Design and synthesis of polytopic metalloligands based on fluoroaryl gold(I) organometallic compounds

Article abstract of DOI:10.1021/om200318c

New neutral and anionic fluoroaryl gold(I) complexes featuring terminal pyridine rings were prepared following different strategies. The homoleptic anionic compounds NBu₄[Au(C₅F₄N)₂] (1) and NBu₄[Au(C₆F₄py)₂] (2) were obtained by reacting [AuCl(tht)] (tht = tetrahydrothiophene) with the organolithium derivatives of BrC₅F₄N and BrC ₆F₄py, respectively. This route required the previous synthesis of the new fluorinated compound BrC₆F₄py, which was produced by a Stille cross-coupling between (4-pyridyl)trimethylstannane and 1,4-dibromotetrafluorobenzene. The neutral phosphane compounds [Au(C ₆F₄N)(PPh₃)] (3) and [Au(C₆F ₄py)(PPh₃)] (4) were obtained by treatment of [AuCl(PPh₃)] with the organolithium reagents LiC₆F ₄N and LiC₆F₄py, respectively. However, this synthetic strategy failed for organogold compounds containing a polyphosphane ligand. Consequently, an alternative synthetic procedure, based on displacement reactions of the weakly coordinated tht ligand from [Au(C₆F ₄py)(tht)] by the appropriate polyphosphane, was undertaken. Thus, the following complexes were isolated and characterized: [(AuC₆F ₄py)₂(μ₂-diphosphane)] [diphosphane = bis(diphenylphosphanyl)methane (dppm) (9), 2,2-bis(diphenylphosphanyl)propane (dppip) (10), 1,2-bis(diphenylphosphanyl)ethane (dppe) (11), trans-1,2-bis(diphenylphosphanyl)ethylene (dppet) (12), 1,2- bis(diphenylphosphanyl)acetylene (dppa) (13), 1,3-bis(diphenylphosphanyl)propane (dppp) (14), 1,4-bis(diphenylphosphanyl)butane (dppb) (15), 4,4′-bis(diphenylphosphanyl)-1,1′-biphenyl (dppdph) (16)], [(AuC₆F₄py)₃(μ₃-triphosphane)] [triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane (triphos) (17), 1,3,5-tris(diphenylphosphanyl)benzene (triphosph) (18)], and [(AuC ₆F₄py)₄(μ₄-tetraphosphane)] [tetraphosphane = tetra(diphenylphosphanyl)methane (tetraphos) (19), 1,2,3,5-tetra(diphenylphosphanyl)benzene (tetraphosph) (20)]. Coordination reaction assays of compounds 1, 2, 3, and 4 with [M(diphosphane)(H ₂O)₂](OTf)₂ (M = Pd, Pt) were performed in order to test their potential as building blocks in the self-assembly of discrete species. The crystal structures of compounds BrC₆F ₄py, 1, 4, 17, and 19 were determined. Extensive noncovalent interations, particularly fluorine interactions such as C- F???π_F, C-F???H, and F???F, have been found to influence the molecular packing of these species.

Full text of DOI:10.1021/om200318c

ARTICLE
pubs.acs.org/Organometallics
Design and Synthesis of Polytopic Metalloligands Based on
Fluoroaryl Gold(I) Organometallic Compounds
Montserrat Ferrer,*,† Albert Gutiꢀerrez,† Mounia Mounir,† Laura Rodríguez,† Oriol Rossell,†
Mercꢁe Font-Bardia,‡,§ Pilar Gꢀomez-Sal,§ Avelino Martín,^ and Xavier Solans‡
†Departament de Química Inorgꢁanica, Universitat de Barcelona, c/Martí i Franquꢁes 1-11, 08028 Barcelona, Spain
‡Departament de Cristal lografia, Mineralogia i Dipꢁosits Minerals, Universitat de Barcelona, c/Martí i Franquꢁes s/n,
3
08028 Barcelona, Spain
§Unitat de Difracciꢀo de RX, Centre Científic i Tecnolꢁogic de la Universitat de Barcelona (CCiTUB), c/Solꢀe i Sabarís 1-3,
08028 Barcelona, Spain
^Departamento de Química Inorgꢀanica, Campus Universitario-Edificio de Farmacia, Universidad de Alcalꢀa,
28871 Alcalꢀa de Henares, Spain
S Supporting Information
b
ABSTRACT: New neutral and anionic fluoroaryl gold(I) com-
plexes featuring terminal pyridine rings were prepared following
different strategies. The homoleptic anionic compounds NBu4-
[Au(C5F4N)2] (1) and NBu4[Au(C6F4py)2] (2) were obtained
by reacting [AuCl(tht)] (tht = tetrahydrothiophene) with the
organolithium derivatives of BrC5F4N and BrC6F4py, respec-
tively. This route required the previous synthesis of the new
fluorinated compound BrC6F4py, which was produced by a Stille
cross-coupling between (4-pyridyl)trimethylstannane and 1,4-dibromotetrafluorobenzene. The neutral phosphane compounds
[Au(C6F4N)(PPh3)] (3) and [Au(C6F4py)(PPh3)] (4) were obtained by treatment of [AuCl(PPh3)] with the organolithium
reagents LiC6F4N and LiC6F4py, respectively. However, this synthetic strategy failed for organogold compounds containing a
polyphosphane ligand. Consequently, an alternative synthetic procedure, based on displacement reactions of the weakly
coordinated tht ligand from [Au(C6F4py)(tht)] by the appropriate polyphosphane, was undertaken. Thus, the following complexes
were isolated and characterized: [(AuC6F4py)2(μ2-diphosphane)] [diphosphane = bis(diphenylphosphanyl)methane (dppm) (9),
2,2-bis(diphenylphosphanyl)propane (dppip) (10), 1,2-bis(diphenylphosphanyl)ethane (dppe) (11), trans-1,2-bis-
(diphenylphosphanyl)ethylene (dppet) (12), 1,2-bis(diphenylphosphanyl)acetylene (dppa) (13), 1,3-bis(diphenylphosphanyl)-
propane (dppp) (14), 1,4-bis(diphenylphosphanyl)butane (dppb) (15), 4,40-bis(diphenylphosphanyl)-1,10-biphenyl (dppdph)
(16)], [(AuC6F4py)3(μ3-triphosphane)] [triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane (triphos) (17), 1,3,5-
tris(diphenylphosphanyl)benzene (triphosph) (18)], and [(AuC6F4py)4(μ4-tetraphosphane)] [tetraphosphane = tetra-
(diphenylphosphanyl)methane (tetraphos) (19), 1,2,3,5-tetra(diphenylphosphanyl)benzene (tetraphosph) (20)]. Coordination
reaction assays of compounds 1, 2, 3, and 4 with [M(diphosphane)(H2O)2](OTf)2 (M = Pd, Pt) were performed in order to test
their potential as building blocks in the self-assembly of discrete species. The crystal structures of compounds BrC6F4py, 1, 4, 17, and
19 were determined. Extensive noncovalent interations, particularly fluorine interactions such as CꢀF πF, CꢀF H, and
3 3 3
3 3 3
F
F, have been found to influence the molecular packing of these species.
3 3 3
’ INTRODUCTION
ligand” or “metalloligand” strategy, i.e., the use of metal com-
plexes with “free” donor groups for further metal bonding as
synthetic precursors, has also been developed.6ꢀ11 Such ligands
are the basis for the preparation of multinuclear complexes and
coordination arrays of various dimensionalities. Conceptually, in
an expanded ligand the spacer groups introduced are replaced by
metal-containing moieties.
The design and synthesis of supramolecular self-organized
systems with specific properties and functions in order to obtain
advanced materials has increased in recent years. In particular,
noteworthy advances have occurred in the field of engineering
crystalline materials built from selected molecular components.1ꢀ5
Molecular subunits are particularly effective when they incorpo-
rate multiple sites in particular orientations that favor the self-
assembly of the building blocks to yield the predesigned supra-
molecular species.
The use of metallic complexes as building block precursors has
proved to be a very useful strategy for the design and syntheses of
While most metalꢀorganic systems have been synthesized
Received: April 14, 2011
Published: May 23, 2011
directly from metal ions and organic ligands, the “complex as
r
2011 American Chemical Society
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Scheme 1
Figure 1. Molecular structure of the anion of complex 1. Ellipsoids are
set at the 50% probability level. Selected bond lengths (Å) and angles
(deg): AuꢀC1 = 2.017(9), AuꢀC6 = 2.025(9); C1ꢀAuꢀC6 =
177.4(4).
Analytical and spectroscopic data agree with the proposed
structure. The IR spectrum shows absorptions at 1620, 1413,
1202, and 818 cmꢀ1 that correspond to the C6F4N and at
921 cmꢀ1 arising from the NBu4þ. The 19F NMR shows two
multiplets that agree with the existence of two types of inequiv-
alent fluorine atoms. The FAB(ꢀ) mass spectrum shows the
parent peak at m/z = 497.1, which corresponds to the
[Au(C5F4N)2]ꢀ species. In addition, the structure of 1 was
confirmed by X-ray diffraction (Figure 1). A single crystal of the
compound was obtained by slow diffusion of diethyl ether into a
solution of 1 in dichloromethane. The lattice is built up by well-
separated NBu4þ cations and aurate anions. The coordination at
gold is quasi linear (C1ꢀAuꢀC6 = 177.4(4)ꢀ), and the AuꢀC
distances are found to be 2.017(9) and 2.025(9) Å. These values
are similar to those reported in the literature for related gold
compounds.24ꢀ30 The pyridine rings are tilted 19ꢀ with respect
to each other. In general, the value of this angle has been reported
to be less than 10ꢀ for bis-perfluorinated derivatives except in the
case of the tetrabutylammonium derivative NBu4[Au(C6F5)2]26
and the closely related silver compound PNP[Ag(C6F4N)2],31
where this angle is ca. 80ꢀ. Interestingly, the structure of the
materials with specific structures and functions in areas such as
catalysis1,12 or molecular recognition and sensing.2,13
Our focus in this area is on the complementary use of
directional spacers and geometrically defined metals to prepare
small polygons with functional value. In particular, we have been
studying the self-assembly reactions between cis-blocked PdII and
PtII square-planar complexes and the tetrafluorophenylene pyr-
idyl ligands 1,4-bis(4-pyridyl)tetrafluorobenzene14,15 and 4,40-
bis(4-pyridyl)octafluorobiphenyl16 with the aim of generating
electron-poor cavities capable of interacting with electron-rich
compounds.
With this in mind, we thought of extending our studies by
using fluorinated organometallic compounds, and more specifi-
cally, we chose gold(I) compounds for several reasons; fluoroaryl
gold(I) compounds are known to have both thermodynamic and
kinetic stability, adopt linear two coordination, and have the
possibility of forming supramolecular structures due to the
establishment of short d10ꢀd10 aurophilic interactions, and,
moreover, can display optical properties that could allow the
study of their interactions with other species in molecular
recognition processes.
compound presents weak intermolecular CꢀF πF interactions
Although a significant number of fluoroaryl gold(I) com-
3 3 3
pounds have been described so far,17ꢀ19 and their behavior as
(3.32 Å) that result in a well-defined zigzag molecular arrange-
ment (Supporting Information, Figure S1). Although these con-
tacts have been found in many fluorinated organic compounds,32ꢀ34
this is the first time that this kind of interaction is pointed out
for the related fluoroaryl Au(I) compounds. A search of struc-
tural data from CSD have shown that the compounds
[(pdma)2][Au(C6F5)2],24 [NEt4]2[S(AuC6F5)3],35 and [Au2-
(C6F5)2{μ-2,2-Ph2As(5,5-Me2C6H3C6H3)AsPh2}]36 present
Lewis bases to generate unsupported Au M interactions (M =
3 3 3
acidic closed-shell metal atom) have been explored,19ꢀ22 none of
them have been specifically synthesized to contain terminal
donor groups that are responsible for their basic properties.
In this paper we report the synthesis of a series of organome-
tallic fluorinated gold(I) compounds containing terminal pyr-
idine groups. These compounds have been designed to act as
donor building blocks in self-assembly reactions. Preliminary
assays of the donor capability of the synthesized compounds are
also reported.
CꢀF πF interactions that have an influence on their crystal
3 3 3
packing.
The donor capability of 1 was tested in reactions with acceptor
complexes such as [M(dppp)(H2O)2](OTf)2 (M = Pd, Pt).
However, no coordination of the pyridine to the metal centers
was detected. The very poor donor ability of 1 is possibly due to
the high electronegativity of the fluorine substituents on pyridine
ligands. In order to overcome this drawback, we attempted to
synthesize a longer symmetrical organometallic gold compound
containing perfluoraryl groups directly attached to the gold(I)
center and pyridine rings relatively far from the fluorine atoms,
i.e., NBu4[Au(C5F4py)2] (2). To do this, the new organic
compound BrC6F4py had to be synthesized. First, a Kumada
coupling between the Grignard derivative of 1,4-dibromotetra-
fluorobenzene and 1 equiv of 4-bromopyridine was attempted,
but this method produced the desired compound only in very
’ RESULTS AND DISCUSSION
Ditopic Anionic Metalloligands. As mentioned in the Intro-
duction, we wanted to synthesize gold(I) derivatives closely
related to the linear fluorinated dipyridyl compounds indicated
above, i.e., py-(C6F4)n-py (n = 1, 2). Obviously, the simplest
perfluoroarylgold(I) species containing terminal pyridine rings is
the symmetrical organoaurate [Au(C5F4N)2]ꢀ.
The compound NBu4[Au(C5F4N)2] (1) was obtained by
reaction of LiC5F4N and [AuCl(tht)] following the procedure
previously reported for analogous complexes (Scheme 1).23
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ARTICLE
Scheme 2
Scheme 3
Figure 2. Molecular structure of compound 4. Ellipsoids are set at the
50% probability level. Selected bond lengths (Å) and angles (deg):
AuꢀC9 = 2.046(4), AuꢀP = 2.2861(11), C3ꢀC6 = 1.497(6);
C9ꢀAuꢀP = 174.7(2).
low yields. As an alternative, the [PdCl2(PPh3)2]/LiCl-pro-
moted Stille cross-coupling between 1 equiv of (4-pyridyl)tri-
methylstannane and 1,4-dibromotetrafluorobenzene (Scheme 2)
gave us better results.
downfield with respect to the free BrC6F4py, which agrees with
the existence of two types of fluorine atoms. The FAB(ꢀ) mass
spectrum showed the parent peak at m/z = 649.1 that corre-
sponds to the [Au(C6F4py)2]ꢀ species.
Although this kind of coupling had already been used by us to
obtain the ditopic ligand 1,4-bis(4-pyridyl)tetrafluorobenzene,14
the synthesis of BrC6F4py turned out to be more complicated
mainly due to the formation of significant amounts of the
homocoupling product whatever the molar ratio was. Thus, the
purification of BrC6F4py proved to be very challenging, and we
finally isolated the target compound in moderate yield (30%)
after chromatographic workup and successive sublimations. The
compound was characterized by elemental analyses and 1H, 13C,
and 19F NMR and IR spectroscopies. The mass spectrum showed
the peaks dueto[M þ H]þ (m/z = 307.1) and[M ꢀ Br]þ (m/z =
226.1) fragments. In addition, suitable crystals for single-crystal
X-ray diffraction were obtained by slow diffusion of diethyl ether
into a dichloromethane solution of the compound. The resolved
structure (Supporting Information, Figure S2) shows a dihedral
angle between the aromatic rings of 58.4(2)ꢀ, close to the
50.47(5)ꢀ found in the related pyC6F4py. The rest of the
intramolecular bonds and angles are in the expected range.
The crystal packing of BrC6F4py (Supporting Information,
As indicated above, the perfluorinated compound 1 did not
show basic properties and consequently could not be used as a
donor fragment in self-assembly reactions. Compound 2, however,
upon reaction with acceptors such as [M(dppp)(H2O)2](OTf)2
(M = Pd, Pt), led only to the formation of highly insoluble and
untreatable solids that could not be characterized and that most
probably correspond to coordination polymers. Changes in the
reaction conditions (concentration, solvent, temperature, reaction
time, etc.) did not modify the nature of the resulting products.
At this point, it seemed decisive to find the reason that self-
assembled Pd(II) or Pt(II) squares and/or triangles are readily
obtained from the analogous organic ditopic ligands, py-C6F4-
py14,15 or py-C6F4ꢀC6F4-py,16 and why this kind of discrete
species could not be obtained by using the anionic gold complex
2. To test if it was the anionic character of the gold complex that
precluded the success of the self-assembly processes, we decided
to synthesize new heteroleptic neutral gold(I) compounds
bearing the donor “C6F4py” group and the ligand PPh3 since it
is known that phosphanes stabilize gold complexes due to the
back bonding (dꢀd)π of the AuꢀP bond.
Figure S3) clearly shows the presence of N Br interactions
3 3 3
with an intermolecular distance of 2.811(4) Å, which is con-
siderably shorter than the sum of the van der Waals radii
Neutral Monotopic Metalloligands. The compounds
[Au(C6F4N)(PPh3)] (3) and [Au(C6F4py)(PPh3)] (4) were
obtained by treatment of [AuCl(PPh3)] with an excess of freshly
prepared diethyl ether (compound 3) or thf (compound 4)
solution of the appropriate organolithium reagent (LiC6F4N or
LiC6F4py, respectively). The 31P{1H} NMR spectra confirmed
the formation of the compounds since a triplet due to the
coupling between the phosphorus and the ortho-fluorine atoms
to the gold center was observed (4J(PꢀF) ≈ 7 Hz). The FAB(þ)
mass spectra displayed the cationic molecular peaks [3 þ H]þ
and [4 þ H]þ at m/z = 610.1 and 686.0, respectively. Moreover,
the structure of compound 4 was confirmed by X-ray diffraction
(Figure 2). Each Au(I) center has a linear ligand coordination
(3.40 Å). The N BrꢀC angle is 180ꢀ, and the molecules are
3 3 3
aligned in one-dimensional infinite head-to-tail chains as a result
of these attractive forces. The adjacent chains run parallel to the
crystallographic c-axis with an interchain distance of ca. 5 Å.
Once the synthesis of the BrC6F4py ligand was accomplished,
the target compound 2 was obtained in a similar way to 1
(Scheme 3).
Characterization data agree with the proposed formulation.
1
þ
The H NMR spectrum showed, together with the NBu4
signals, those corresponding to R- and β-protons of the terminal
pyridine ring. The 19F NMR showed two multiplets shifted
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with geometric parameters inside the narrow range found in
other triphenylphosphine ortho-substituted phenylgold(I) com-
pounds.37ꢀ43 The angle between the pyridine and the fluorinated
ring is 50.7(3)ꢀ, a bit smaller than that indicated above for the
brominated ligand BrC6F4py. Interestingly, the establishment of
These results confirmed that neutral organometallic gold
compounds containing fluorinated C6F4py terminal units co-
ordinate efficiently to acidic metal centers. Since the formation of
the desired heterometallic metallomacrocycles of diverse dimen-
sionalities implied the presence of more than one pyridine group
in the metalloligand to generate cyclic structures, we undertook
the synthesis of a series of gold(I)-containing di-, tri-, and
tetraphosphanes closely related to 4.
rather strong secondary CꢀH F interactions (d(CꢀH) =
3 3 3
0.93 Å, d(H F) = 2.33 Å, d(C F) = 3.105(8) Å, CꢀHꢀF =
3 3 3
3 3 3
141ꢀ) between one phenyl group of the PPh3 and a C6F4 ring of a
different molecule gives rise to association of the molecules in
pairs (Figure 3) that associate among themselves by weaker
nonclassical hydrogen bonds (Supporting Information, Figure
S4). Fluorine interactions of this kind have been pointed out for
other fluoroaryl gold(I) compounds.44ꢀ46
Neutral Polytopic Metalloligands. Attempts to prepare the
corresponding diphosphane complexes [(AuC6F4py)2(μ2-
diphosphane)] by the procedure described above for 4 were
unsuccessful. The treatment of the appropriate chlorogold(I)
phosphanes with a large excess of the organolithium reagent
LiC6F4py did not allow the complete substitution of the terminal
chlorine atoms by the desired C6F4py moiety, in spite of the
excess. Most probably, the poor reproducibility together with the
low yield in the formation of the lithium derivative of BrC6F4py
precluded the completion of the reaction. An alternative syn-
thetic procedure that allows a better control of the molar ratio
between the reacting species is based on the use of the neutral
derivatives [AuR(tht)] as precursors, since they allow the synth-
esis of gold(I) complexes through displacement reactions of the
weakly coordinated ligand tht by other neutral or anionic
ligands.47 The treatment of a dichloromethane solution of
recently prepared [Au(C6F4py)(tht)] with a series of diphos-
phanes in a 2:1 molar ratio at room temperature gave the desired
dinuclear gold derivatives in good yields, [(AuC6F4py)2(μ2-
diphosphane)] (Scheme 5) [diphosphane = dppm (9), dppip
(10), dppe (11), dppet (12), dppa (13), dppp (14), dppb (15),
dppdph (16)]. Analogous reactions with tri- or tetraphosphanes
in 3:1 and 4:1 molar ratios, respectively, allowed the isolation of
the corresponding tri-gold [(AuC6F4py)3(μ3-triphosphane)]
[triphosphane = triphos (17), triphosph (18)] or tetranuclear
gold [(AuC6F4py)4(μ4-tetraphosphane)] [tetraphosphane =
tetraphos (19), tetraphosph (20)] compounds (Scheme 5).
All the synthesized compounds gave satisfactory elemental
analysis and were characterized by 1H, 31P{1H}, and 19F NMR
spectroscopies, mass spectrometry (ESI or FAB), and IR spec-
troscopy. Moreover, the structures of complexes 17 and 19 were
determined by X-ray crystallography. 1H NMR spectra showed
the expected signals for both R and β pyridine protons as well as
those attributable to the organic core of the polyphosphane
ligands. 31P{1H} NMR spectra displayed a resonance whose
downfield shift from the free polyphosphane clearly indicates
the coordination of the ligand to the gold center. In most of the
compounds a broad signal is observed that splits into a triplet
(4J(PꢀF) ≈ 8 Hz) for derivatives 14 (dppp), 15 (dppb), and 16
Coordination Reaction Assays. In agreement with the results
reported above, the tetrafluoropyridine derivative 3 was not basic
enough to coordinate to metal centers. However, the reaction of
complex 4 with the acceptor metal complexes [M(diphos-
phane)(H2O)2](OTf)2 (M = Pd, Pt) (diphosphane = dppp,
dppf) in 2:1 molar ratio afforded the corresponding trimetallic
compounds [M(diphosphane){(pyC6F4)Au(PPh3)}2](OTf)2
(5ꢀ8) as a result of the coordination of the pyridine group to
either the palladium or the platinum atom (Scheme 4).
The analytical and spectroscopic properties are in accordance
with the proposed formulation. The observed downfield shifts of
the R-pyridine protons of 4 in the 1H NMR spectra together with
the upfield shifts for the phosphorus atoms of the diphosphane in
the 31P{1H} NMR spectra are in agreement with metal coordi-
nation. Moreover, species containing Pt(diphosphane) frag-
ments have the particular advantage that the 1J(PtꢀP) are very
sensitive to changes in the coordination sphere. These coupling
constants in 5 and 7 are 3065 and 3410 Hz, respectively, ca.
800 Hz smaller than in the [Pt(diphosphane)(H2O)2](OTf)2
precursors, thus clearly indicating the coordination of the
pyridine rings. The mass spectra showed the peak due to [M ꢀ
2OTf]2þ except for compound 8, where the [8 ꢀ 2OTf ꢀ
PPh3]2þ fragment was found instead.
Figure 3. Visualization of the association of 4 in dimers through
CꢀH F interactions.
3 3 3
Scheme 4
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Scheme 5
(dppdph) in an analogous manner to that in compound 3. 19
F
NMR spectra showed two sets of signals that show complicated
patterns corresponding to Fortho and Fmeta to the gold atom. The
mass spectra (ESI or FAB) displayed peaks due to the proton-
ation of one or more of the terminal pyridine groups.
The molecular structure of compound 17 (Figure 4) features
the expected trinuclear compound where each gold center is
coordinated to one C6F4py unit. A long Au Au contact
3 3 3
(3.331(1) Å) can be observed between Au1 and Au3 atoms,
while Au2 was further away. This arrangement is generally
adopted by compounds that contain the “Au3(μ3-triphos)”
unit.48ꢀ51 The disorder in the C24ꢀC29 and C31ꢀC35 aro-
matic rings prevented the analysis of possible weak intermole-
cular interactions.
The molecular structure of compound 19 is shown in Figure 5.
Complex 19 crystallized in the tetragonal I41/a space group; thus
only a unique set of distances and angles corresponding to one of
the four branches of the compound had to be determined.
Figure 4. Molecular structure of compound 17. Ellipsoids are set at the
50% probability level. Phenyl rings are omitted for clarity. Selected bond
lengths (Å) and angles (deg): Au1ꢀAu3 = 3.3310(10), Au1ꢀP1 =
2.287(3), Au2ꢀP2 = 2.300(3), Au3ꢀP3 = 2.295(3), Au1ꢀC114 =
2.06(1), Au2ꢀC24 = 2.11(2), Au3ꢀC314 = 2.08(1); P1ꢀAu1ꢀC114 =
174.3(4), P2ꢀAu2ꢀC24 = 178.3(5), P3ꢀAu3ꢀC314 = 176.1(4),
P1ꢀAu1ꢀAu3 = 78.3(1), P3ꢀAu3ꢀAu1 = 78.3(1).
Although rather long, intramolecular Au Au interactions
3 3 3
(3.343(1) Å) are found between adjacent units. Other tetraphos-
phane gold(I) compounds show the gold atoms associated in
pairs by aurophilic attractions in a similar way to those reported
here.52,53 This disposition is different from that found in the
parent compound [(AuCl)4(μ4-tetraphos)],54 where a pair of
gold centers show short contacts, while the other two lie far apart.
The molecules pack in such a way that fluorophilic contacts
have demonstrated that these kinds of interactions are con-
sistent with intermolecular stabilizing F
F interactions and
between the F(12) (d(F F) = 2.646(8) Å) of different units
3 3 3
3 3 3
expand, giving rise to the 3D structure (Figure 6). Although
have been recently described for a related fluoroaryl gold(I)
traditionally attributed to packing forces, recent calculations55
compound.56
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Figure 6. Molecular packing of 19 following the crystallographic c-axis.
Visualization of fluorophilic contacts between F12 atoms of different
molecules.
Figure 5. Molecular structure of compound 19. Ellipsoids are set at the
50% probability level. Selected bond lengths (Å) and angles (deg):
Au1ꢀAu1c = 3.343(1), Au1ꢀP1 = 2.301(2), Au1ꢀC15 = 2.076(6);
P1ꢀAu1ꢀC15 = 173.3(2), C15ꢀAu1ꢀAu1c = 107.1(2), P1ꢀAu1ꢀ
Au1c = 78.3(1). Symmetry transformations used to generate equivalent
atoms: #1 ꢀyþ1, x, ꢀz; #2 yþ0, ꢀxþ1, ꢀzþ0; #3 ꢀxþ1, ꢀyþ1, zþ0.
agents. Infrared spectra were recorded on an FT-IR 520 Nicolet
spectrophotometer. 31P NMR (δ(85% H3PO4) = 0.0 ppm), 19F
NMR (δ(CFCl3) = 0.0 ppm), 13C NMR (δ(TMS) = 0.0 ppm), and
1H NMR (δ(TMS) = 0.0 ppm) spectra were obtained on Bruker DXR
250, Varian Gemini 200, Varian-Unity 300, Varian-Inova 300, and
Varian Mercury 400 spectrometers. (See numbering scheme for fluorine
assignation.) Elemental analyses of C, H, and N were carried out at the
Institut de Bio-Orgꢁanica in Barcelona. FAB, ESI, and IE mass spectra
were recorded on a Fisions VG Quattro, a LC/MSD-TOF (Agilent
Technologies), and a ThermoFinnigan TRACE DSQ spectrometer,
respectively. MALDI-TOF spectra were recorded on a Voyager DE-RP
(Perspective Biosystems) time-of-flight (TOF) spectrometer.
’ CONCLUSION
In summary, a series of fluoroaryl compounds featuring one,
two, three, and even four gold centers and terminal pyridine
ligands have been prepared and structurally characterized to be
used as building blocks in the assembly of supramolecular
compounds through coordination bonds.
Since perfluorinated pyridine rings are poorly basic, the design
and synthesis of the new fluorinated compound containing a
pyridine ring has been performed, and a wide variety of deriva-
tives have been prepared. Preliminary studies exploring the
behavior of these Au(I) species as metalloligands have shown
that neutral [Au(C6F4py)(PPh3)] (4) allowed the synthesis of
discrete species in high yields, while symmetrical anionic
[Au(C6F4py)2]ꢀ (1) led to the formation of complex polymeric
mixtures that could not be characterized.
Commercial reagents triphenylphosphine, dppet, dppa, dppp, triphos,
4-bromopyridine hydrochloride, 1,4-dibromotetrafluorobenzene, and tri-
methyltin chloride were used as received. Compounds dppm,57 dppip,57
dppe,57 dppb,57 dppdph,58,59 triphosph,60 tetraphos,54 tetraphosph,60 (4-
pyridyl)trimethylstannane,61 [Au(C6F4py)(tht)],62 [Pt(dppp)(H2O)2]-
(OTf)2,63 [Pd(dppp)(H2O)2](OTf)2,63 [Pt(dppf)(H2O)2](OTf)2,63
and [Pd(dppf)(H2O)2](OTf)263 were prepared as described previously.
X-ray Structure Determinations. Crystal data for all the com-
plexes are presented in Table 1. A suitable crystal was selected with the aid of
a microscope, attached to a glass fiber, and in the case of BrC6F4py, 17, and
19 immediately placed in the low-temperature nitrogen stream (100 K
BrC6F4py and 200 K 17 and 19) after being covered with a layer of a viscous
perfluoropolyether (Fomblin Y). Crystals of 1 and 4 were mounted on a
MAR345 diffractometer with an image plate detector, while a Bruker-
Nonius Kappa CCD diffractometer equipped with an Oxford Cryostream
700 unit was used for compounds BrC6F4py, 17, and 19. Intensities were
collected with graphite-monochromatized Mo KR radiation.
Interestingly, the X-ray structures of the fluoroaryl gold(I)
compounds 1, 4, and 19 are good examples of CꢀF πF,
3 3 3
CꢀF H, and F F interactions, showing that these types of
3 3 3
3 3 3
secondary bonds can be found in fluoroaryl gold(I) organome-
tallics in the same way as has been described for a wide range of
organic fluorinated compounds.33 The establishment of these
interactions increases the dimensionality of discrete supramole-
cular species, giving rise to more complex structures.
We are currently investigating the self-assembly reactions be-
tween the polytopic metalloligands reported here and acceptor
coordination compounds in order to synthesize new heterometal-
lomacrocycles whose potential properties deserve to be investigated.
The structures were solved, using the WINGX package,64 by direct
methods (SHELXL-97) and refined by least-squares against F2
(SHELXL-97).65 Absorption correction procedures were carried out
using the multiscan SORTAV program66 for BrC6F4py, 17, and 19 and
the empirical SADABS program for 1 and 4.
All H atoms were calculated and refined, using a riding model, with an
isotropic temperature factor equal to 1.2 times the equivalent temperature
factor of the atom to which they are linked. All the non-hydrogen atoms
’ EXPERIMENTAL SECTION
All manipulations were performed under prepurified N2 using standard
Schlenk techniques. All solvents were distilled from appropriate drying
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Organometallics
ARTICLE
Table 1. Crystal and Structure Determination Data
BrC6F4py
1
4
17
19
empirical formula
fw
C
11H4BrF4N
C26H36AuF8N3
739.54
C29H19AuF4NP
685.39
C74H51Au3F12N3P3
1893.99
C97H64Au4F16N4P4
2501.27
153.03
temperature (K)
wavelength (Å)
cryst syst
100(2)
293(2)
293(2)
200(2)
200(2)
0.71073
orthorhombic
Pcnb
0.71069
0.71073
0.71073
0.71073
monoclinic
P21/n
orthorhombic
Pbcn
monoclinic
C2/c
tetragonal
I41/a
space group
unit cell dimens
a (Å)
7.809(1)
9.7080(10)
17.2870(10)
17.7240(10)
90
13.4380(10)
18.4960(10)
20.214(10)
90
35.584(2)
24.932(5)
22.090(6)
90
14.984(2)
14.984(2)
46.536(10)
90
b (Å)
10.747(2)
c (Å)
11.826(1)
R (deg)
90
β (deg)
90
93.5850(10)
90
90
119.13(1)
90
90
γ (deg)
90
90
90
V (Å3)
992.5(4)
2968.7(4)
4
5024(3)
15676(5)
8
10449(3)
4
Z
4
8
Dcalc (mg/m3)
absorp coeff (mmꢀ1
F(000)
2.048
1.655
1.812
1.605
1.590
)
4.173
5.025
5.968
5.731
5.731
592
1456
2640
7248
4776
cryst size (mm3)
0.45 ꢁ 0.35 ꢁ 0.33
0.2 ꢁ 0.1 ꢁ 0.1
1.65ꢀ24.96
ꢀ11 e h e10
0 e k e 20
0 e l e 20
14 405
0.2 ꢁ 0.1 ꢁ 0.1
1.87ꢀ29.01
0 e h e18
0 e k e 25
0 e l e 27
46 064
0.2 ꢁ 0.1 ꢁ 0.1
5.00ꢀ26.93
ꢀ41 e h e 36
ꢀ31 e k e 31
0 e l e 28
138 589
0.3 ꢁ 0.2 ꢁ 0.2
3.07ꢀ27.61
ꢀ19 e h e 19
ꢀ19 e k e 18
0 e l e 60
101 976
θ range for data collection (deg) 3.13ꢀ27.49
index ranges
ꢀ9 e h e9
ꢀ13 e k e 13
0 e l e 15
8734
reflns collected
indep reflns
1105 [R(int) = 0.067 4489 [R(int) = 0.068]
96.8%/27.50 86.1%/24.99
full-matrix least-squares on F2
6605 [R(int) = 0.0494]
98.6%/29.01
16 775 [R(int) = 0.039] 5629 [R(int) = 0.078]
completeness/θ(max, deg)
refinement method
data/restraints/params
goodness-of-fit on F2
final R indices [I > 2σ(I)]
R indices (all data)
98.7%/26.93
92.5%/27.61
1105/0/80
1.090
4489/24/345
0.820
6605/20/325
1.232
16 775/0/921
1.140
5629/0/282
0.938
R1 = 0.036, wR2 = 0.085 R1 = 0.0423, wR2 = 0.0894 R1 = 0.0374, wR2 = 0.0839 R1= 0.066, wR2= 0.189 R1= 0.048, wR2= 0.099
R1= 0.059, wR2 = 0.094 R1 = 0.1070, wR2 = 0.1011 R1 = 0.0735, wR2 = 0.1061 R1 = 0.146, wR2 = 0.217 R1 = 0.089, wR2 = 0.107
largest diff peak/hole (e Åꢀ3
)
0.805/ꢀ1.122
0.792/ꢀ0.470
0.803/ꢀ0.583
2.488/ꢀ1.469
1.397/ꢀ1.241
were refined anisotropically except C(213) and C(222), which were
isotropically refined in 17.
(326 mg, 7.50 mmol) were added to a toluene solution (60 mL) of
(4-pyridyl)trimethylstannane (373 mg, 1.54 mmol). The reaction was
refluxed for 72 h; after cooling, the mixture was treated with 50 mL of
H2O. The organic phase was removed, and the aqueous layer was
extracted with CH2Cl2 (3 ꢁ 40 mL). The combined organic layers were
dried (MgSO4) and concentrated to dryness under reduced pressure.
The resulting crude residue was purified by column chromatography on
silica gel using first CH2Cl2 and subsequently CH2Cl2/MeOH (98:2) as
eluents. The obtained cream solid was further purified by two subse-
quent sublimations (40 and 60 ꢀC), giving 185 mg of a white product
(yield: 40%). 1H NMR (298 K, acetone-d6): 8.79 (m, 2H, HR-pyr), 7.57
(m, 2H, Hβ-pyr). 13C NMR (298 K, CDCl3): 150.7 (CR-pyr), 147.2 (d,
J(CꢀF) = 105 Hz, CꢀFX), 143.2 (d, J(CꢀF) = 105 Hz, CꢀFA), 135.5
(Cγ-pyr), 124.9 (Cβ-pyr), 117.1 (m, Cqꢀpy), 101.0 (m, CqꢀBr). 19F
NMR (298 K, CDCl3): ꢀ134.7 (m, 2F, FX), ꢀ144.1 (m, 2F, FA). IE m/
z: 306.0 ([BrC6F4py þ H]þ, calc 306.0), 226.1 ([BrC6F4py ꢀ Br]þ, calc
226.0). IR (KBr, cmꢀ1): 1598, 1467, 973, 803. Anal. Calc: C, 43.17; H,
1.32; N, 4.58. Found: C, 43.29; H, 1.30; N, 4.66.
Molecules of 17 presented disorder in the C24ꢀC29 and C31ꢀC35
aromatic rings. Both cases were treated with the use of the SHELXL PART
command together with the corresponding occupancy free variables in the
refinement process. Both 17 and 19 crystallized with solvent molecules. All
attempts to model these molecules failed, and the Platon Squeeze procedure
was used to remove their contribution to the structure factors. However, the
poor quality of crystals in the case of complex 17 precluded the complete
removal of the solvent residues, and still a fairly large difference peak of
2.488 e Åꢀ3 could be found in the Fourier difference map.
Synthesis of (NBu4)[Au(C5F4N)2] (1). nBuLi (1.6 mL, 2.60
mmol) was added dropwise to a precooled (ꢀ78 ꢀC) solution of
4-bromotetrafluoropyridine (0.3 mL, 2.50 mmol) in diethyl ether
(15 mL). After 1 h of stirring a suspension of [AuCl(tht)] (267 mg,
0.83 mmol) in diethyl ether (15 mL) was added, and the stirring was
Synthesis of BrC6F4py. 1,4-Dibromotetrafluorobenzene (475 mg,
1.54 mmol), [PdCl2(PPh3)2] (54 mg, 0.075 mmol), and LiCl
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Organometallics
ARTICLE
maintained until solubilization of the gold complex (ca. 30 min). Then,
solid NBu4Br was added (268 mg, 0.83 mmol) and the solution was
allowed to warm slowly to room temperature. A white precipitate was
obtained, filtered under vacuum, and washed with diethyl ether. Yield:
mmol). After 3 h of stirring at room temperature, the mixture was
concentrated to ca. 2 mL, and diethyl ether was added in order to
complete the precipitation of the product. A white solid was obtained in
79% yield (31 mg). H NMR (298 K, CDCl3): 9.12 (d, J(HꢀH) =
1
1
65% (400 mg). H NMR (298 K, acetone-d6): 3.45 (m, 8H, NCH2),
5.2 Hz, 4H, HR-pyr), 7.62ꢀ7.36 (m, 50H, Ph), 7.22 (d, J(HꢀH) = 5.2 Hz,
4H, Hβ-pyr), 3.32 (br, 4H, PCH2), 2.24 (m, 2H, PCH2CH2). 31P{1H}
NMR (298 K, CDCl3): 41.9 (t, 4J(PꢀF) = 7.8 Hz, PPh3), ꢀ15.8
(s, 1J(PꢀPt) = 3066 Hz, dppp). 19F NMR (298 K, CDCl3, inset D2O
with CF3COOH): ꢀ81.1 (s, 6F, OTf), ꢀ118.7 (m, 4F, FX), ꢀ146.8 (m,
4F, FA). FAB(þ) m/z: 989.5 ([5 ꢀ 2OTf]2þ, calc 988.6), 756.1
([Pt(dppp)(OTf)]þ, calc 756.1), 686.1 ([Au(C6F4py)(PPh3) þ H]þ,
calc 686.1). IR (KBr, cmꢀ1): 1480, 946 (C6F4), 1436, 1423, 1101, 695
(dppp, PPh3), 1280, 1250, 1155, 1030, 640, 513 (OTf). Anal. Calc: C,
45.90; H, 2.83; N, 1.23. Found: C, 45.79; H, 2.79; N, 1.30.
1.83 (m, 8H, NCH2CH2), 1.43 (m, 8H, NCH2CH2CH2), 0.97 (t, 12H,
J(HꢀH) = 7.3 Hz, CH3). 19F NMR (298 K, CH2Cl2, inset D2O with
CF3COOH): ꢀ101.9 (m, 4F, FX), ꢀ124.9 (m, 4F, FA). FAB(ꢀ) m/z:
497.1 ([Au(C5F4N)2]ꢀ, calc 497.0). IR (KBr, cmꢀ1): 2968, 1474, 921
(NBu4), 1620, 1413, 1202, 818 (C5F4N). Anal. Calc: C, 42.22; H, 4.91;
N, 5.68. Found: C, 42.33; H, 4.87; N, 5.72.
Synthesis of (NBu4)[Au(C6F4py)2] (2). nBuLi (0.8 mL, 1.30
mmol) was added dropwise to a precooled (ꢀ78 ꢀC) solution of
(4-bromotetrafluorophenyl)pyridine (400 mg, 1.30 mmol) in tetra-
hydrofuran (20 mL). After 1 h of stirring, [AuCl(tht)] (139 mg, 0.43
mmol) was added, and the mixture was left to react at ꢀ40 ꢀC for 1 h.
Then, solid NBu4Br was added (140 mg, 0.43 mmol), and the suspen-
sion was allowed to warm slowly to room temperature and then
concentrated to dryness. The resulting solid was extracted with tetra-
hydrofuran (10 mL), and diethyl ether was added to precipitate a white
solid, which was filtered and dried under vacuum. Yield: 60% (230 mg).
1H NMR (298 K, CD2Cl2): 8.67 (d, J(HꢀH) = 4.7 Hz, 4H, HR-pyr), 7.47
(d, J(HꢀH) = 4.7 Hz, 4H, Hβ-pyr), 3.18 (m, 8H, NCH2), 1.67 (m, 8H,
NCH2CH2), 1.46 (m, 8H, NCH2CH2CH2), 1.02 (t, 12H, J(HꢀH) =
7.3 Hz, CH3). 19F NMR (298 K, CD2Cl2, inset D2O with CF3COOH):
ꢀ118.1 (m, 4F, FX), ꢀ148.1 (m, 4F, FA). FAB(ꢀ) m/z: 649.1
([Au(C6F4py)2]ꢀ, calc 649.0). IR (KBr, cmꢀ1): 2966, 1472, 946
(NBu4), 1443, 826 (C6F4). Anal. Calc: C, 51.18; H, 4.97; N, 4.71.
Found: C, 51.37; H, 4.99; N, 4.68.
Synthesis of [Pd(dppp){(pyC6F4)Au(PPh3)}2](OTf)2] (6).
Details of the synthesis of [Pt(dppp){pyC6F4)Au(PPh3)}2](OTf)2]
were also applied to the preparation of 6, but in this case, hexane was
1
used to precipitate instead of diethyl ether. Yield: 80% (35 mg). H
NMR (298 K, CDCl3): 9.08 (d, J(HꢀH) = 5.5 Hz, 4H, HR-pyr),
7.67ꢀ7.36 (m, 50H, Ph), 7.18 (d, J(HꢀH) = 5.2 Hz, 4H, Hβ-pyr),
3.23 (br, 4H, PCH2), 2.26 (m, 2H, PCH2CH2). 31P{1H} NMR (298 K,
CDCl3):42.0(t, 4J(PꢀF) = 8.8 Hz, PPh3), 5.7 (s, dppp). 19FNMR(298K,
CDCl3, inset D2O with CF3COOH): ꢀ81.0 (s, 6F, OTf), ꢀ118.8
(m, 4F, FX), ꢀ146.9 (m, 4F, FA). FAB(þ) m/z: 944.2 ([6 ꢀ 2OTf]2þ
,
calc 944.6), 686.1 ([Au(C6F4py)(PPh3) þ H]þ, calc 686.1), 667.8
([Pd(dppp)(OTf)]þ, calc 668.0), 518.1 ([Pd(dppp) ꢀ H]þ, calc
518.0). IR (KBr, cmꢀ1): 1480, 946 (C6F4), 1435, 1424, 1101, 695
(dppp, PPh3), 1283, 1253, 1155, 1030, 635, 516 (OTf). Anal. Calc: C,
47.76; H, 2.95; N, 1.28. Found: C, 47.59; H, 2.99; N, 1.31.
Synthesis of [Au(C5F4N)(PPh3)] (3). nBuLi (0.18 mL, 0.30
mmol) was added dropwise to a precooled (ꢀ78 ꢀC) solution of
4-bromotetrafluoropyridine (0.036 mL, 0.30 mmol) in diethyl ether
(25 mL). After 1 h of stirring a suspension of [AuCl(PPh3)] (150 mg,
0.30 mmol) in diethyl ether (15 mL) was added, and the mixture was
maintained on stirring 1 h. The solution was allowed to warm slowly to
room temperature and then filtered and concentrated to dryness. The
obtained white solid was recrystallized with dichloromethane/hexane,
Synthesis of [Pt(dppf){(pyC6F4)Au(PPh3)}2](OTf)2 (7). Solid
[Pt(dppf)(H2O)2](OTf)2 (11 mg, 0.01 mmol) was added to a dichloro-
methane (5 mL) solution of [Au(C6F4py)(PPh3)] (14 mg, 0.02 mmol).
The solution was stirred under reflux for 24 h. Then, the mixture was
filtered and concentrated to ca. 2 mL, and diethyl ether was added in
order to complete the precipitation of the product. A yellow solid was
1
obtained in 81% yield (20 mg). H NMR (298 K, CDCl3): 9.01 (d,
J(HꢀH) = 3.8 Hz, 4H, HR-pyr), 7.88ꢀ7.46 (m, 50H, Ph), 7.17 (d,
1
giving 118 mg of the corresponding product (yield: 65%). H NMR
J(HꢀH) = 5.8 Hz, 4H, Hβ-pyr), 4.82 (br, 4H, HR-ferr), 4.56 (br, 4H,
(298 K, CDCl3): 7.60ꢀ7.50 (m, 15H, Ph). 31P{1H} NMR (298 K,
H
β-ferr). 31P{1H} NMR (298 K, CDCl3): 41.9 (t, 4J(PꢀF) = 7.8 Hz, PPh3),
4
CDCl3): 37.5 (t, J(PꢀF) = 7.0 Hz). 19F NMR (298 K, CDCl3, inset
3.5 (s, 1J(PꢀPt) = 3410 Hz, dppf). 19F NMR (298 K, CDCl3, inset D2O
with CF3COOH): ꢀ80.5 (s, 6F, OTf), ꢀ118.0 (m, 4F, FX), ꢀ146.1
(m, 4F, FA). ESI(þ) m/z: 1060.0 ([7 ꢀ 2OTf]2þ, calc 1059.6), 898.0
([Pt(dppf)(OTf)]þ, calc 898.0), 749.0 ([Pt(dppf)]þ, calc 749.0), 687.0
([Au(C6F4py)(PPh3) þ H]þ, calc 686.1). IR (KBr, cmꢀ1): 1480, 946
(C6F4), 1435, 1424, 1097, 695 (dppf, PPh3), 1281, 1247, 1153, 1030,
636, 495 (OTf). Anal. Calc: C, 46.68; H, 2.75; N, 1.16. Found: C, 46.55;
H, 2.80; N, 1.11.
D2O with CF3COOH): ꢀ99.7 (m, 2F, FX), ꢀ124.5 (m, 2F, FA).
FAB(þ) m/z: 610.1 ([3 þ H]þ, calc 610.1), 459.1 ([AuPPh3]þ, calc
459.1), 262.1 (PPh3, calc 262.1). IR (KBr, cmꢀ1): 1620, 1446, 1201,
920, 827 (C5F4N), 1100, 745, 690, 539 (PPh3). Anal. Calc: C, 45.39; H,
2.48; N, 2.30. Found: C, 45.50; H, 2.42; N, 2.40.
Synthesis of [Au(C6F4py)(PPh3)] (4). nBuLi (0.20 mL, 0.32
mmol) was added dropwise to a precooled (ꢀ78 ꢀC) solution of 4-(4-
bromotetrafluorophenyl)pyridine (100 mg, 0.32 mmol) in tetrahydro-
furan (50 mL). After 1 h of stirring, solid [AuCl(PPh3)] (158 mg, 0.32
mmol) was added, and the mixture was stirred for another hour. Then,
the solution was allowed to warm slowly to room temperature. The
mixture was hydrolyzed with a few drops of water, dried with MgSO4,
and concentrated to dryness. The obtained solid was recrystallized with
dichloromethane/hexane, giving 110 mg of a yellow solid (yield: 50%).
1H NMR (298 K, CDCl3): 8.70 (d, J(HꢀH) = 5.4 Hz, 2H, HR-pyr),
7.66ꢀ7.49 (m, 20H, Ph), 7.45 (d, J(HꢀH) = 5.4 Hz, 2H, Hβ-pyr).
31P{1H} NMR (298 K, CDCl3): 37.9 (t, 4J(PꢀF) = 7.8 Hz). 19F NMR
(298 K, CH2Cl2, inset D2O with CF3COOH): ꢀ119.7 (m, 2F, FX),
ꢀ147.6 (m, 2F, FA). FAB(þ) m/z: 686.0 ([4 þ H]þ, calc 686.1). IR
(KBr, cmꢀ1): 1429, 943, 826 (C6F4), 1101, 690 (PPh3). Anal. Calc: C,
50.82; H, 2.79; N, 2.04. Found: C, 50.67; H, 2.73; N, 2.10.
Synthesis of [Pd(dppf){(pyC6F4)Au(PPh3)}2](OTf)2 (8). De-
tails of the synthesis of 5 were also applied to the preparation of this
1
compound. Yield: 78% (36 mg). H NMR (298 K, CDCl3): 8.98 (d,
J(HꢀH) = 6.0 Hz, 4H, HR-pyr), 7.90ꢀ7.46 (m, 50H, Ph), 7.13 (d,
J(HꢀH) = 6.0 Hz, 4H, Hβ-pyr), 4.86 (br, 4H, HR4-ferr), 4.59 (br, 4H,
H
β-ferr). 31P{1H} NMR (298 K, CDCl3): 42.0 (t, J(PꢀF) = 7.8 Hz,
PPh3), 32.2 (s, dppf). 19F NMR (298 K, CDCl3, inset D2O with
CF3COOH): ꢀ81.5 (s, 6F, OTf), ꢀ118.8 (m, 4F, FX), ꢀ146.8 (m,
4F, FA). MALDI(þ) m/z: 884.8 ([8 ꢀ 2OTf-PPh3]2þ, calc 884.5),
809.8 ([Pd(dppf)(OTf)]þ, calc: 810.0), 686.0 ([Au(C6F4py)(PPh3) þ
H]þ, calc 686.1), 659.9 ([Pd(dppf) ꢀ H]þ, calc 660.). IR (KBr, cmꢀ1):
1483, 946 (C6F4), 1436, 1424, 1098, 695 (dppf, PPh3), 1280, 1248,
1152, 1029, 635, 495 (OTf). Anal. Calc: C, 48.46; H, 2.85; N, 1.20; S,
2.75. Found: C, 48.31; H, 2.82; N, 1.21; S, 2.82.
Synthesis of [Pt(dppp){(pyC6F4)Au(PPh3)}2](OTf)2 (5).
Solid [Pt(dppp)(H2O)2](OTf)2 (16 mg, 0.02 mmol) was added to a
dichloromethane (5 mL) solution of [Au(C6F4py)(PPh3)] (27 mg, 0.04
Synthesis of [(AuC6F4py)2(μ2-dppm)] (9). A dichloromethane
solution (10 mL) of dppm (58 mg, 0.15 mmol) was added to a
dichloromethane solution (10 mL) of [Au(C6F4py)(tht)] (150 mg,
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1
0.30 mmol) at room temperature. After 1 h of stirring, the reaction
mixture was filtered through Celite, concentrated to 5 mL under
vacuum, and precipitated with hexane (20 mL). During all the manip-
ulations the solution was protected from light in order to avoid
decomposition. A white solid was obtained in 79% yield (145 mg). 1H
NMR (298 K, CDCl3): 8.52 (d, J(HꢀH) = 5.5 Hz, 4H, HR-pyr),
7.75ꢀ7.35 (m, 20H, Ph), 7.20 (d, J(HꢀH) = 4.8 Hz, 4H, Hβ-pyr),
3.70 (t, 2H, J(HꢀP) = 10.8 Hz, PꢀCH2ꢀP). 31P{1H} NMR (298 K,
CDCl3): 33.7 (s). 19F NMR (298 K, CDCl3): ꢀ117.0 (m, 4F, FX),
ꢀ145.5 (m, 4F, FA). FAB(þ) m/z: 1231.4 ([9 þ H]þ, calc 1231.1),
1004.5 ([9 ꢀ C6F4py]þ, calc 1005.0), 808.4 ([9 ꢀ AuC6F4py]þ, calc
808.1). IR (KBr, cmꢀ1): 1436, 1101, 690 (dppm). Anal. Calc: C, 45.87;
H, 2.46; N, 2.28. Found: C, 45.77; H, 2.45; N, 2.23.
A white solid was obtained in 70% yield (130 mg). H NMR (298 K,
CDCl3): 8.71 (d, J(HꢀH) = 6.0 Hz, 4H, HR-pyr), 7.74ꢀ7.45 (m, 20H, Ph),
7.44 (d, J(HꢀH) = 5.4 Hz, 4H, Hβ-pyr), 2.54 (m, 4H, PꢀCH2ꢀ
(CH2)2ꢀCH2ꢀP), 1.97 (br, 4H, PꢀCH2ꢀ(CH2)2ꢀCH2ꢀP). 31P{1H}
NMR (298 K, CDCl3): 39.2 (t, J(PꢀF) = 8.0 Hz). 19F NMR (298 K,
4
CDCl3): ꢀ116.9 (m, 4F, FX), ꢀ144.8 (m, 4F, FA). FAB(þ) m/z: 1272.3
([15 þ H]þ, calc 1273.1); 1046.2 ([15 ꢀ C6F4py]þ, calc 1047.1) . IR
(KBr, cmꢀ1): 1435, 1098, 693 (dppb). Anal. Calc: C, 47.19; H, 2.85; N,
2.20. Found: C, 47.07; H, 2.84; N, 2.25.
Synthesis of [(AuC6F4py)2(μ2-dppdph)] (16). Details of the
synthesis of 9 were also applied to the preparation of this compound. A
1
white solid was obtained in 58% yield (120 mg). H NMR (298 K,
CDCl3): 8.70 (d, J(HꢀH) = 5.1 Hz, 4H, HR-pyr), 7.72ꢀ7.47 (m, 28H,
Ph þ Pꢀ(C6H4)ꢀP), 7.28 (br, 4H, Hβ-pyr). 31P{1H} NMR (298 K,
CDCl3): 42.9 (t, 4J(PꢀF) = 8.0 Hz). 19F NMR (298 K, CDCl3): ꢀ116.7
(m, 4F, FX), ꢀ144.8 (m, 4F, FA). ESI(þ) m/z: 1369.5 ([16 þ H]þ, calc
1369.2); 685.8 ([16 þ 2H]2þ, calc 685.1). IR (KBr, cmꢀ1): 1436, 1104,
692 (dppdph). Anal. Calc: C, 50.89; H, 2.65; N, 2.05. Found: C, 50.71;
H, 2.69; N, 2.03.
Synthesis of [(AuC6F4py)2(μ2-dppip)] (10). Details of the
synthesis of 9 were also applied to the preparation of this compound.
1
A white solid was obtained in 65% yield (122 mg). H NMR (298 K,
CDCl3): 8.52 (d, J(HꢀH) = 4.2 Hz, 4H, HR-pyr), 8.05ꢀ7.36 (m, 20H,
Ph), 7.20 (d, J(HꢀH) = 4.2 Hz, 4H, Hβ-pyr), 1.80 (t, 6H, J(HꢀP) =
14.7 Hz, PꢀC(CH3)2ꢀP). 31P{1H} NMR (298 K, CDCl3): 56.7 (br).
19F NMR (298 K, CDCl3): ꢀ117.3 (m, 4F, FX), ꢀ145.5 (m, 4F, FA).
ESI(þ) m/z: 1259.1 ([10 þ H]þ, calc 1259.1); 630.3 ([10þ2H]þ, calc
630.1). IR (KBr, cmꢀ1): 1436, 1100, 693 (dppip). Anal. Calc: C, 46.76;
H, 2.72; N, 2.23. Found: C, 46.62; H, 2.74; N, 2.24.
Synthesis of [(AuC6F4py)3(μ3-triphos)] (17). A dichloro-
methane solution (10 mL) of triphos (60 mg, 0.10 mmol) was added
to a dichloromethane solution (15 mL) of [Au(C6F4py)(tht)] (153 mg,
0.30 mmol) at room temperature. After 1 h of stirring, the reaction
mixture was filtered through Celite, concentrated to 5 mL under
vacuum, and precipitated with hexane (20 mL). During all the manip-
ulations the solution was protected from the light in order to avoid
decomposition. A white solid was obtained in 84% yield (160 mg). 1H
NMR (298 K, CDCl3): 8.67 (d, J(HꢀH) = 6.0 Hz, 6H, HR-pyr),
7.75ꢀ7.29 (m, 36H, Ph þ Hβ-pyr), 3.32 (d, J(HꢀP) = 10.8 Hz, 6H,
Synthesis of [(AuC6F4py)2(μ2-dppe)] (11). Details of the
synthesis of 9 were also applied to the preparation of this compound.
1
A white solid was obtained in 85% yield (158 mg). H NMR (298 K,
CDCl3): 8.70 (d, J(HꢀH) = 6.4 Hz, 4H, HR-pyr), 7.85ꢀ7.45 (m, 20H,
Ph), 7.42 (d, 4H, Hβ-pyr), 2.86 (s, br, 2H, Pꢀ(CH2)2ꢀP). 31P{1H}
NMR (298 K, CDCl3): 39.0 (s). 19F NMR (298 K, CDCl3): ꢀ117.3 (m,
4F, FX), ꢀ144.8 (m, 4F, FA). FAB(þ) m/z: 1244.9 ([11 þ H]þ, calc
1244.9); 1018.3 ([11 ꢀ C6F4py], calc 1018.0); 821.8 ([11 ꢀ
AuC6F4py], calc 821.0). IR (KBr, cmꢀ1): 1442, 1409, 1104 (dppe).
Anal. Calc: C, 46.32; H, 2.59; N, 2.25. Found: C, 46.45; H, 2.61; N, 2.28.
Synthesis of [(AuC6F4py)2(μ2-dppet)] (12). Details of the
synthesis of 9 were also applied to the preparation of this compound.
CH2), 1.19 (s, 3H, CH3). 31P{1H} NMR (298 K, CDCl3): 21.4 (br). 19
F
NMR (298 K, CDCl3): ꢀ117.8 (m, 6F, FX), ꢀ144.5 (m, 6F, FA).
ESI(þ) m/z: 1894.5 ([17 þ H]þ, calc 1894.2). IR (KBr, cmꢀ1): 1442,
1409, 1097 (C6F4py). Anal. Calc: C, 46.93; H, 2.71; N, 2.22. Found: C,
46.99; H, 2.73; N, 2.23.
Synthesis of [(AuC6F4py)3(μ3-triphosph)] (18). Details of the
synthesis of 17 were also applied to the preparation of this compound. A
1
A white solid was obtained in 60% yield (111 mg). H NMR (298 K,
1
CDCl3): 8.71 (d, J(HꢀH) = 4.0 Hz, 4H, HR-pyr), 7.74ꢀ7.53 (m, 22H,
Ph þ PꢀCHdCHꢀP), 7.42 (d, J(HꢀH) = 4.0 Hz, 4H, Hβ-pyr).
31P{1H} NMR (298 K, CDCl3): 39.4 (br). 19F NMR (298 K, CDCl3):
ꢀ117.3 (m, 4F, FX), ꢀ144.7 (m, 4F, FA). ESI(þ) m/z: 1243.1 ([12 þ
H]þ, calc 1243.1); 622.1 ([12 þ 2H]2þ, calc 622.1). IR (KBr, cmꢀ1):
1436, 1100, 688 (dppet). Anal. Calc: C, 46.39; H, 2.43; N, 2.25. Found:
C, 46.31; H, 2.44; N, 2.21.
Synthesis of [(AuC6F4py)2(μ2-dppa)] (13). Details of the
synthesis of 9 were also applied to the preparation of this compound. A
white solid was obtained in 70% yield (130 mg). 1H NMR (298 K, CDCl3):
8.72 (d, J(HꢀH) = 5.1 Hz, 4H, HR-pyr), 7.90ꢀ7.54 (m, 20H, Ph), 7.47 (d,
J(HꢀH) = 4.8 Hz, 4H, Hβ-pyr). 31P{1H} NMR (298 K, CDCl3): 19.4 (br).
19F NMR (298 K, CDCl3): ꢀ116.8 (m, 4F, FX), ꢀ144.5 (m, 4F, FA).
ESI(þ) m/z: 1241.6 ([13 þ H]þ, calc 1241.1); 621.7 ([13 þ 2H]2þ, calc
621.1). IR (KBr, cmꢀ1): 1436, 1099, 692 (dppa). Anal. Calc: C, 46.47; H,
2.27; N, 2.26. Found: C, 46.39; H, 2.24; N, 2.22.
white solid was obtained in 60% yield (114 mg). H NMR (298 K,
CD2Cl2): 8.65 (d, J(HꢀH) = 6.0 Hz, 6H, HR-pyr), 7.82 (t, J(HꢀP) =
12.0 Hz, 3H, PꢀC6H3ꢀP), 7.54ꢀ7.41 (m, 30H, Ph), 7.37 (d, J(Hꢀ
H) = 4.4 Hz, 6H, Hβ-pyr). 31P{1H} NMR (298 K, CD2Cl2): 43.3. 19F
NMR (298 K, CD2Cl2): ꢀ117.2 (m, 6F, FX), ꢀ145.5 (m, 6 F, FA).
ESI(þ) m/z: 1900.2 ([18 þ H]þ, calc 1900.2); 950.6 ([18 þ 2H]2þ
,
calc 950.6). IR (KBr, cmꢀ1): 1436, 1101, 691 (triphosph). Anal. Calc: C,
47.41; H, 2.39; N, 2.21. Found: C, 47.46; H, 2.41; N, 2.20.
Synthesis of [(AuC6F4py)4(μ4-tetraphos)] (19). A dichloro-
methane solution (10 mL) of tetraphos (80 mg, 0.10 mmol) was added
to a dichloromethane solution (20 mL) of [Au(C6F4py)(tht)] (204 mg,
0.40 mmol) at room temperature. After 45 min of stirring, the reaction
mixture was filtered through Celite, concentrated to 5 mL under
vacuum, and precipitated with hexane (20 mL). During all the manip-
ulations the solution was protected from light in order to avoid
decomposition. A white solid was obtained in 64% yield (160 mg). 1H
NMR (298 K, CDCl3): 8.68 (d, J(HꢀH) = 6.0 Hz, 8H, HR-pyr),
7.99ꢀ6.65 (m, 48H, Ph þ Hβ-pyr), 3.14 (s, br, 8H, CH2). 31P{1H}
NMR (298 K, CDCl3): 24.1. 19F NMR (298 K, CDCl3): ꢀ114.9 (m, 8F,
FX), ꢀ145.3 (m, 8F, FA). FAB(þ) m/z: 2502.2 ([19 þ H]þ, calc
2501.2); 1251.5 ([19 þ 2H]2þ, calc 1251.1). IR (KBr, cmꢀ1): 1446,
1408, 1099 (tetraphos). Anal. Calc: C, 46.58; H, 2.58; N, 2.24. Found: C,
46.60; H, 2.59; N, 2.23.
Synthesis of [(AuC6F4py)2(μ2-dppp)] (14). Details of the
synthesis of 9 were also applied to the preparation of this compound.
1
A white solid was obtained in 88% yield (165 mg). H NMR (298 K,
CDCl3): 8.73 (d, J(HꢀH) = 6.1 Hz, 4H, HR-pyr), 7.78ꢀ7.44 (m, 24H,
Ph þ Hβ-pyr), 3.06ꢀ2.97 (m, 4H, PꢀCH2ꢀCH2ꢀCH2ꢀP), 2.12ꢀ1.98
(m, 2H, PꢀCH2ꢀCH2ꢀCH2ꢀP). 31P{1H} NMR (298 K, CDCl3):
34.6 (t, 4J(PꢀF) = 7.5 Hz). 19F NMR (298 K, CDCl3): ꢀ116.7 (m, 4F,
FX), ꢀ145.0 (m, 4F, FA). FAB(þ) m/z: 1258.3 ([14 þ H]þ, calc
1259.1). IR (KBr, cmꢀ1): 1445, 1104, 691 (dppp). Anal. Calc: C, 46.76;
H, 2.72; N, 2.23. Found: C, 46.89; H, 2.75; N, 2.28.
Synthesis of [(AuC6F4py)4(μ4-tetraphosph)] (20). Details of
the synthesis of 19 were also applied to the preparation of this
compound. A white solid was obtained in 64% yield (161 mg). H
1
Synthesis of [(AuC6F4py)2(μ2-dppb)] (15). Details of the
synthesis of 9 were also applied to the preparation of this compound.
NMR (298 K, CDCl3): 8.60 (d, J(HꢀH) = 5.8 Hz, 8H, HR-pyr),
7.40ꢀ7.10 (m, 50H, Ph þ PꢀC6H2ꢀP þ Hβ-pyr). 31P{1H} NMR
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Organometallics
ARTICLE
(298 K, CDCl3): 36.9 (br). 19F NMR (298 K, CDCl3): ꢀ116.6 (m, 8F,
FX), ꢀ145.1 (m, 8F, FA). ESI(þ) m/z: 2507.7 ([20 þ H]þ, calc
2507.2); 1254.6 ([20 þ 2H]2þ, calc 1254.1); 836.7 ([20 þ 3H]3þ, calc
836.4). IR (KBr, cmꢀ1): 1436, 1105, 690 (tetraphosph). Anal. Calc: C,
46.95; H, 2.33; N, 2.23. Found: C, 46.90; H, 2.31; N, 2.20.
(22) Fernandez, E. J.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Monge,
M.; Montiel, M.; Olmos, M. E.; Rodriguez-Castillo, M. Dalton Trans.
2009, 7509.
(23) Usꢀon, R.; Laguna, A. Organomet. Synth. 1986, 3, 322.
(24) Uson, R.; Laguna, A.; Vicente, J.; Garcia, J.; Jones, P. G.;
Sheldrick, G. M. J. Chem. Soc., Dalton Trans. 1981, 655.
(25) Jones, P. G. Z. Naturforsch., B: J. Chem. Sci. 1982, 37, 937.
(26) Jones, P. G. Z. Kristallogr. 1993, 208, 347.
’ ASSOCIATED CONTENT
(27) Bardaji, M.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Laguna,
M.; Merchan, F.; Romeo, I. Organometallics 1997, 16, 1083.
(28) Cerrada, E.; Laguna, M.; Bartolome, J.; Campo, J.; Orera, V.;
Jones, P. G. Synth. Met. 1998, 92, 245.
(29) Fernandez, E. J.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Monge,
M.; Montiel, M.; Olmos, M. E.; Perez, J. Organometallics 2004, 23, 774.
(30) Fernandez, E. J.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Monge,
M.; Nema, M.; Olmos, M. E.; Perez, J.; Silvestru, C. Chem. Commun.
2007, 571.
S
Supporting Information. CIF file giving X-ray crystal-
b
lographic data for the structural characterization of compounds
BrC6F4py, 1, 4, 17, and 19. X-ray structure of BrC6F4py and
views of crystal packing of BrC6F4py, 1, 4, and 19. This material is
available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
(31) Tyrra, W.; Aboulkacem, S.; Pantenburg, I. J. Organomet. Chem.
2006, 691, 514.
(32) Prasanna, M. D.; Guru Row, T. N. Cryst. Eng. 2000, 3, 135.
(33) Reichenbacher, K.; Suss, H. I.; Hulliger, J. Chem. Soc. Rev. 2005,
34, 22.
Corresponding Author
*E-mail: montse.ferrer@qi.ub.es.
(34) Rybalova, T. V.; Bagryanskaya, I. Y. J. Struct. Chem. 2009,
50, 741.
(35) Vicente, J.; Chicote, M. T.; Gonzalez Herrero, P.; Grunwald,
C.; Jones, P. G. Organometallics 1997, 16, 3381.
(36) Kitadai, K.; Takahashi, M.; Takeda, M.; Bhargava, S. K.; Priver,
S. H.; Bennett, M. A. Dalton Trans. 2006, 2560.
’ ACKNOWLEDGMENT
Financial support for this work was provided by the Ministerio
de Ciencia e Innovaciꢀon (Project CTQ2009-08795) and Factoría
de Cristalizaciꢀon (CONSOLIDER-INGENIO 2010).
(37) Baker, R. W.; Pauling, P. J. J. Chem. Soc., Dalton Trans.
1972, 2264.
’ REFERENCES
(38) Riley, P. E.; Davis, R. E. J. Organomet. Chem. 1980, 192, 283.
(39) Rabe, G. W.; Mitzel, N. W. Inorg. Chim. Acta 2001, 316, 132.
(40) Contel, M.; Stol, M.; Casado, M. A.; van Klink, G. P. M.; Ellis,
D. D.; Spek, A. L.; van Koten, G. Organometallics 2002, 21, 4556.
(41) Croix, C.; Balland-Longeau, A.; Allouchi, H.; Giorgi, M.;
Duchene, A.; Thibonnet, J. J. Organomet. Chem. 2005, 690, 4835.
(42) Osawa, M.; Hoshino, M.; Hashizume, D. Chem. Phys. Lett.
2007, 436, 89.
(43) Melgarejo, D. Y.; Chiarella, G. M.; Fackler, J. P. Acta Crystallogr.,
Sect. C: Cryst. Struct. Commun. 2009, 65, M299.
(44) Bardaji, M.; Jones, P. G.; Laguna, A.; Villacampa, M. D.;
Villaverde, N. Dalton Trans. 2003, 4529.
(45) Aguado, J. E.; Canales, S.; Gimeno, M. C.; Jones, P. G.; Laguna,
A.; Villacampa, M. D. Dalton Trans. 2005, 3005.
(1) Lee, S. J.; Hupp, J. T. Coord. Chem. Rev. 2006, 250, 1710.
(2) Kumar, A.; Sun, S. S.; Lees, A. J. Coord. Chem. Rev. 2008,
252, 922.
(3) Ariga, K.; Hill, J. P.; Lee, M. V.; Vinu, A.; Charvet, R.; Acharya, S.
Sci. Technol. Adv. Mater. 2008, 9, 1.
(4) Lee, S. J.; Lin, W. B. Acc. Chem. Res. 2008, 41, 521.
(5) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450.
(6) Constable, E. C. Coord. Chem. Rev. 2008, 252, 842.
(7) Hiraoka, S.; Sakata, Y.; Shionoya, M. J. Am. Chem. Soc. 2008,
130, 10058.
(8) Ge, Q. C.; Hor, T. S. A. Dalton Trans. 2008, 2929.
(9) Song, L. C.; Jin, G. X.; Zhao, L. Q.; Wang, H. T.; Zhang, W. X.;
Hu, Q. M. Eur. J. Inorg. Chem. 2009, 419.
(46) Crespo, O.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Naranjo,
M.; Villacampa, M. D. Eur. J. Inorg. Chem. 2008, 5408.
(47) Fernandez, E. J.;Jones, P. G.;Laguna, A.;Lopez-de-Luzuriaga, J. M.;
Monge, M.; Olmos, M. E.; Puelles, R. C. Organometallics 2007, 26, 5931.
(48) Cooper, M. K.; Henrick, K.; Mcpartlin, M.; Latten, J. L. Inorg.
Chim. Acta 1982, 65, L185.
(49) Sevillano, P.; Garcia, M. E.; Habtemariam, A.; Parsons, S.;
Sadler, P. J. Met.-Based Drugs 1999, 6, 211.
(50) Ferrer, M.; Gutierrez, A.; Rodriguez, L.; Rossell, O.; Lima, J. C.;
Font-Bardia, M.; Solans, X. Eur. J. Inorg. Chem. 2008, 2899.
(51) He, X. M.; Cheng, E. C. C.; Zhu, N. Y.; Yam, V. W. W. Chem.
Commun. 2009, 4016.
(10) Vicente, J.; Gil-Rubio, J.; Barquero, N.; Camara, V.; Masciocchi,
N. Chem. Commun. 2010, 46, 1053.
(11) Wei, K. J.; Ni, J.; Liu, Y. Z. Inorg. Chem. 2010, 49, 1834.
(12) Mokuolu, Q. F.; Duckmanton, P. A.; Hitchcock, P. B.; Wilson,
C.; Blake, A. J.; Shukla, L.; Love, J. B. Dalton Trans. 2004, 1960.
(13) de Wolf, P.; Waywell, P.; Hanson, M.; Heath, S. L.; Meijer, A. J.
H. M.; Teat, S. J.; Thomas, J. A. Chem.—Eur. J. 2006, 12, 2188.
(14) Ferrer, M.; Mounir, M.; Rossell, O.; Ruiz, E.; Maestro, M. A.
Inorg. Chem. 2003, 42, 5890.
(15) Ferrer, M.; Gutierrez, A.; Mounir, M.; Rossell, O.; Ruiz, E.;
Rang, A.; Engeser, M. Inorg. Chem. 2007, 46, 3395.
(16) Ferrer, M.; Pedrosa, A.; Rodriguez, L.; Rossell, O.; Vilaseca, M.
Inorg. Chem. 2010, 49, 9438.
(52) Yam, V. W. W.; Choi, S. W. K.; Cheung, K. K. Organometallics
1996, 15, 1734.
(17) Laguna, A.; Gimeno, M. C. Trends Organomet. Chem. 1994,
(53) Fernandez, E. J.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Monge,
M.; Montiel, M.; Olmos, M. E.; Puelles, R. C.; Sanchez-Forcada, E. Eur.
J. Inorg. Chem. 2007, 4001.
(54) Schmidbaur, H.; Stutzer, A.; Bissinger, P. Z. Naturforsch., B:
J. Chem. Sci. 1992, 47, 640.
1, 231.
(18) Fernandez, E. J.; Laguna, A.; Olmos, M. E. Adv. Organomet.
Chem. 2005, 52, 77.
(19) Fernandez, E. J.; Laguna, A.; Olmos, M. E. Coord. Chem. Rev.
2008, 252, 1630.
(55) Barcelo-Oliver, M.; Estarellas, C.; Garcia-Raso, A.; Terron, A.;
Frontera, A.; Quinonero, D.; Mata, I.; Molins, E.; Deya, P. M. Crys-
tEngComm 2010, 12, 3758.
(56) Coco, S.; Cordovilla, C.; Dominguez, C.; Espinet, P. Dalton
Trans. 2008, 6894.
(20) Fernandez, E. J.; Hardacre, C.; Laguna, A.; Lagunas, M. C.;
Lopez-de-Luzuriaga, J. M.; Monge, M.; Montiel, M.; Olmos, M. E.;
Puelles, R. C.; Sanchez-Forcada, E. Chem.—Eur. J. 2009, 15, 6222.
(21) Fernandez, E. J.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Olmos,
M. E.; Puelles, R. C. Z. Naturforsch., B: J. Chem. Sci. 2009, 64, 1500.
3428
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Organometallics
ARTICLE
(57) Hewertso., W; Watson, H. R. J. Chem. Soc. 1962, 1490.
(58) Baldwin, R. A.; Cheng, M. T. J. Org. Chem. 1967, 32, 1572.
(59) Jia, G. C.; Puddephatt, R. J.; Scott, J. D.; Vittal, J. J. Organome-
tallics 1993, 12, 3565.
(60) Christina, H.; Mcfarlane, E.; Mcfarlane, W. Polyhedron 1988,
7, 1875.
(61) Phillips, J. E.; Herber, R. H. J. Organomet. Chem. 1984, 268, 39.
(62) Ferrer, M.; Mounir, M.; Rodriguez, L.; Rossell, O.; Coco, S.;
Gomez-Sal, P.; Martin, A. J. Organomet. Chem. 2005, 690, 2200.
(63) Stang, P. J.; Cao, D. H.; Saito, S.; Arif, A. M. J. Am. Chem. Soc.
1995, 117, 6273.
(64) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837.
(65) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112.
(66) Blessing, R. H. Acta Crystallogr. 1995, A51, 33.
3429
dx.doi.org/10.1021/om200318c |Organometallics 2011, 30, 3419–3429