), 3.25 (s, 2H, CH2), 7.57 (m, 10 H, PPh2).
1
13C{ H} NMR (CDCl3) d: 10.7 (s, C5Me4), 10.8 (s, C5Me4), 26.6
(d, JPH = 18 Hz, CH2), 97.5 (s, C5Me4), 98.6 (s, C5Me4), 99.5 (s,
C5Me4), 128.6 (d, JPC = 7 Hz Ph), 130.8 (d, JPC = 11 Hz Ph), 136.8
1
(d, JPC = 15 Hz Ph), 133.2 (d, JPC = 19 Ph), 197.9 (s, CO). 31P{ H}
NMR d: -14.7. MS (EI, based on 187Re) m/z: 562 [M+ - CO], 532
[M+ - 2CO - 2H].
1
6H, Ph), 7.77 (m, 4H, Ph). 13C{ H} NMR (CDCl3) d: 11.7 (s,
C5Me4), 12.2 (s, C5Me4), 20.0 (d, JPC = 33 Hz, CH2), 80.7 (d,
JPC = 7 Hz, C5Me4), 102.0 (s, C5Me4), 106.5 (s, C5Me4), 124.1 (d,
JPC = 58 Hz, Cipso Ph), 130.1 (d, JPC = 13 Hz, Cortho, Ph), 130.8 (d,
JPC = 11 Hz, Cmeta, Ph), 133.3 (d, JPC = 3 Hz, Cpara, Ph), 187.8 (d,
(a) From complex 3
(g5-C5Me4CH2PPh2)Re(CO)3 (4a). A sample of 3 (10 mg,
0.018 mmol) in benzene-d6 in an NMR tube was left under a
CO atmosphere for 12 h at room temperature. After this time the
NMR spectrum showed the complete disappearance of 3 and the
presence of 4a.
1
JPC = 18 Hz, CO). 31P{ H} NMR (CDCl3) d: -148.1 (s, PPh2). MS
(IES, based on 187Re) m/z : 689 [M+]; 661 [M+ - CO]. Anal. Calcd.
for C24H24O2I2PRe: C, 35.37; H, 2.97. Found: C, 36.03; 3.11.
trans-[(g5:g1-C5Me4CH2PPh2)Re(H)(CO)2]+ BF4 (5b). To a
-
(g5-C5Me4CH2PPh2)Re(PMe3)(CO)2 (4b). To a solution of
complex 3 (30 mg; 0.054 mmol) in benzene-d6 was added PMe3
(6 mL, 0.057 mmol, d = 0.735 g/mL; 97%) the reaction was
monitored by 1H NMR spectroscopy. After 5 min at room
temperature, the spectrum showed the complete disappearance
of the chelated complex 3 and the presence of the 4b, the reaction
mixture was filtered through Celite, the solvent was pumped off
and the complex 4b was isolated as a white solid. Yield 33 mg
(0.052 mmol, 96%). IR [hexanes, n(CO), cm-1]: 1920 (s), 1856 (vs).
1H NMR (C6D6). d: 1.33 (d, JPH = 9.10 Hz, 9H, PMe3), 1.86 (s,
6H, C5Me4), 1.90 (s, 6H, C5Me4), 3.41 (s, 2H, CH2), 7.11 (m, 6H,
solution of 3 (30 mg, 0.053 mmol) in chloroform-d was added
HBF4 (8 mL; 0.0581 mmol, d = 1.180 g/mL, 54%, in Et2O). The
re◦action was monitored by 1H NMR spectroscopy. After 5 min at
0 C, the spectrum showed the complete disappearance of 3 and
the presence of 5b. This compound could not be isolated as a pure
sample and was only identified in situ by spectroscopic techniques.
IR [CH2Cl2, n(CO), cm-1]: 2038 (s), 1977 (vs). 1H-NMR (CDCl3)
d: -6.56 (d, JPH = 20.8 Hz, 1H, Re-H), 2.39 (s, 6H, C5Me4), 2.42
(s, 6H, C5Me4), 4.80 (d, JPH = 10.2 Hz, 2H, CH2), 7.61 (m, 10H,
1
Ph). 13C{ H}-NMR (CDCl3) d: 10.7 (s, C5Me4), 12.1 (s, C5Me4),
1
Ph), 7.44 (m, 4H, Ph). 13C{ H}-NMR (C6D6) d: 11.3 (s, C5Me4),
16.4 (d, JPC = 36 Hz, CH2), 81.4 (s, C5Me4), 99,3 (s, C5Me4), 103.0
(s, C5Me4); 126.2 (d, JPC = 56 Hz, Cipso Ph), 129.9 (d, JPC = 13 Hz,
Cortho, Ph), 131.8 (d, JPC = 12 Hz, Cmeta, Ph); 132.6 (d, JPC = 3 Hz,
11.0 (s, C5Me4), 22.1 (d, JPC = 35 Hz, PMe3), 27.6 (d, JPC = 18 Hz,
CH2), 94.6 (d, JPC = 19 Hz, C5M4), 95.0 (s, C5Me4), 96.7 (d, JPC
=
1
Cpara, Ph); 193.0 (d, JPC = 15 Hz, CO). 31P{ H} (CDCl3) d: -152.82
2 Hz, C5Me4), 128.5 (d, JPC = 7 Hz, Ph), 133.5 (d, JPC = 19 Hz,
1
Ph), 138.6 (d, JPC = 16 Hz, Ph), 206.0 (d, JPC = 8 Hz, CO). 31P{ H}
(s, PPh2).
NMR (C6D6) d: -28.4 (s, PMe3), -14.3 (s, PPh2). MS (EI, based on
187Re) m/z : 637 [M+ - H], 610 [M+ - CO], 562 [M+ - PMe3].
trans-[(g5:g1-C5Me4CH2PPh2)Re(Me)(CO)2]+ OTf- (5c). To a
solution of 3 (30 mg, 0.053 mmol) in chloroform-d was added
MeOTf (6 mL, 0.054 mmol, d = 1.450 g/mL, 99%). The
(g5-C5Me4CH2PPh2)Re(CNtBu)(CO)2 (4c). To a solution of
3 (30 mg, 0.054 mmol) in benzene-d6 was added CNtBu (6 mL,
1
reaction was monitored by H NMR spectroscopy. After 5 min
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at room temperature, under argon, the NMR spectrum showed
the complete disappearance of 3 and the presence of 5c. The
reaction mixture was concentrated under vacuum to dryness and
the residue was dissolved in CH2Cl2 and filtered through Celite.
The filtrate was evaporated to ca. 2 mL and carefully layered with
hexanes. Complex 5c was isolated as a brownish-red solid. Yield:
21 mg (0.029 mmol, 55%) IR [CH2Cl2, n(CO), cm-1]: 2029 (s), 1966
(vs). 1H NMR (CDCl3) d: 0.90 (d, JHP = 2.8 Hz, 3H, Re-Me), 1.84
(s, 6H, C5Me4), 2.35 (s, 6H, C5Me4), 4.81 (d, JPH = 9.3 Hz, 2H,
110.3 (s, C5Me4), 124.6 (d, JPC = 58 Hz, Cipso Ph), 130.1 (d, JPC
=
=
13 Hz, Cortho, Ph). 131.8 (d, JPC = 12 Hz, Cmeta, Ph), 133.2 (d, JPC
1
2 Hz, Cpara, Ph), 192.2 (d, JPC = 17 Hz, CO). 31P{ H} (CDCl3) d:
-147.8 (s, PPh2). MS (IES, based on 187Re and 35Cl) m/z: 597 [M+],
569 [M+ - CO].
cis-(g5:g1-C5Me4CH2PPh2)Re(I)2(CO) (6a). To a solution of
5a (75 mg, 0.092 mmol) in 15 mL of CH2Cl2 was added
Me3NO·2H2O (11 mg, 0.099 mmol) and KI (33 mg, 0.199 mmol).
The reaction mixture was stirred at room temperature for 30 min.
At this time, the IR spectrum showed the disappearance of the
starting complex and one new CO absorption band at 1906 cm-1.
The solvent was removed under vacuum and the solid residue
was chromatographed on a short Florisil column. Elution with
hexanes–CH2Cl2 (1 : 4) moved the complex 6a. The solvent was
pumped off, and the red–brown residue was dissolved in the
minimum amount of CH2Cl2 and crystallized by diffusion of a
hexanes layer. Yield: 45 mg (0.0571 mmol, 62%). IR [CH2Cl2,
n(CO), cm-1]: 1906 (s). 1H NMR (CDCl3) d: 2.10 (s, 6H, C5Me4),
2.18 (s, 3H, C5Me4), 2.52 (s, 3H, C5Me4), 4.15 (dd, JPH = 15.3 Hz,
JHH = 9.0 Hz, 1H, CH2), 4.42 (dd, JPH = 15.3 Hz, JHH = 9.0 Hz,
1H, CH2), 7.41 (m, 5H, Ph), 7.53 (m, 3H, Ph), 7.72 (m, 2H, Ph).
1
CH2), 7.58 (m, 6H, Ph), 7.63 (m, 4H, Ph). 13C{ H} NMR (CDCl3)
d: -16.2 (Re-Me), 8.3 (s, C5Me4), 10.7 (s, C5Me4), 19.6 (d, JPC
=
36 Hz, CH2), 79.5 (d, JPC = 4 Hz, C5Me4), 99.5 (s, C5Me4), 103.1
(s, C5Me4), 126.3 (d, JPC = 57 Hz, Cipso Ph), 129.9 (d, JPC = 12 Hz,
Cortho, Ph), 131.8 (d, JPC = 11 Hz, Cmeta, Ph), 132.6 (s, Cpara, Ph);
1
195.6 (d, JPC = 16 Hz, CO). 31P{ H} NMR (CDCl3) d: -148.7
(s, PPh2). MS (IES, based on 187Re) m/z: 577 [M+], 549 [M+
-
CO]. Anal. Calcd. for C24H24O2I2PRe: C, 35.37; H, 2.97. Found:
C, 36.03; H, 3.11.
trans-[(g5:g1-C5Me4CH2PPh2)Re(Cl)(CO)2]+ BF4 (5d). The
-
hydride complex 5b was dissolved in chloroform-d and the solution
was left for 16 h. The solvent was removed under vacuum and the
residue was dissolved in a minimum amount of CH2Cl2; then it
was filtered through a short Celite column (1 cm). The solvent
was pumped off to yield a residue which was crystallised from
CH2Cl2/hexanes. 5d was obtained as an orange–red solid (15 mg,
0.022 mmol, 42% yield). IR (CH2Cl2, n(CO), cm-1): 2051 (s) 1989
(vs).1H NMR (CDCl3) d: 1.93 (s, 6H, C5Me4), 2.42 (s, 6H, C5Me4),
4.81 (d, JPH = 10.2 Hz, 2H, CH2), 7.63 (m, 6H, Ph). 7.73 (m, 4H,
1
13C{ H} NMR (CDCl3) d: 10.9 (s, C5Me4), 11.1 (s, C5Me4), 11.4
(s, C5Me4), 12.9 (s, C5Me4), 18.0 (d, JPC = 32 Hz, CH2), 76.4 (d,
JPC = 7 Hz, C5Me4), 91.1 (d, JPC = 3 Hz, C5Me4), 92.2 (s, C5Me4),
104.9 (d, JPC = 3 Hz, C5M4), 109.1 (s, C5Me4), 127–132 (Ph); 217.5
1
(d, JPC = 17 Hz, CO). 31P{ H} NMR (CDCl3) d: -150.5 (s, PPh2).
MS (EI, based on 187Re) m/z: 788 [M+], 661 [M+ - I]. Anal. Calcd
for C23H24I2OPRe: C, 35.04; H, 3.07. Found: C, 34.81; H, 2.95.
1
Ph). 13C{ H} NMR (CDCl3) d: 8.6 (s, C5Me4), 10.5 (s, C5Me4),
(g5:g1-C5Me4CH2PPh2)Re(I)(Me)(CO) (6b). To a solution of
5c (prepared from 3, 50 mg, 0.089 mmol) in 15 mL of CH2Cl2,
19.9 (d, JPC = 36 Hz, CH2), 81.4 (s, C5Me4), 101.6 (s, C5Me4);
5
1
5
1
Table 2 Crystal data and structure refinement for (h :h -C5Me4CH2PPh2)Re(CO)2 (3) and (h :h -C5Me4CH2PPh2)Re(I)2CO (6a)
3
6a
Empirical Formula
Formula weight
Temperature
C24H24O2PRe
561.60
C23H24I2OPRe
787.39
293 (2) K
298 (2) K
˚
˚
Wavelength
0.71073 A
0.71073 A
Cryst. Syst.
Space group
Monoclinic
P21/n
Monoclinic
P21/n
Unit cell dimensions
˚
a, (A)
9.7394 (5)
21.5708 (1)
10.2864 (5)
102.685 (1)
2108.29 (2)
4
1.769
5.856
15.136 (2)
8.7980 (8)
17.966 (2)
103.464 (2)
2326.7 (4)
4
2.248
7.957
˚
b, (A)
˚
c, (A)
b (◦)
V. (A )
3
˚
Z
D
calcd /(g cm-3)
Absorption coefficient/(mm-1)
F(000)
1096
1464
Crystal size (mm)
0.43 ¥ 0.25 ¥ 0.25
0.27 ¥ 0.12 ¥ 0.02
q range for data collection (◦)
Limiting indices
1.89–28.05
2.01–28.10
-12 ≤ h ≤ 12, -13 ≤ k ≤ 27, -13 ≤ l ≤ 13
12358/4710
99.9%
-19 <= h <= 19, -11 <= k <= 11, -22 <= l <= 23
16711/5271
Reflections collected/unique
Completeness to q = 26.00
Min/max transmission
Refinament method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I >2s (I)]
R indices (all data)
99.9%
0.556/1
0.555/1
Full-matrix least-squares on F2
4710/0/253
Full-matrix least-squares on F2
5271/1/262
0.997
1.045
R1 = 0.0221, wR2 = 0.0521
R1 = 0.0271, wR2 = 0.0534
0.314 and -0.910
R1 = 0.0561, wR2 = 0.1088
R1 = 0.088, wR2 = 0.119
1.690 and -1.097
-3
˚
Largest difference peak and hole (e A )
3050 | Dalton Trans., 2009, 3044–3051
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was added KI (30 mg, 0.181 mmol) and Me3NO·2H2O (11 mg,
0.135 mmol). The reaction mixture was stirred at room tem-
perature for 1 h. After this time, the IR spectrum showed the
disappearance of the starting complex and one new absorption
band at 1885 cm-1. The solvent was removed under vacuum. The
solid residue was chromatographed on a short Florisil column.
Elution with hexanes–CH2Cl2 (1:4) moved the complex 7b. The
solvent was pumped off, and the orange residue was dissolved in
the minimum amount of CH2Cl2 and recrystallized by diffusion
of a hexanes layer. Yield: 21.9 mg (0.032 mmol, 47%). IR [CH2Cl2,
n(CO), cm-1]: 1885 (s). 1H NMR (CDCl3) d: 1.25 (s, 3H, Re-Me),
1.47 (s, 3H, C5Me4), 1.61 (s, 3H, C5Me4), 2.06 (s, 3H, C5Me4), 2.49
(s, 3H, C5Me4), 4.1 (dd, JPH = 15.0 Hz, JHH = 8.1 Hz, 1H, CH2),
4.25 (dd, JPH = 15.0 Hz, JHH = 8.1 Hz, 1H, CH2), 7.33 (m, 5H,
Vollmerhaus, Organometallics, 2000, 19, 1507; (f) X.-F. Hou, Y.-Q.
Cheng, P.-C. Zhang and G.-Z. Jin, Inorg. Chem. Comm., 2006, 9, 423.
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M. Bullock, Organometallics, 2005, 24, 6220.
5 (a) C. P. Casey, C. J. Czerwinski and M. E. Fraley, Inorg. Chim. Acta.,
1998, 280, 316; (b) C. P. Casey, C. J. Czerwinski, K. A. Fusie and R. K.
Hayashi, J. Am. Chem. Soc., 1997, 119, 3971; (c) Z. Pang, T. J. Burkey
and R. F. Johnston, Organometallics, 1997, 16, 120.
6 (a) T.-F. Wang, C.-C. Hwu, C.-W. Tsai and K.-J. Lin, Organometallics,
1997, 16, 3089; (b) T.-F. Wang, C.-C. Hwu and Y.-S. Wen,
Organometallics, 2004, 689, 411.
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Organometallics, 2005, 24, 245.
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Organometallics, 2004, 23, 2362.
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10 R. M. Bellabarba, G. P. Clancy, A. M. Martins, L. H. Rees and M. L.
H. Green, J. Organomet. Chem., 2001, 640, 93.
11 (a) V. Quindt, D. Saurenz, O. Schmitt, M. Scha¨rr, T. Dezember, G.
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12 D. P. Krut,’ko, M. V. Borzov, E. N. Veksler, R. S. Kirsanov and A. V.
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38, 1926.
1
Ph), 7.48 (m, 3H, Ph), 7.72 (m, 2H, Ph). 13C{ H} NMR (CDCl3)
d: -7.8 (d, JPC = 12 Hz, Re-Me), 7.5 (s, C5Me4), 8.5 (s, C5Me4), 11.3
(s, C5Me4), 11.4 (s, C5Me4), 20.9 (d, JPC = 27 Hz, CH2), (overlap,
C5Me4), 87.5 (d, JPC = 3 Hz, C5Me4), 89.5 (s, C5M4), 100.3 (d,
JPC = 2 Hz, C5Me4), 103.7 (d, JPC = 3 Hz, C5Me4), 127.6–132.8
1
(Ph); 219.8 (d, JPC = 15 Hz, CO). 31P{ H} (CDCl3) d: -154.8 (s,
PPh2). MS (EI, based on 187Re) m/z: 661 [M+ - Me], 648 [M+ -
CO]. Calcd for C24H27OPIRe: C, 42.70; H, 4.03. Found: C, 41.59;
H, 3.89.
Structure determination of complexes 3 and 6a
14 F. Godoy, A. H. Klahn, F. J. Lahoz, A. I. Balana, B. Oelckers and L.
A. Oro, Organometallics, 2003, 22, 4861.
Crystals of 3 and 6a suitable for X-ray diffraction studies were
obtained by recrystallization from CH2Cl2/hexanes diffusion at
room temperature by slow cooling to -18 ◦C. A summary of crystal
data, data collection, and refinement parameters for the structural
analyses is given in Table 2. A pale yellow (3) or red–brown crystal
(6a) was glued to a glass fiber and mounted on a Bruker SMART
APEX diffractometer, equipped with a CCD area detector.
Data collection was collected with SMART-NT.30 Both data
sets were integrated with the Bruker SAINTPLUS program31and
absorption corrections were applied using the SADABS routine.
The structures were solved by Patterson, completed by difference
Fourier techniques, and refined by full-matrix least squares on F2
(SHELXL-97)32 with initial isotropic, but subsequent anisotropic
thermal parameters. Hydrogens in 3 and 6a, were introduced from
observed positions and refined as isotropic atoms.
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R. N. Perutz, J. Chem. Soc. Dalton Trans., 1998, 3079; (b) A. H. Klahn,
M. H. Moore and R. N. Perutz, J. Chem. Soc. Chem. Commun., 1992,
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16 F. Godoy, C. Higgit, A. H. Klahn, B. Oelckers, S. Parsons and R. N.
Perutz, J. Chem. Soc. Dalton. Trans., 1999, 2039.
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K. Raptis, J. Rebizant and M. L. Ziegler, J. Organomet. Chem., 1995,
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19 R. G. Bergman, P. F. Seidler and T. T. Wenzel, J. Am. Chem. Soc., 1985,
107, 4358.
20 B. E. Bosch, G. Erker, G. R. Fro¨hlinch and O. Meyer, Organometallics,
1997, 16, 5449.
21 A. C. Filipou, B. Lungwitz, G. Kociok-Ko¨hn and I. Hinz, J. Organomet.
Chem., 1996, 524, 133.
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A. K. Howard, Polyhedron, 1999, 17, 3889; (b) D. P. Krut,’ko, M. V.
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23 A. H. Klahn-Oliva, R. D. Singer, J. M. Aramini and D. Sutton, Inorg.
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Acknowledgements
F.G acknowledges FONDECYT (project 2010033 and 11060524).
We thank Fundacion Andes for financial support for an X-ray
diffractometer (Convenio C-13575).
24 L. Lefort, T. W. Crane, M. D. Farwell, D. M. Baruch, J. A. Kaeuper,
R. J. Lachicotte and W. D. Jones, Organometallics, 1998, 17, 3889.
25 S. T. Klei, D. Tilley and G. Bergman, Organometallics, 2002, 21,
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26 J. W. Faller and A. S. Anderson, J. Am. Chem. Soc., 1970, 5852.
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