Synthesis of Au(I) trifluoromethyl complexes. Oxidation to Au(III) and reductive elimination of halotrifluoromethanes

Article abstract of DOI:10.1021/om500669j

Au(I) trifluoromethyl complexes [Au(CF₃)L] (L = N-heterocyclic carbene (NHC), isonitrile, phosphine, P(OMe)₃) and [Au₂(CF₃)₂(-dppe)] are prepared by reaction of [Au(X)L] (X = Cl, I) or [Au₂Cl₂(-dppe)], respectively, with AgF and Me₃SiCF₃. The analogous reaction of PPN[Au(C₆F₅)Cl] (PPN⁺ = [Ph₃PNPPh₃]⁺) gives a mixture of complexes of the type PPN[Au(CF₃)_x(C₆F₅)_2-x] (x = 0, 1, 2). Single crystals of the new complex PPN[Au(CF₃)(C₆F₅)] are obtained by liquid diffusion from this mixture, and its crystal structure was determined by X-ray diffraction. Acyclic diaminocarbene complexes [Au(CF₃){C(NEt₂)(NHR)}] (R = ^tBu, 2,6-dimethylphenyl) are obtained by reaction of [Au(CF₃)(CNR)] with NHEt₂. Oxidation of the NHC complex [Au(CF₃)(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with PhICl₂, Br₂, I₂ or ICl affords [Au(CF₃)(X)(Y)(IPr)] (X = Y = Cl, Br I; X = Cl, Y = I). The dicloro, dibromo, and chloro(iodo) complexes are stable in solution in the dark. In contrast, the diiodo complex is unstable and decomposes to [AuI(IPr)] and ICF₃. Under photoirradiation, complexes [Au(CF₃)(X)(Y)(IPr)] undergo reductive elimination to give YCF₃ and [AuX(IPr)] (X = Y = Cl, Br; X = Cl, Y = I).

Full text of DOI:10.1021/om500669j

Article
pubs.acs.org/Organometallics
Synthesis of Au(I) Trifluoromethyl Complexes. Oxidation to Au(III)
and Reductive Elimination of Halotrifluoromethanes
†
‡
,†
,†
María Blaya, Delia Bautista, Juan Gil-Rubio,* and Jose
†
́
Vicente*
́ ́
Grupo de Química Organometalica, Departamento de Química Inorganica, Facultad de Química, Universidad de Murcia, E−30071
Murcia, Spain
‡
SAI, Universidad de Murcia, E−30071 Murcia, Spain
S Supporting Information
*
ABSTRACT: Au(I) trifluoromethyl complexes [Au(CF )L] (L = N-heterocyclic
3
carbene (NHC), isonitrile, phosphine, P(OMe) ) and [Au (CF ) (μ-dppe)] are
3
2
3 2
prepared by reaction of [Au(X)L] (X = Cl, I) or [Au Cl (μ-dppe)], respectively,
2
2
+
with AgF and Me SiCF . The analogous reaction of PPN[Au(C F )Cl] (PPN =
Ph PNPPh ] ) gives a mixture of complexes of the type PPN[Au(CF ) (C F )
3
3
6 5
+
[
]
3
3
3 x
6
5 2−x
(
x = 0, 1, 2). Single crystals of the new complex PPN[Au(CF )(C F )] are obtained
3
6 5
by liquid diffusion from this mixture, and its crystal structure was determined by X-
ray diffraction. Acyclic diaminocarbene complexes [Au(CF ){C(NEt )(NHR)}] (R
3
2
= tBu, 2,6-dimethylphenyl) are obtained by reaction of [Au(CF )(CNR)] with
3
NHEt . Oxidation of the NHC complex [Au(CF )(IPr)] (IPr = 1,3-bis(2,6-
2
3
diisopropylphenyl)imidazol-2-ylidene) with PhICl , Br , I or ICl affords [Au(CF )-
2
2
2
3
(
X)(Y)(IPr)] (X = Y = Cl, Br I; X = Cl, Y = I). The dicloro, dibromo, and chloro(iodo) complexes are stable in solution in the
dark. In contrast, the diiodo complex is unstable and decomposes to [AuI(IPr)] and ICF . Under photoirradiation, complexes
3
[
Au(CF )(X)(Y)(IPr)] undergo reductive elimination to give YCF and [AuX(IPr)] (X = Y = Cl, Br; X = Cl, Y = I).
3
3
INTRODUCTION
To explore the reactivity and potential synthetic applications
■
of Au(I) and (III) trifluoromethyl complexes, we initiated a
study from a different point of view that involves, in the first
stage, the synthesis of Au(I)CF3 complexes, followed by
investigating oxidative addition reactions with halogens and
pseudohalogens. A second step will be the study of trans-
Following the demand for high added-value trifluoromethylated
1
−4
aromatic compounds,
new synthetic protocols for the
selective trifluoromethylation of aromatic substrates involving
in situ generated or preformed trifluoromethyl complexes of
Pd, Cu, or Ag have been recently developed.
2
,5−13
These
metalation reactions with the resulting Au(III)CF complexes.
3
important advances have shown the potential of fluorinated
organometallic compounds in organic synthesis and stimulated
the research on new types of transition-metal perfluoroalkyls.
Reductive elimination of trifluoromethylated compounds is a
key step in many of these reactions, but due to the stability of
The synthesis of gold(I) perfluoroalkyls is still a challenging
14−16,28
objective.
Thus, the first Au(I) trifluoromethyl was
obtained in the reaction of [AuMe(PPh )] with ICF to give
3
3
29
[
Au(CF )(PPh )]. Complexes of the type [Au(CF )L] (L =
3
3
3
PMe , PEt , PPh , PCy , PMe Ph, PF R, CNMe) were
3
3
3
3
2
2
14−16
17−20
30−33
the metal−CF bond,
it is generally a slow process.
3
prepared by using Cd(CF ) as transmetalating agent,
or
3
2
Thus, Toste and co-workers have very recently shown that
thermal decomposition of complexes of the type [Au(Ar)-
by the reaction of [Au(OR)L] (R = CH(CF ) , Ph) with
3
2
34
−
Me SiCF . Recently, salts of the [Au(CF3)2] anion have
3
3
(
[
CF )I(PR )], prepared by oxidative addition of CF I to
3
3
3
been obtained by reaction of AuCl or [AuCl(tht)] with
21
−
35,36
Au(Ar)(PR )], affords ArI instead of ArCF . This contrasts
Me SiCF and F .
Interestingly, BF -assisted hydrolysis of
3
3
3
3
3
−
37
with the very mild elimination of biaryls and nonfluorinated
[Au(CF ) ] gives [Au(CF )(CO)], which undergoes CO
3 2 3
t
36
alkylarenes from the corresponding diorganogold(III) com-
substitution by tht, BuNC, MeCN, or py ligands, making this
carbonyl complex a valuable synthon to prepare species
2
2−26
plexes.
However, the above-mentioned work of the Toste
group also reports that fast ArCF reductive elimination at
containing the Au(CF ) unit. However, the synthesis of these
3
3
room or low temperature occurs by abstraction of the iodo
ligand from the studied Au(III) complexes. This suggests the
viability of gold-catalyzed arylic trifluoromethylation. Apart
from this report, reductive elimination of trifluoromethylated
compounds from Au(III) trifluoromethyl complexes has never
been documented, and very little is known about the reactivity
and potential applications in organic synthesis of gold
complexes requires previous preparation of [PPh ][Au(CF ) ]
and the handling of moisture-sensitive and unstable com-
pounds.
Most Au(III) trifluoromethyl complexes have been obtained
by oxidative addition to Au(I) complexes. Thus, addition of
4
3 2
Received: June 24, 2014
Published: October 24, 2014
2
1,27,28
perfluoroalkyl derivatives.
©
2014 American Chemical Society
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Organometallics
halogens to [Au(CF )(PR )] or [Au(CF ) ] gave [Au(CF )-
Article
−
3
3
3 2
3
Scheme 1. Synthesis of Gold(I) Trifluoromethyl Complexes
(1−13)
3
0,31
−
X (PR )] (X = Br, I; R = Me, Et, Ph)
or [Au(CF ) X ] (X
2
3
3 2 2
3
6
=
Cl, Br, I), respectively. Oxidative addition of ICF to
3
30,31 29,38
[
[
[
Au(CF )(PR )] (R = Me, Et)
or [AuMe(PMe )]
gave
3
3
3
Au(CF ) I(PR )], or mixtures of [AuMe (CF )(PMe )] and
3
2
3
2
3
3
AuI(PMe )], respectively. Photoinitiated oxidative addition of
3
ICF to [Au(Ar)(PR )] (R = Cy or Ph) gave [Au(Ar)(CF )-
3
3
3
2
1
I(PR )]. Au(CF ) and [Au(CF ) (μ-X)] were obtained by
condensation of Au atoms with XCF (X = Br or I).
3
3 3
3 2
2
3
9,40
Only
3
one trifluoromethylation reaction of a Au(III) compound has
been reported, namely, the reaction of AuCl with Me SiCF
3
3
3
−
−
36
and F , which gave [Au(CF ) ] . The reaction of [Au-
3
4
−
(
[
CN) ] with ClF gave a mixture of complexes of the type
] (x = 0−4, y = 0−2).
In the search for straighforward methods to prepare Au(I)
4
−
41
AuF Cl (CF )
x
y
3 4−x−y
trifluoromethyl compounds, we turned our attention to Ag(I)
trifluoromethyl complexes. Solutions of “Ag(CF )” can be
3
generated by reaction of AgF with Me SiCF and have been
3
3
used as transmetalating agents toward compounds of elements
42
from the groups 14−16, as well as in the trifluoromethylation
1
2,13,43−46
of organic substrates.
Herein, we report the synthesis
of a series of Au(I) trifluoromethyl complexes by reaction of
easily available [AuCl(L)] complexes with AgF and Me SiCF ,
3
3
which includes the first gold trifluoromethyl complexes
containing carbene ligands. We have also studied the oxidative
addition of PhICl , Br , I and ICl to [Au(CF )(IPr)] (IPr =
2
2
2
3
1
,3-bis(2,6-diisopropylphenyl)imidazol-2-ydene). The isolated
Au(III) complexes, except for the diiodo derivative, are
thermally stable, but on photoirradiation undergo reductive
elimination to give YCF and [AuX(IPr)] (X = Y = Cl, Br; X =
Cl, Y = I).
3
[Au(CF )L]. However, the NMR and ESI-MS spectra of the
3
isolated neutral complexes do not show any evidence of ligand
exchange at room temperature (see below), suggesting that
these byproducts should be formed by side reactions or by
ligand exchange catalyzed by Ag(I) salts present in the reaction
mixture.
RESULTS AND DISCUSSION
■
Synthesis of Au(I) Trifluoromethyl Complexes. Com-
t
plexes [AuXL] (X = Cl, L = IPr, BuNC, XyNC, PMe , PPh ,
3
3
P(p-Tol) , P(OMe) ; X = I, L = SIPr, IMes, IBz, IBzMe,
3
3
+
+
n
The reaction of PPN[Au(C F )Cl] (PPN = [Ph PNPPh ] )
I BuMe) or [Au Cl (μ-dppe)] react with AgF (1.5−1.8 equiv)
6 5 3 3
2
2
with AgF and Me SiCF gave a mixture containing mainly
and an excess of Me SiCF at room temperature to give
3
3
3
3
complexes PPN[Au(CF ) (C F5)2−x] (x = 0, 1, 2) and minor
trifluoromethyl complexes 1−13 (Scheme 1). The Au(I)
trifluoromethyl complexes were separated from the reaction
crude by column chromatography on silica and isolated in
3 x
6
−
amounts of [Ag(CF ) ] , which were detected in the reaction
3 2
−
crude by negative ESI-MS. Complexes [Au(CF ) ] , [Au-
3 2
−
−
19
36
29,30,34
(C F ) ] , and [Ag(CF ) ] were also identified by F NMR
yields ranging from 25 to 78%. Compounds 7, 9,
and
6 5 2 3 2
3
0,34
spectroscopy (see the Experimental Section). Single crystals of
the new complex PPN[Au(CF )(C F )] were obtained by
10
have been previously reported (see the Introduction),
but the present method allows one to prepare them directly
from the corresponding chloro complexes, without using the
toxic Cd(CF ) . The new trifluoromethyl complexes are air-
3
6 5
liquid diffusion from this mixture, and its crystal structure was
determined by X-ray diffraction (see the Crystal Structures
section). To the best of our knowledge, this is the first complex
containing both CF and C F ligands bonded to the same
3
2
stable and can be stored at room temperature, except in the
case of the trimethylphosphite complex 12, which slowly
decomposes to metallic gold at room temperature. The low
yields obtained in some cases are attributed to the formation of
side products, or to partial decomposition during chromato-
graphic separation. Thus, NMR analysis of the reaction crudes
3
6 5
metal.
Au(I) trifluoromethyl complexes containing ADC (acyclic
diaminocarbene) ligands (14 and 15, Scheme 2) were obtained
by reaction of the isocyanide complexes 7 or 8 with NHEt2.
They are less stable than their NHC counterparts and must be
stored at low temperature.
revealed that, although complexes 1−13 are the major reaction
products, significant amounts of the known complexes [AuL ]
+
2
were also formed. The highest amount of the cationic side
Scheme 2. Synthesis of Gold(I) Trifluoromethyl Complexes
14 and 15 Containing ADC Ligands
product was observed for L = IMes, which gave a ca. 1:1
+
47
+
mixture of 3 and [Au(IMes) ] . Minor amounts of [AuL ]
2
2
4
8
48
n
49
were detected for L = IBz, IBzMe, I BuMe, XyNC, and
1
9
PMe . In the two latter cases, the F NMR and ESI-MS spectra
3
−
of the crude revealed the presence of [Au(CF ) ] (see the
3
2
Experimental Section). On the basis of this observation, we
hypothesized that salts of the type [AuL ][Au(CF ) ] could be
2
3 2
formed by ligand exchange between two molecules of
6
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Article
Reactions of Complex 1 with PhICl , Br , or I . The
mixture, and [AuI(IPr)], ICF , and a new complex (18) were
also detected. A temperature rise led to progressive reduction of
the amount of 1, with a concomitant increase of 18, [AuI(IPr)]
2
2
2
3
reactions of 1 with 1 equiv of PhICl or an excess of Br (1.2−3
2
2
equiv) led to trans-[Au(CF )X (IPr)] (X = Cl (16), Br (17)),
3
2
which were isolated as white or yellow solids, respectively
Scheme 3). Their trans configuration was determined by
and ICF . Finally, at room temperature, the signals of 1 and 18
3
(
progresively vanished, and only those of [AuI(IPr)] and ICF
3
single-crystal X-ray diffraction (see the Crystal Structures
section).
were finally observed. Considering the behavior of 18 and the
similarity of its H NMR resonances with those of 16 or 17, we
1
assigned it to the oxidative addition product trans-[Au(CF )-
3
Scheme 3. Formation and Decomposition of Au(III)
Trifluoromethyl Complexes
I2(IPr)]. The simultaneous presence of 1, 18, [AuI(IPr)], and
ICF in the reaction mixture suggests that the rates of I
3
2
oxidative addition to 1 and ICF reductive elimination from 18
3
do not differ greatly.
The reaction of 1 with ICl (1 equiv) gave quantitatively (SP-
4
-2)-[Au(CF )(Cl)(I)(IPr)] (19, Scheme 3), which was
3
isolated as a yellow-orange crystalline solid by crystallization
at low temperature. Its NMR spectra (see below) suggest that,
in 19, the CF3 and IPr ligands are disposed in a trans
arrangement, as for 16−18. In addition, we carried out several
attempts to determine its X-ray structure. Although a full
structure determination was not possible because of the low
quality of the crystals measured, the obtained data confirmed
the trans disposition of the CF3 and IPr ligands. It is
noteworthy that, although a large number of halogen oxidative
additions to Au(I) complexes have been reported, 19 is the first
isolated Au(III) complex resulting from an interhalogen
oxidative addition reaction. Complex 19 is stable in the solid
state at room temperature, but in solution (CD Cl ), at room
2
2
temperature, and in the dark, it undergoes a slow partial
halogen redistribution to give the dichloro and diiodo
complexes 16 and 18. Thus, after 4 days, the amounts of 16,
18, and 19 were in a 1:1:14 relative proportion. This contrasts
with the fast halogen scrambling reported in complexes
Remarkably, good yields of 16 were obtained only if the
53,54
[
AuCl Br3−xL] (L = tertiary phosphine or phosphole).
x
addition of PhICl is carried out at low temperature (−90 °C).
2
Along with these compounds, small amounts of [AuI(IPr)] and
ICF3 are also observed, likely formed through reductive
elimination from 18. Analogously to 17, complex 19 underwent
reductive elimination after 30 min under photoirradiation to
quantitatively give [AuCl(IPr)] and ICF3.
Carrying out the addition at room temperature led to mixtures
50
51
containing mainly 16, [AuCl (IPr)], [AuCl(IPr)], ClCF3,
3
and 1 (see the Supporting Information). The side products
AuCl(IPr)] and ClCF3 are not formed by reductive
[
elimination from 16 because it is stable in solution (see
below). Instead, they could be formed through reductive
elimination from a Au(III) intermediate, as previously reported
Previous studies on the reductive elimination of R-I, Ar-Cl,
52,55
or R-F from complexes trans-[Au(R)I (IPr)] (R = alkyl),
2
56
trans-[Au(Ar)Cl (IPr)] (Ar = C H , C F ), or cis-[Au(R)-
52
2
6
5
6 5
for the reaction of [Au(Me)(IPr)] with I2, or by direct
55
F2(IPr)], respectively, suggest that these reactions proceed
through halide dissociation, to give a cationic tricoordinated
intermediate, which decomposes to give the organic halide and
the Au(I) complex (Scheme 4). According to this mechanism,
halogenation of the Au−CF bond. [AuCl (IPr)] could be
3
3
formed through oxidation of [AuCl(IPr)] by the remaining
PhICl2.
Both 16 and 17 are thermally stable in the solid state
(
decomposition temperature > 200 °C), as well as in solution
Scheme 4. Proposed Mechanism for the Reductive
Elimination from Au(III) Complexes
under ambient laboratory light. Thus, they remained unaltered
after heating their CD Cl solutions at 80 °C, for 16 h. In
2
2
contrast, 17 was quantitatively converted into [AuBr(IPr)] and
BrCF on irradiation of a CD Cl solution with UV−visible
3
2
2
light of λ > 260 nm, whereas irradiation of 16 under the same
conditions gave a solution containing [AuCl(IPr)] (main
organometallic product), ClCF , and several organic fluorinated
3
products that could not be identified (see the Supporting
Information).
The reaction of 1 with I (1 or 3 equiv) at room temperature
2
51
quantitatively gave [AuI(IPr)] and ICF (Scheme 3). In order
3
to detect possible reaction intermediates, we mixed the reagents
in an NMR tube at −90 °C, inserted the tube into the NMR
probe at −80 °C, and progressively increased the temperature
(
−
see the Supporting Information). At low temperatures (from
80 to −40 °C), 1 was the main component of the reaction
6
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Organometallics
Article
Figure 1. Molecular structures of complexes 3 (left), 4 (middle), and 5 (right). Thermal ellipsoids have been drawn at 50% probability.
the kinetic barrier to reductive elimination should be smaller as
containing 16 and 17 was stored in the dark for 1 h, and
57
the Au−halide dissociation energy becomes lower. Although
then it was irradiated for a short time to avoid complete
decomposition. NMR analysis of the mixture showed that no
changes occurred in the dark, but after irradiation, 16, 17,
58
Au(III) is considered as a soft acid in aqueous solution, the
−
computed dissociation energies of complexes [AuX ] in the
4
−
−
−
−
59−61
gas phase follow the sequence F > Cl > Br > I ,
which
[Au(CF )(Br)(Cl)(IPr)], and photodecomposition products
3
is in line with the generally observed lower stability of Au(III)
iodo complexes with respect to their chloro or bromo
were detected (see the Supporting Information). Formation of
the mixed-halogen complex suggests that photoirradiation can
induce halide dissociation on these complexes, although this
complex could also be formed by halide exchange between 16
or 17 and the decomposition products [AuX(IPr)] (X = Cl,
6
2
analogues. Thus, the easier reductive elimination observed
in the diiodo complex 18 can be attributed to a lower halide
dissociation energy. In addition, the kinetic stability of 16 with
56
67
respect to trans-[Au(Ph)Cl (IPr)] could be attributed to the
Br).
2
strengthening of the Au−Cl bond produced by the enhanced
Lewis acidity of the metal center in the trifluoromethyl
complex.
Spectroscopic Characterization. The ν(CN) band of
−
1
compound 8 appears at 2215 cm , a value similar to those
6
8
69
reported for the analogous chloro or nitrato complexes
−1
Reductive elimination in complexes 16, 17, and 19 could
take place by photoexcitation to a state where one of the Au−
halogen bonds is weakened. Spectroscopic and theorethical
studies on Au(III) carbene halides show that the lowest-energy
excited states of these complexes are of the LMCT type,
involving the transfer of electron density from the halide-based
HOMO to the metal-based LUMO, which presents Au−X
(2215.8 or 2215 cm , respectively), which is in agreement with
the high electronegativity of the CF group.
3
The NMR data of compounds 7, 9, and 10 coincide with
3
0,31,36
19
those previously reported.
The δ( F) values of the CF
3
groups of complexes [Au(CF )L] (1−15) and PPN[Au(CF )-
3
3
(C
F
)] fall in a narrow range (from −31.4 to −26.1 ppm),
)(X)(Y)(IPr)], they spread
6 5
whereas, in complexes [Au(CF
3
4
8,56,63,64
antibonding character.
Similarly, the lowest-energy
over a wider range depending on the nature of the halogens (I:
absorption maxima of 16−18 move to lower energies as the
halogen electronegativity decreases, which is characteristic for
LMCT transitions (λmax = 272, 312, and 365 nm for 16, 17, and
−9.5 ppm; Br: −24.5 ppm; Cl: −32.4 ppm; Cl and I: −21.5
19
ppm). In the phosphine complexes 9−12, the F NMR signal
31
appears as a doublet due to coupling with P. Conversely, a
3
1
1
19
18, respectively), and 19 gives two maxima at 291 and 376 nm,
quartet is observed in their P{ H} NMR spectra. The F and
31
1
which are assigned to Cl → Au and I → Au LMCT transitions,
respectively (the spectra are included in the Supporting
Information). Interestingly, complex 19 reductively eliminates
ICF instead of ClCF . According to the proposed mechanism,
P{ H} NMR spectra of complex 13 display a virtual doublet
and a second-order multiplet, respectively, corresponding to an
AA′X X′ spin system (see the Supporting Information).
3
3
1
3
1
In the C{ H} NMR spectra, the gold-bound carbons of the
carbene and isonitrile ligands give a quartet due to their
3
3
this could be explained by considering that photoexcitation of
the lower energy LMCT (I → Au) state would increase the
electron density al the metal center and weaken the Au−Cl
3
coupling with the fluorine nuclei of CF groups. The J values
3
FC
are smaller for the Au(I) complexes (12.8−19.8 Hz) than for
the Au(III) complexes (16: 28.5; 17: 29.5; 19: 27.9 Hz). The
existence of these couplings suggests that ligand exchange, as
found in some Cu(I) or Ag(I) trifluoromethyl complexes,
−
+
bond, leading to Cl dissociation, to give [Au(CF )I(IPr)] ,
3
which would reductively eliminate ICF3.
To obtain experimental evidence of the proposed photo-
activated halide dissociation, we treated a CD Cl solution of
which are in equilibrium with ionic species of the type
2
2
n
10,13,70,71
the dibromo complex 17 with (N Bu )Cl. However, halide
[ML ][M(CF ) ],
does not occur (in CD Cl ). The
4
2
3 2
2 2
exchange took place in the dark, giving a mixture of 16, 17, and
Au-bound carbenic carbon of the IPr ligand is shielded on
going from the Au(I) complex 1 (188.5 ppm) to its Au(III)
congeners 16, 17, and 19 (165.5, 168.0, and 162.5 ppm,
65
[
Au(CF )(Br)(Cl)(IPr)], probably through an associative
3
6
6
pathway. In another experiment, a CD Cl2 solution
2
6
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Organometallics
Article
Figure 2. Molecular structures of complexes 7 (left) and 9 (right) showing the formation of aurophilic dimers. Thermal ellipsoids have been drawn
at 50% probability.
respectively), and the carbenic carbons of 1, 16, 17, and 19 are
deshielded with respect to their halogenated analogues
5
1
[
AuX(IPr)] (Cl: 175.7 ppm; Br: 179.0 ppm), or [Au-
50 72
Cl (IPr)] (Cl: 145.7 ppm; Br: 146.2 ppm ). The CF carbon
3
3
is deshielded in the Au(I) complexes (δ 155.9−166.5 ppm)
with respect to the Au(III) ones (δ 123.9−125.3 ppm).
In agreement with the trans configuration observed in the
i
1
crystal structures, all Pr groups appear equivalent in the H
NMR spectra of 16 and 17. The same was observed for 18,
which suggests that this complex has also a trans configuration.
According to its lower symmetry, complex 19 shows duplicated
i
signals for the Pr groups. The coupling constant between the
carbenic carbon and the three fluorine nuclei of 19 is very
similar to those of 16 and 17, which suggests that, in complex
1
9, the CF group is disposed trans to the IPr ligand.
3
Crystal Structures. The crystal structures of complexes 3,
4
, 5, 7, 9, 13, 14·(CH Cl ) , 15, PPN[Au(CF )(C F )]·
2
2 0.5
3
6 5
(
CH Cl ) , 16, and 17 have been determined by single-crystal
2 2 0.5
X-ray diffraction (Figures 1−6). Important bond distances and
angles are displayed in Table 1. The coordination geometries
are linear (Au(I) complexes), or square-planar (Au(III)
Figure 3. Molecular structure of complex 13 showing the formation of
aurophilic cyclic dimers. Thermal ellipsoids have been drawn at 50%
probability.
complexes) with slight distortions. The Au−CF distances are
3
very similar for all Au(I) trifluoromethyl complexes containing
carbene, isonitrile, or C F ligands (2.031−2.046 Å), with the
9 are composed of aurophilic dimers (Figure 2) with short Au···
Au distances (3.1526 Å (7); 3.1020 and 3.1282 Å (9)). In these
cases, the lower sterical demand of the isonitrile and PMe3
ligands and the skew relative disposition of the interacting
molecules allow a close approach between both Au centers,
while minimizing the steric repulsions. Aurophilic interactions
between two inversion related molecules of complex 13 give
rise to the formation of cyclic dimers (Figure 3), where the
mutually interacting P−Au−C units adopt a skew disposition
(Au···Au distance: 3.2024 Å). Similar aurophilic dimers are also
6
5
exception of complex 3. In contrast, the PMe and dppe
3
complexes 9 and 13 show sligthly longer Au−C bond distances
(
2.056−2.075 Å). Similar distances have been reported for
35
PPN[Au(CF ) ] (2.059, 2.073 Å), [Au(CF )(PPh )] (2.045
Å), and [Au(CF )(CO)] (2.047 Å). In PPN[Au(CF )-
3
2
3
3
7
3
37
3
3
(
C F )], the Au−CF and Au−C F distances do not differ
6
5
3
6 5
significantly. In the Au(III) complexes, the Au−CF distance is
considerably larger for the dibromo complex 17 than for the
dichloro complex 16 (2.112 vs 2.052 Å)
3
The ADC ligands of complexes 14 and 15 adopt a planar
disposition with the Bu or Xy groups oriented away from the
found in the crystal structures of complexes [Au X (μ-dppe)]
2 2
74,75 76
t
(X = Cl,
C Ph ).
2
NEt group to minimize steric repulsions (Figure 4).
2
CONCLUSIONS
The reaction of Au(I) chloro complexes with AgF and
Carbene complexes 3, 4, 5, 14, and 15 do not show
aurophilic interactions, which can be attributed to the steric
hindrance produced by the CF3 and carbene ligands.
Accordingly, the shortest distance between two Au centers
■
TMSCF allows the preparation of a wide range of Au(I)
3
trifluoromethyl complexes in a single step from easily available
Au(I) chloro complexes. By using this method, the first Au(I)
trifluoromethyl complexes containing carbene ligands have
(
3.939 Å) is found in complex 5, which contains the less bulky
carbene ligand of the series. In contrast, the structures of 7 and
6
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Organometallics
Article
Figure 4. Molecular structures of complexes 14 (left) and 15 (right). Thermal ellipsoids have been drawn at 50% probability.
been prepared, and representative examples of all synthesized
types of complexes have been characterized by single-crystal X-
ray diffraction.
Oxidation of [Au(CF )(IPr)] with Cl , Br , I , or ICl gives
3
2
2
2
the corresponding square-planar Au(III) complexes, where the
CF and IPr ligands are disposed in a trans arrangement. trans-
3
[
Au(CF )I (IPr)] decomposes to [AuI(IPr)] and ICF even at
3
2
3
low temperature. In contrast, complexes trans-[Au(CF )-
3
X2(IPr)] (X = Cl, Br) are stable in solution in the dark, but
reductively eliminate XCF (X = Cl, Br) when irradiated with
3
UV−visible light. Analogously, (SP-4-2)-[Au(CF )(Cl)(I)-
3
(
IPr)] reductively eliminates ICF , but not ClCF , under
3 3
UV−visible irradiation. The observed behavior in the
halotrifluoromethane elimination reactions is in agreement
with a mechanism involving halide dissociation to give a
cationic tricoordinate Au(III) intermediate [Au(CF )X(IPr)]Y,
3
Figure 5. Molecular structure of the anion of the salt PPN[Au(CF )-
which undergoes reductive elimination to give [AuY(IPr)] and
3
(
C F )]. Thermal ellipsoids have been drawn at 50% probability.
6 5
XCF . Studies of the synthesis of other types of Au(III)
3
perfluoroalkylated complexes and the reductive elimination of
perfluoroalkylated molecules are underway in our laboratories.
Figure 6. Molecular structures of complexes 16 (left) and 17 (right). Thermal ellipsoids have been drawn at 50% probability. Hydrogen atoms have
been omitted for clarity.
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Article
Table 1. Selected Bond Lengths (Å) and Angles (deg) for Complexes [Au(CF )L] and [Au(CF )X L]
3
3
2
L (Complex)
X
Au−CF3
Au−L
E−Au−E′
a
IMes (3)
2.013(13), 2.030(14)
2.039(3)
Au−C: 2.041(8)
Au−C: 2.022(2)
Au−C: 2.026(3)
C−Au−C: 177.3(5), 176.0(5)
C−Au−C: 177.80(9)
C−Au−C: 175.82(12)
IBz (4)
IBzMe (5)
2.041(3)
t
BuNC (7)
2.034(3), 2.031(4)
Au−C: 1.988(4), 1.996(4)
C−Au−C: 179.16(15), 177.44(13)
PMe (9)
2.070(8), 2.056(8),
Au−P: 2.291(2), 2.284(2), 2.290(2)
C−Au−P: 175.4(2), 175.9(2), 176.4(2)
3
2
.062(9)
1
/2 dppe (13)
2.063(3), 2.075(3)
2.036(4)
Au−P: 2.2960(7), 2.2895(7)
Au−C: 2.048(3)
C−Au−P: 173.09(9), 173.96(9)
C−Au−C: 178.54(15)
t
C(NH Bu)NEt (14)
2
C(NHXy)NEt (15)
2.043(2)
Au−C: 2.043(2)
Au−C: 2.047(3)
C−Au−C: 174.81(9)
C−Au−C: 175.4(4), 177.9(3)
C−Au−C: 178.68(14), 179.83(17)
2
a
C6F5
2.044(8), 2.046(10)
IPr (16)
Cl 2.086(3)
.085(4)
Au−C: 2.052(3), 2.059(3)
Au−Cl: 2.2650(8), 2.2816(9),
2
CNHC−Au−Cl: 86.48(9), 93.87(9),
2
.2716(9), 2.2763(9)
87.51(9), 92.33(9)
CCF3−Au−Cl: 92.24(10), 87.39,
9
2.34(13), 87.82(13)
Cl−Au−Cl: 177.52(4), 179.75(4)
C−Au−C: 178.99(9)
IPr (17)
Br 2.112(3)
Au−C: 2.073(2)
Au−Br: 2.4123(3), 2.4172(3)
CNHC−Au−Br: 89.19(6), 89.83(7)
CCF3−Au−Br: 91.51(6), 89.45(7)
Br−Au−Br: 176.332(11)
a
The CF group is disordered over two positions.
3
1
EXPERIMENTAL SECTION
5.59. H NMR (400.9 MHz, CD
2
Cl
2
): δ 7.36 (m, 5H, Ph), 6.95 (d,
■
3
3
JHH = 1.6 Hz, 1H, imidazole), 6.92 (d, 1H, J = 1.6 Hz, imidazole),
5.38 (s, 2H, CH
CD Cl
(Ph), 122.6 (CH imidazole), 120.7 (CH imidazole), 55.0 (CH
(Me). (+)ESI-MS m/z: 497 (MH ), 541 ([Au(IBzMe)
5
1
HH
1
General Considerations. Complexes [AuCl(IPr)], [AuI-
), 3.85 (s, 3H, Me). 13C{ H} NMR (75.5 MHz,
7
7
51
78
79
2
(
(
SIPr)], [AuI(IMes)], [AuCl(IBz)], [AuCl(IBzMe)], [AuCl-
49 80 81 82
n
2
2
): δ 182.2 (CAu), 135.9 (i-Ph), 129.3 (Ph), 128.9 (Ph), 128.3
I BuMe)], [AuCl(PR )] (R = Ph, p-tolyl, Me, OMe ),
3
83
t
84
68
2
), 38.2
] ), 865
[
(AuCl) (μ-dppe)], and [AuCl(CNR)] (R = Bu, Xy ) were
2
+
+
8
5
2
prepared by reacting [AuCl(SMe )] with 1 equiv of the
2
+
(
[Au (IBzMe) I] ).
2
2
corresponding ligand in CH Cl at room temperature. Other reagents
2
2
n
[
AuI(I BuMe)]. This was prepared in the same way as for
AuI(IBz)], starting from NaI (371 mg, 2.48 mmol) and [AuCl-
I BuMe)] (294 mg, 0.79 mmol) in MeCN (6 mL). A pale brown
were obtained from commercial sources and used without further
purification. Commercial 2 M solutions of Me SiCF in THF (Aldrich
or Acros) were used. The trifluoromethylation reactions were carried
[
(
3
3
n
solid was obtained. Yield: 264 mg, 72%. mp 97−99 °C. Anal. Calcd for
out under a N atmosphere using standard Schlenck techniques. Test
2
C H AuIN : C, 20.79; H, 3.05; N, 6.06. Found: C, 20.79; H, 3.02; N,
8
14
2
reactions were performed in screw-cap NMR tubes equipped with a
PTFE-covered rubber septum. EtCN was distilled over P O and
1
3
6
.11. H NMR (400.9 MHz, CD Cl ): δ 6.96 (d, J = 1.6 Hz, 1H,
2 2 HH
2
5
3
2
imidazole), 6.94 (d, J = 1.6 Hz, 1H, imidazole), 4.17 (t, J = 7.2
Hz, 2H, CH N), 3.82 (s, 3H, NMe), 1.83 (sext, J = 7.2 Hz, 2H,
HH
HH
stored under N . CH Cl was distilled over CaH .
2
2
2
2
3
−
1
2
H
H
Infrared spectra were recorded in the range of 4000−200 cm with
3
3
Nujol mulls between polyethylene sheets. 1H NMR spectra were
CH ), 1.38 (sept, J = 7.2 Hz, 2H, CH ), 0.96 (t, J = 7.2 Hz, 2H,
2 HH 2 HH
1
3
1
Me). C{ H} NMR (75.5 MHz, CD Cl ): δ 181.5 (CAu), 121.9
2
2
referenced to residual CHDCl (5.32 ppm), CHCl (7.24 ppm), and
2
3
19
31
(imidazole), 120.6 (imidazole), 51.0 (NCH ), 38.1 (NMe), 33.3 (C2,
Bu), 19.9 (C3, Bu), 13.7 (s, Me). (+)ESI-MS m/z: 363
[Au(CO)(I BuMe)] ), 463 (MH ), 473 ([Au(I BuMe) ] ), 480
[M + NH ] ), 797 ([Au (I BuMe) I] )
2
C D H (7.15 ppm). F or P{H} NMR spectra were referenced to
6
5
n
n
external CFCl or H PO (0 ppm). ESI-MS and HR-MS spectra were
3
3
4
n
+
+
n
+
(
(
measured using a solution of HCO H (1.01 mM) and (NH )(HCO )
2
2
4
2
+
n
+
(
5 mM) in MeOH/H O (75:25 v:v) as carrier. Melting points were
4
2
2
2
[
Au(CF )(IPr)] (1). Me SiCF (1.58 mmol) was added to a
determined on a Reichert apparatus in an air atmosphere.
AuI(IBz)]. NaI (180 mg, 1.20 mmol) was added to a solution of
AuCl(IBz)] (154 mg, 0.38 mmol) in MeCN (6 mL). After 1 h at
room temperature, the mixture was evaporated under vacuum. The
residue was extracted with 15 mL of CH Cl and the extract was
3 3 3
suspension of AgF (40 mg, 0.32 mmol) in EtCN (3 mL). The
mixture was stirred at room temperature for 1.5 h in the darkness. To
the resulting suspension, [AuCl(IPr)] (196 mg, 0.31 mmol) and EtCN
3 mL) were added. The mixture was stirred for 17 h at room
temperature in the darkness. The resulting dark gray suspension was
brougth to dryness under vacuum. The residue was extracted with
[
[
(
2
2
filtered through a Celite pad. The solution was concentrated under
vacuum to ca. 1 mL. Addition of n-pentane (5 mL) gave a pale brown
solid, which was filtered, washed with n-pentane (3 × 5 mL) and dried
under vacuum. Yield: 156 mg, 83%. mp: 127−129 °C. Anal. Calcd for
C H AuIN : C, 35.68; H, 2.82; N, 4.90. Found: C, 35.65; H, 2.94; N,
CH
column using CH
colorless fraction (R
Cl
(20 mL), and the extract was chromatographed on a silica gel
Cl /n-hexane (2:1) as eluent. The collected
= 0.74) was concentrated to ca. 1 mL. Addition
2
2
2
2
17
16
2
f
1
4
.99. H NMR (400.9 MHz, CD Cl ): δ 7.36 (m, 10H, Ph), 6.92 (s, 2
of n-pentane (5 mL) gave a white solid, which was washed with n-
pentane (3 × 2 mL), and dried under vacuum. Yield: 125 mg, 61%.
mp: 210 °C (d). Anal. Calcd for C28H36AuF N : C, 51.38; H, 5.54; N,
4.28. Found: C, 51.23; H, 5.39; N, 4.60. IR (Nujol, cm ): 1132, 971
ν(C−F). H NMR (400.9 MHz, CD
2H, p-C
imidazole), 2.55 (sept, JHH = 6.8 Hz, 4H, CHMe ), 1.33 (d, JHH = 6.8
Hz, 12H, CHMe
NMR (75.5 MHz, CD Cl ): δ 188.5 (q, J = 13.7 Hz, CAu), 162.6
(q, J = 345.4 Hz, CF ), 146.1 (o-C H ), 134.2 (i-C H ), 130.9 (p-
CF 3 6 3 6 3
2
2
13
1
H, imidazole), 5.41 (s, 4H, CH2). C{ H} NMR (75.5 MHz,
CD Cl ): δ 181.7 (CAu), 135.7 (i-Ph), 129.3 (Ph), 128.9 (Ph), 128.3
3 2
2
2
−1
(
(
(
Ph), 121.2 (CH imidazole), 55.0 (CH ). (+)ESI-MS m/z: 462
2
+
+
+
1
3
[Au(IBz)(NH )] ), 573 (MH ), 590 ([M + NH ] ), 693 ([Au-
2
Cl
2
): δ 7.56 (t, JHH = 7.8 Hz,
), 7.22 (s, 2H,
3
4
+
+
3
IBz) ] ), 1017 ([Au (IBz) I] ).
6
H
3
), 7.35 (d, JHH = 7.8 Hz, 4H, m-C
6
H
3
2
2
2
3
3
[
AuI(IBzMe)]. This was prepared in the same way as for
AuI(IBz)], starting from NaI (270 mg, 1.80 mmol) and [AuCl-
IBzMe)] (305 mg, 0.58 mmol) in MeCN (6 mL). A pale brown solid
2
3
13
1
[
), 1.23 (d, JHH = 6.8 Hz, 12H, CHMe ). C{ H}
2 2
3
(
2
2
CF
1
was obtained. Yield: 316 mg, 95%. mp 159−161 °C. Anal. Calcd for
C H AuIN : C, 26.63; H, 2.44; N, 5.65. Found: C, 26.73; H, 2.47; N,
C H ), 124.5 (m-C H ), 124.0 (CH imidazole), 29.2 (s, CHMe ), 24.5
6 3 6 3 2
11
12
2
6
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Organometallics
Article
1
9
−1
(
(
CHMe ), 24.0 (CHMe ). F NMR: (188.3 MHz, CD Cl ): δ −28.4
6.93. Found: C, 26.87; H, 3.58; N, 6.79. IR (cm ): 1126, 1082, 975
2
2
2
2
+
1
3
s). (+)ESI-MS m/z: 635 ([Au(CF )(IPr)] ), 647.
ν(C−F). H NMR (400.9 MHz, CD Cl ): δ 6.97 (d, 1H, J = 1.6
2
2
2
HH
3
2
[
Au(CF )(SIPr)] (2). Me SiCF (1.04 mmol) and AgF (43 mg, 0.34
Hz, imidazole), 6.94 (d, 1H, J = 1.6 Hz, imidazole), 4.17 (t, J
=
HH
3
3
3
HH
3
mmol) were added to a solution of [AuI(SIPr)] (144 mg, 0.23 mmol)
in EtCN (6 mL). The mixture was stirred for 24 h at room
temperature in the darkness. The resulting dark gray suspension was
brought to dryness under vacuum, and the residue was extracted with
CH Cl2 (20 mL). The extract was filtered through a Celite pad,
concentrated under vacuum to ca. 3 mL, and chromatographed on a
7.2 Hz, 2H, CH ), 3.84 (s, 3H, NMe), 1.86 (quint, J = 7.2 Hz, 2H,
2
H
H
3
3
CH ), 1.38 (sext, J = 7.2 Hz, 2H, CH ), 0.98 (t, J = 7.2 Hz, 2H,
CH2). C{ H} NMR (75.5 MHz, CD Cl ): δ 184.9 (q, J = 14.5
Hz, N CAu), 164.3 (q, J = 345.1 Hz, CF ), 122.4 (CH imidazole),
121.1 (CH imidazole), 51.1 (C1, Bu), 38.2 (NMe), 33.6 (C2, Bu),
2
HH
2
HH
13
1
3
2
2
CF
1
2
CF
3
n
n
2
n
n
19
19.9 (C3, Bu), 13.7 (C4, Bu). F NMR (188.3 MHz, CD Cl ): δ
2 2
n
+
silica gel column using CH Cl /n-hexane (1:1) as eluent. The
collected colorless fraction (R = 0.48) was concentrated to ca. 1
−28.4 (s). (+)ESI-MS m/z: 363 ([Au(CO)(I BuMe)] ), 385
n + n +
2
2
([Au(I BuMe)(CF )] ), 397 ([Au{CF(OMe)}(I BuMe)] ).
f
2
t
36
mL. Addition of n-pentane (10 mL) gave a white solid, which was
washed with n-pentane (3 × 5 mL), and dried under vacuum. Yield: 96
mg, 71%. mp: 218−220 °C. Anal. Calcd for C H F AuN : C, 51.22;
[Au(CF )(CN Bu)] (7). This was prepared in the same way as for
2, starting from Me SiCF (4.20 mmol), AgF (160 mg, 1.26 mmol),
and [AuCl(CN Bu)] (262 mg, 0.83 mmol), in EtCN (10 mL). The
compound was purified by chromatography on a silica gel column
using acetone as eluent (R = 0.70), and the eluate was concentrated
up to ca. 2 mL. After addition of CH Cl (10 mL), the solution was
stirred with MgSO for 5 min and then filtered. The filtrate was
evaporated to ca. 0.5 mL under vacuum, and n-hexane (10 mL) was
added. The resulting white solid was washed with n-hexane (3 × 2
mL) and dried under vacuum. Yield: 205 mg, 71%. Anal. Calcd for
3
3
3
t
28
38
3
2
−1
H, 5.83; N, 4.27. Found: C, 51.00; H, 5.81; N, 4.25. IR (Nujol, cm ):
1
3
1
7
4
=
131, 972 ν(C−F). H NMR (400.9 MHz, CD Cl ): δ 7.47 (t, J
=
2
2
HH
f
3
.6 Hz, 2H, p-C H ), 7.29 (d, J = 7.6 Hz, 4H, m-C H ), 4.04 (s,
6
3
HH
6
3
2
2
3
3
H, imidazole), 3.06 (sept, J = 6.8 Hz, 4H, CHMe ), 1.39 (d, J
HH
2
HH
4
3
6.8 Hz, 12H, CHMe ), 1.34 (d, J = 6.8 Hz, 12H, CHMe ).
C{ H} NMR (75.5 MHz, CD Cl ): δ 209.2 (q, J = 13.3 Hz,
N CAu), 162.7 (q, J = 345.8 Hz, CF ), 147.2 (o-C H ), 134.3 (i-
C H ), 130.2 (p-C H ), 124.8 (m-C H ), 54.3 (CH ), 29.3 (CHMe ),
2
HH
2
1
3
1
3
2
2
CF
1
2
CF
3
6
3
C
H
9
AuF
N: C, 20.64; H, 2.60; N, 4.01. Found: C, 20.95; H, 2.52; N,
6
3
6
3
6
3
2
2
6
3
19
−1
1
2
−
5.1 (CHMe ), 24.2 (CHMe ). F NMR (188.3 MHz, CD Cl ): δ
4.01. IR (Nujol, cm ): 2249 ν(CN), 1136, 993 ν(C−F). H NMR
2 2 2 2
+
13
1
29.1 (s). (+)ESI-MS m/z: 637 ([Au(CF )(SIPr)] ), 649.
Au(CF )(IMes)] (3). This was prepared in the same way as for 2,
starting from Me SiCF (1.30 mmol), AgF (50 mg, 0.39 mmol), and
AuI(IMes)] (144 mg, 0.23 mmol) in EtCN (6 mL). CH Cl /n-
hexane (3:1) was used as eluent (R = 0.74). Yield: 35 mg, 25% (white
solid). mp: 214−216 °C. Anal. Calcd for C H AuF N : C, 46.33; H,
.24; N, 4.91. Found: C, 46.56; H, 4.13; N, 5.16. IR (Nujol, cm ):
132, 1129, 1077, 1018, 978 ν(C−F). H NMR (300.1 MHz,
CD Cl ): δ 7.15 (s, 2H, imidazole), 7.08 (s, 4H, Ar), 2.38 (s, 6 H, p-
Me), 2.13 (s, 12 H, o-Me). C{ H} NMR (100.8 MHz, CD Cl ): δ
86.8 (q, J = 14.0 Hz, N CAu), 162.9 (q, J = 345.2 Hz, CF3),
40.2 (Ar), 135.2 (Ar), 135.0 (Ar), 129.6 (Ar), 123.1 (Ar), 21.3 (p-
Me), 17.9 (o-Me). F NMR (282.4 MHz, CD Cl ): δ −28.5 (s).
+)ESI-MS m/z: 551 ([Au(CF )(IMes)] ), 563.
Au(CF )(IBz)] (4). This was prepared in the same way as for 2,
starting from Me SiCF (1.26 mmol), AgF (53 mg, 0.42 mmol), and
AuI(IBz)] (153 mg, 0.25 mmol) in EtCN (6 mL). Reaction time: 20
h. CH Cl /n-hexane (3:1) was used as eluent (R = 0.60). Yield: 45
mg, 35% (white solid). mp: 138−140 °C. Anal. Calcd for
C H AuF N : C, 42.04; H, 3.14; N, 5.45. Found: C, 41.86; H,
.07; N, 5.40. IR (Nujol, cm ): 1132, 1017, 994, 950 ν(C−F). H
NMR (300.1 MHz, CD Cl ): δ 7.37 (m, 10H, Ph), 6.93 (s, 2H,
(400.9 MHz, CDCl
MHz, CDCl ): δ 155.9 (q, JCF = 340.4 Hz, CF
19.8, CN), 58.9 (s, CMe
CDCl ): δ −29.6 (s, CF
([Au(CF
[Au(CF
starting from Me
3
): δ 1.55 (s, 9 H, CH ). C{ H} NMR (75.5
3
2
1
3
[
3
3
), 145.0 (q, JFC
). F NMR (188.3 MHz,
). (+)ESI-MS m/z: 252, 274, 286, 330
3
=
3
19
), 29.7 (s, CMe
3 3
3
3
[
3
2
2
t
+
+
)( BuNC)] ), 372 (MNa ).
)(CNXy)] (8). This was prepared in the same way as for 7,
SiCF (1.60 mmol), AgF (62 mg, 0.49 mmol), and
f
2
22
24
3
2
3
−1
4
1
3
3
1
[AuCl(CNXy)] (114 mg, 0.31 mmol) in EtCN (5 mL). Reaction
time: 16 h. Yield: 53 mg, 43% (white solid). mp: 148−150 °C. Anal.
Calcd for C10H AuF N: C, 30.24; H, 2.28; N, 3.53. Found: C, 30.04;
2
2
13
1
2
2
9 3
3
1
−1
1
1
H, 2.22; N, 3.66. IR (Nujol, cm ): 2215 ν(CN), 1130, 995 ν(C−
CF
2
CF
1
3
F). H NMR (300.1 MHz, CDCl
): δ 7.34 (t, JHH = 7.2 Hz, 1H, p-
), 2.43 (s, 6H, Me).
): δ 157.8 (m, CN), 156.0 (q,
1J = 340.6 Hz, CF ), 136.4 (o-C H ), 131.3 (p-C H ), 128.5 (m-
3
19
3
C
H
), 7.17 (d, JHH = 7.5 Hz, 2H, m-C
H
2
2
6
3
6
3
+
13
1
(
C{ H} NMR (100.8 MHz, CDCl
3
2
[
3
CF
3
6
3
6
19
3
1
3
3
C H ), 123.8 (t, J = 13.5 Hz, i-C H ), 14.1 (Me). F NMR (188.3
6 3 CN 6 3
[
MHz, CDCl ): δ −29.5 (s, CF ). (+)ESI-MS m/z: 356 ([Au(CO)-
+ +
3
3
2
2
f
(XyNC)] ), 378 ([Au(CF )(XyNC)] ), 390 ([Au{CF(OMe)}-
2
+
+
(XyNC)] ), 402 ([Au{C(OMe) }(XyNC)] ). Spectroscopic data of
[Au(CNXy) ][Au(CF ) ] in the reaction crude: H NMR (400.9
2
1
18
16
3
2
2
3 2
−1
1
3
3
MHz, CDCl ): δ 7.31 (t, J = 7.6 Hz, 1H, p-C H ), 7.15 (d, 2H, m-
3 HH 6 3
1
9
2
2
C H ), 2.47 (s, 6H, Me). F NMR (188.3 MHz, CDCl ): δ −26.9.
6
3
3
13
1
+
imidazole), 5.39 (s, 4H, CH ). C{ H} NMR (75.5 MHz, CD Cl ): δ
85.2 (q, J = 14.4 Hz, N CAu), 163.8 (q, J = 344.8 Hz, CF3),
(+)ESI-MS m/z: 459 ([Au(CNXy) ] ); (−)ESI-MS m/z: 235
2
2
2
2
3
1
−
−
−
1
1
([AuF ] ), 285 ([AuF(CF )] ), 335 ([Au(CF ) ] ), 497.
CF
2
CF
2
3
3 2
2
9,30,34
35.9 (Ph), 129.4 (Ph), 129.0 (Ph), 128.3 (Ph), 121.7 (CH
[Au(CF )(PMe )] (9).
Me SiCF (1.60 mmol) and AgF (60
mg, 0.47 mmol) were added to a solution of [AuCl(PMe )] (119 mg,
0.31 mmol) in EtCN (6 mL). The mixture was stirred for 24 h at room
temperature in the darkness. The resulting dark gray suspension was
brought to dryness under vacuum. The mixture was extracted with
CH Cl (20 mL), and the extract was filtered through a Celite pad,
concentrated under vacuum to ca. 3 mL, and chromatographed. The
crude product was a 5:1 mixture of 9 and [Au(PMe ) ][Au(CF ) ].
Pure 9 was obtained by column chromatography on a silica gel column
using acetone/n-hexane (1:2) as eluent (R = 0.43). The eluate was
concentrated up to ca. 2 mL. After addition of CH Cl (10 mL), the
solution was stirred with MgSO for 5 min and then evaporated to ca.
0.5 mL under vacuum. Addition of n-hexane (10 mL) precipitated a
white solid, which was filtered, washed with n-hexane (3 × 2 mL), and
dried under vacuum. Yield: 58 mg, 55%. H NMR (200.1 MHz,
3
3
3 3
1
9
imidazole), 55.2 (CH2). F NMR (282.4 MHz, CD Cl ): δ −28.5
2
2
3
+
(
(
s). (+)ESI-MS m/z: 473 ([Au(CO)(IBz)] ), 495 ([Au(CF )-
2
+
+
IBz)] ), 507 ([Au{CF(OMe)}(IBz)] ).
Au(CF )(IBzMe)] (5). This was prepared in the same way as for 4,
starting from Me SiCF (1.08 mmol), AgF (45 mg, 0.35 mmol), and
AuI(IBzMe)] (106 mg, 0.21 mmol) in EtCN (6 mL). Yield: 29 mg,
1% (white solid). mp: 130−132 °C. Anal. Calcd for C H F AuN :
C, 32.89; H, 2.76; N, 6.39. Found: C, 32.56; H, 2.67; N, 6.27. IR
Nujol, cm ): 1134, 1119, 1018, and 965 ν(C−F). H NMR (300.1
MHz, CD Cl ): δ 7.36 (m, 5H, Ph), 6.95 (d, 1H, J = 1.5 Hz,
[
3
3
3
2
2
[
3
12
12
3
2
3
2
3 2
−1
1
(
f
3
2
2
HH
2
2
3
imidazole), 6.93 (d, 1H, J = 1.5 Hz, imidazole), 5.36 (s, 2H, CH2),
HH
4
.86 (s, 3H, Me). 13C{ H} NMR (75.5 MHz, CD Cl ): δ 185.3 (q,
1
3
2
2
3
1
JCF = 14.6 Hz, N CAu), 164.1 (q, J = 344.5 Hz, CF ), 136.1 (Ph),
29.3 (Ph), 128.9 (Ph), 128.3 (Ph), 122.9 (CH imidazole), 121.1 (CH
imidazole), 54.9 (CH ), 38.2 (Me). F NMR (282.4 MHz, CD Cl ):
δ −28.6 (s). (+)ESI-MS m/z: 397 ([Au(CO)(IBzMe)] ), 419
[Au(CF )(IBzMe)] ), 431([Au{CF(OMe)}(IBzMe)] ).
Au(CF )(I BuMe)] (6). This was prepared in the same way as for 2,
starting from Me SiCF (1.77 mmol), AgF (69 mg, 0.54 mmol), and
AuI(I BuMe)] (160 mg, 0.35 mmol) in EtCN (6 mL). CH Cl /n-
hexane (3:1) was used as eluent (R = 0.70). Yield: 71 mg, 51%
colorless oil). Anal. Calcd for C H AuF N : C, 26.74; H, 3.49, N,
2
CF
3
1
1
19
2
19
CDCl ): δ 1.49 (d, 9 H, J = 10.2 Hz). F NMR (188.3 MHz,
2
2
2
3 HP
+
3
31
1
CDCl ): δ −30.5 (d, J = 49.1 Hz, CF ). P{ H} NMR (162.3
3
FP
3
+
+
3
(
MHz, CDCl ): δ −0.30 (q, J = 49.0 Hz). Spectroscopic data of
2
3
PF
n
1
[
[Au(PMe ) ][Au(CF ) ] in the reaction crude: H NMR (300.1 MHz,
3
3 2 3 2
19
CDCl ): δ 1.65 (vt, 18 H, N = 8.1 Hz). F NMR (282.4 MHz,
3
CDCl ): δ −26.1 (s). P{ H} NMR (121.5 MHz, CDCl ): δ 3.9 (s).
(+)ESI-MS m/z: 349 ([Au(PMe ) ] ); (−)ESI-MS m/z: 335
3
3
n
31
1
[
2
2
3
3
+
f
3 2
−
(
([Au(CF ) ] ).
3 2
9
14
3
2
6
365
dx.doi.org/10.1021/om500669j | Organometallics 2014, 33, 6358−6368

Organometallics
Article
3
0,34
−
−
[
Au(CF )(PPh )] (10).
This was prepared in the same way as
p-F of [Au(C F ) ] ), −164.8 (m, m-F of [Au(CF )(C F )] and
3
3
6
5
2
3
6 5
−
−
−
for 9, starting from Me SiCF (1.14 mmol), AgF (43 mg, 0.34 mmol),
and [AuCl(PPh )] (111 mg, 0.22 mmol) in EtCN (7 mL). R = 0.49.
Yield: 70 mg, 59% (white solid). H NMR (400.1 MHz, CDCl ): δ
[Au(C F ) ] ). The signals of [Ag(CF ) ] and [Au(CF ) ] were
3
3
6
5
2
3
2
3 2
3
5,71
assigned by comparison with reported values.
The signals of
F ) ] were assigned by comparison with those of a sample of
6 5 2
3
f
1
−
[Au(C
PPN[Au(C
(81.0 MHz, CDCl
3
19
3
86 31
1
7
=
=
.49 (m, 15 H, Ph). F NMR (188.3 MHz, CDCl ): δ −29.9 (d, J
6
F
5
)
2
] prepared by a reported method.
): δ 21.6 (s, PPN). (−)ESI-MS (MeCN) m/z: 242
([AuF(CN)] ), 285 ([AuF(CF
P{ H} NMR
3
FP
45.0 Hz, CF3). 31P{ H} NMR (162.29 MHz, CDCl ): δ 38.7 (q, J
1
3
3
PF
3
−
−
−
44.8 Hz).
[
3
F
)] ), 335 ([Au(CF
5
)
3
2
] ), 383 ([AuF-
−
−
−
Au(CF ){P(p-Tol) }] (11). This was prepared in the same way as
for 9, starting from Me SiCF (1.40 mmol), AgF (53 mg, 0.42 mmol),
and [AuCl{P(p-Tol) }] (143 mg, 0.27 mmol) in EtCN (6 mL).
Reaction time = 20 h. R = 0.58. Yield: 119 mg, 78% (white solid). mp:
(C
([Au(C
[Au(CF
mmol) in NHEt
resulting colorless solution was evaporated to dryness under vacuum,
and the residue was extracted with CH Cl (10 mL). After filtration
through Mg SO , the extract was concentrated under vacuum to ca.
6
F
5
)] ), 390 ([Au(CN)(C
6
)] ), 433 ([Au(CF
3
)(C
6
F
5
)] ), 531
3
3
−
F
)
5
] ).
){(C(NH Bu)(NEt
(2 mL) was stirred for 5 h at room temperature. The
3
3
6
2
t
)}] (14). A solution of 7 (46 mg, 0.13
2
3
3
f
2
1
93−195 °C. Anal. Calcd for C H AuF P: C, 46.33; H, 3.71. Found:
22
21
3
−1 1
C, 46.03; H, 3.54. IR (Nujol, cm ): 1127, 994 ν(C−F). H NMR
2
2
(
400.1 MHz, CDCl ): δ 7.36 (m, 6 H, C H ), 7.25 (m, 6H, C H ),
2
4
3
6
4
6
4
1
3
1
2
.38 (s, 9 H, CH ). C{ H} NMR (100.81 MHz, CDCl ): 166.3 (dq,
0.5 mL. Addition of n-hexane precipitated a white solid, which was
filtered, washed with n-hexane (2 × 2 mL), and dried under vacuum.
The solid was stored at −32 °C because it slowly decomposes at room
temperature. Yield: 28 mg, 50%. mp: 51−53 °C (dec). Anal. Calcd for
3
3
1
2
JCF = 353.7 Hz, J = 180.4 Hz, CF ), 142.2 (s, p-C H ), 134.1 (d,
CP
3
6
4
2
3
JCP = 13.4 Hz, o-C H ), 130.0 (d, J = 11.1 Hz, m-C H ), 126.1 (d,
6
4
CP
19
6
4
1J = 56.9 Hz, i-C H ), 21.5 (s, Me). F NMR (188.3 MHz, CDCl ):
CP
6
4
3
3
31
1
C H20AuF N : C, 28.45; H, 4.77; N, 6.63. Found: C, 28.24; H, 4.57;
10 3 2
δ −29.9 (d, JFP = 44.8 Hz, CF ). P{ H} NMR (162.3 MHz,
CDCl ): δ 36.8 (q, J = 44.8 Hz). (+)ESI-MS m/z: 501 ([Au{(P(p-
Tol) }] ), 551 ([Au(CF ){(P(p-Tol) }] ), 563 ([Au{CF(OMe)}{(P-
3
−1
3
N, 6.68. IR (Nujol, cm ): 3377 ν(N−H), 1539 ν(CN), 1120, 964
3
PF
1
+
+
ν(C−F). H NMR (300.1 MHz, CDCl
3
): δ 5.80 (br s, 1H, NH), 3.93
3
2
3
3
3
+
(q, JHH = 7.1 Hz, 2H, CH
2
Me), 3.22 (q, JHH = 7.3 Hz, 2H, CH
2
Me),
(
p-Tol) }] ).
[
t
3
3
3
1
.60 (s, 9H, Bu), 1.27 (t, J = 7.1 Hz, 3H, CH Me), 1.15 (t, J
=
HH
2
HH
Au(CF ){P(OMe) }] (12). This was prepared in the same way as for
13
1
3
3
7
.1 Hz, 3H, CH Me). C{ H} NMR (75.5 MHz, CDCl ): δ 204.1 (q,
2
3
7
[
, starting from Me SiCF (2.20 mmol), AgF (88 mg, 0.69 mmol), and
3
1
3
3
JCF = 12.8 Hz, N CAu), 162.2 (q, J = 346.5 Hz, CF ), 54.1
2
CF
3
AuCl{P(OMe) }] (155 mg, 0.43 mmol) in EtCN (6 mL). Reaction
time: 20 h. CH Cl /n-hexane (1:1) was used as eluent (R = 0.55).
Yield: 109 mg, 64% (white solid; it becomes purple at room
3
(
1
CH Me), 54.0 (CMe ), 40.1 (CH Me), 31.9 (CMe ), 14.8 (CH Me),
2 3 2 3 2
2
2
f
19
1.8 (CH Me). F NMR (282.4 MHz, CDCl ): δ −27.5 (s, CF ).
t +
2
3
3
(
(
+)ESI-MS m/z: 381, 403 ([Au{C(NH Bu)(NEt )}(CF )] ), 415
2 2
temperature and was stored at −32 °C to avoid decomposition). mp:
t
+
[Au{C(NH Bu)(NEt )}(CF )] ).
2
2
5
2−54 °C. Anal. Calcd for C H AuF O P: C, 12.32; H, 2.33. Found:
4
9
3
3
−
1
1
[Au(CF
3
){(C(NHXy)(NEt )}] (15). This was prepared in the same
2
C, 12.29; H, 2.18. IR (Nujol, cm ): 1137, 1018, 968 ν(C−F). H
2
way as for 14, starting from 8 (50 mg, 0.13 mmol). The white solid
was stored at −32 °C because it slowly decomposes to metallic gold at
room temperature. Yield: 33 mg, 56%. mp: 119−121 °C (dec). Anal.
Calcd for C H AuF N : C, 35.76; H, 4.29; N, 5.96. Found: C, 35.66;
NMR (300.1 MHz, CDCl ): δ 3.77 (d, 9H, J = 12.9 Hz, Me).
3
PH
1
3
1
1
C{ H} NMR (100.81 MHz, CDCl ): δ 166.5 (dq, J = 350.9 Hz,
3
19
CF
2J = 262.7 Hz, CF ), 52.8 (s, Me). F NMR (282.4 MHz, CDCl ): δ
CP
3
3
14
20
3
2
3
31
1
−
31.4 (d, J = 61.8 Hz, CF3). P{ H} NMR (121.5 MHz, CDCl ):
δ 145.0 (q, J = 61.8 Hz). (+)ESI-MS m/z: 321 ([Au{P(OMe) }] ),
−1
FP
3
H, 4.16; N, 5.99. IR (Nujol, cm ): 3363, 3330 ν(N−H), 1543 ν(C
3
+
1
PF
3
N), 1126, 975 ν(C−F). H NMR (300.1 MHz, CDCl ): δ 7.17−7.08
3
+
+
3
(
49 ([Au(CO){P(OMe) }] ) 371 ([Au(CF ){P(OMe) }] ), 383
3
3
2
3
(m, 3H, Ar), 6.80 (br s, 1H, NH), 3.95 (q, J = 7.2 Hz, 2H, CH ),
HH
2
+
[Au{CF(OMe)}{P(OMe) }] ).
Au (CF ) (μ-dppe)] (13). This was prepared in the same way as
for 7, starting from Me SiCF (0.82 mmol), AgF (53 mg, 0.42 mmol),
and [Au Cl (μ-dppe)] (100 mg, 0.12 mmol), in a 1:1 mixture of
EtCN/CH Cl (10 mL). Reaction time: 18 h. Acetone/n-hexane (1:2)
was used as eluent (R = 0.31). Yield: 57 mg, 53% (white solid). mp:
3
3
3
3.44 (q, J = 7.2 Hz, 2H, CH ), 2.23 (s, 6H, Me-Ar), 1.33 (t, J
=
HH
2
HH
[
3
13
1
2
3 2
7.1 Hz, 3H, CH Me), 1.32 (t, J = 7.3 Hz, 3H, CH Me). C{ H}
2 HH 2
3
3
3
NMR (75.5 MHz, CDCl ): δ 205.9 (q, J = 13.1 Hz, N CAu), 161.9
3 CF 2
1
2
2
(q, J = 346.8 Hz, CF ), 136.7 (s, o-C H ), 136.2 (s, p-C H ), 128.5
CF 3 6 3 6 3
2
2
(s, m-C H ), 52.6 (CH ), 40.8 (CH ), 19.0 (Me-Ar), 15.0 (CH Me),
6 3 2 2 2
19
f
12.4 (CH Me); the signal of C−N was not observed. F NMR (282.4
2
2
40 °C (d). Anal. Calcd for C H Au F P : C, 36.15; H, 2.60. Found:
28 24 2 6 2
1 1
MHz, CDCl ): δ −28.0 (s, CF ). (+)ESI-MS m/z: 451 ([Au{C-
3
3
−
+
C, 35.83; H, 2.62. IR (Nujol, cm ): 1125, 967 ν(C−F). H NMR
(
NHXy)(NEt )}(CF )] ), 463 ([Au{CF(OMe)}{C(NHXy)-
2 2
+
(
(
1
400.9 MHz, CDCl ): δ 7.63 (m, 8 H, Ph), 7.50 (m, 12 H, Ph), 2.61
3
(NEt )}] ).
2
2
13
1
d, J = 1.6 Hz, 4 H, CH ). C{ H} NMR (75.5 MHz, CD Cl ): δ
33.7 (d, J = 13.7 Hz, o-Ph), 132.7 (s, p-Ph), 130.0 (d, J = 9.1
PH
2
2
2
trans-[AuCl (CF )(IPr)] (16). A solution of PhICl (16 mg, 0.058
2 3 2
2
2
CP
CP
mmol) in CH Cl (3 mL) was added to a solution of [Au(CF )(IPr)]
2
2
3
1
1
Hz, m-Ph), 128.7 (d, J = 52.4 Hz, i-Ph), 23.7 (d, J = 35.1 Hz,
(38 mg, 0.058 mmol) in CH Cl (3 mL) at −90 °C. The reaction
CP
CP
2
2
19
CH ), the signal of CF was not observed. F NMR (188.3 MHz,
mixture was slowly warmed to room temperature over 2 h with
stirring. The resulting pale yellow solution was evaporated to dryness
under vacuum, and the residue was chromatographed on a silica gel
column using CH Cl /n-hexane (2:1) as eluent. The collected
2
3
31
1
CDCl ): δ −30.2 (vd, J = 45.2 Hz, CF ). P{ H} NMR (162.3 MHz,
3
3
+
CDCl ): δ 35.9 (m). (+)ESI-MS m/z: 861 ([Au (CF )(dppe)] ), 911
3
2
3
+
+
(
[Au (CF )(CF )(dppe)] ), 923 ([Au (CF ){CF(OMe)}(dppe)] ).
2 3 2 2 3
2
2
Reaction of PPN[AuCl(C F )] with AgF and Me SiCF .
Me SiCF (0.60 mmol) and AgF (24 mg, 0.19 mmol) were added
to a solution of PPN[AuCl(C F )] (110 mg, 0.12 mmol) in EtCN (6
mL). The mixture was stirred for 27 h at room temperature and
brought to dryness under vacuum. The residue was extracted with
CH Cl (15 mL), and the extract was filtered through a Celite pad and
concentrated to ca. 1 mL under vacuum. Addition of n-hexane
precipitated an oily residue, which was stirred at 0 °C until it became a
white solid (83 mg). This solid contains a mixture of complexes
colorless fraction (R = 0.76) was evaporated to dryness, and the
6
5
3
3
f
3
3
residue was washed with n-hexane (5 mL), to give a white solid, which
was dried under vacuum. Yield: 32 mg, 75%. mp: 265 °C (d). Anal.
Calcd for C H Cl F AuN : C, 46.36; H, 5.00; N, 3.86. Found: C,
6
5
28
36
2
3
2
−1
46.20; H, 5.00; N, 3.93. IR (Nujol, cm ): 1121, 1081, 1057, 1019
1
3
2
2
ν(C−F). H NMR (400.9 MHz, CD Cl ): δ 7.58 (t, J = 8.0 Hz,
2
2
HH
3
2H, p-C H ), 7.38 (d, J = 8.0 Hz, 4H, m-C H ), 7.31 (s, 2H,
6 3 HH 6 3
3
3
imidazole), 2.82 (sept, J = 6.8 Hz, 4 H, CHMe ), 1.37 (d, J =
HH
6.8 Hz, 12 H, CHMe ), 1.13 (d, J
C{ H} NMR (100.8 MHz, CD Cl ): δ 165.5 (q, J = 29.5 Hz,
HH
2
3
= 6.8 Hz, 12H, CHMe ).
2
HH
2
13
1
3
PPN[Au(CF ) (C F ) ] (x = 0, 1, 2) and PPN[Ag(CF ) ]. Single
3
x
6
5
2−x
3
2
2 2 CF
crystals of PPN[Au(CF )(C F )] were obtained by liquid diffusion
N CAu), 146.4 (o-C H ), 133.2 (i-C H ), 131.5 (p-C H ), 126.1 (CH
2 6 3 6 3 6 3
3
6
5
1
1
between a CH Cl solution of the isolated solid and n-hexane. H
imidazole), 125.3 (q, J = 358.5 Hz, CF ), 124.8 (m-C H ), 29.2
2
2
FC 3 6 3
19
19
NMR (200.1 MHz, CDCl ): δ 7.66−7.41 (m, 30 H, PPN). F NMR
(CHMe ), 26.5 (CHMe ), 22.9 (CHMe ). F NMR (188.3 MHz,
2 2 2
3
2
+
(
188.3 MHz, CDCl ): δ −25.9 (two doublets, J = 100.2 and 87.8
CD Cl ): −32.4 (s). (+)ESI-MS m/z: 602 ([Au(NH )(IPr)] ), 613
3
AgF
2
2
3
−
−
+
+
Hz, [Ag(CF ) ] ), −26.7 (s, [Au(CF )(C F )] ), −28.6 (s, [Au-
([Au(CO)(IPr)] ), 742 ([M + NH ] ).
3
2
3
6
5
4
−
−
(
[
CF ) ] ), −115.6 (m, o-F of [Au(C F ) ] ), −116.0 (m, o-F of
trans-[AuBr (CF )(IPr)] (17). A solution of Br in CH Cl (35 μL,
2 3 2 2 2
3
2
6
5
2
−
−
Au(CF )(C F )] ), −162.9 (t, p-F of [Au(CF )(C F )] ), −163.5 (t,
2.0 M, 0.07 mmol)) was added to a solution of [Au(CF )(IPr)] (30
3
6
5
3
6
5
3
6
366
dx.doi.org/10.1021/om500669j | Organometallics 2014, 33, 6358−6368

Organometallics
Article
mg, 0.05 mmol) in CH Cl (4 mL) at −90 °C. The reaction mixture
were obtained by liquid diffusion between a CH Cl solution and n-
2
2
2
2
was slowly warmed to room temperature over 2 h with stirring. The
orange solution was evaporated to dryness, and the resulting yellow
solid obtained was washed with n-hexane (5 mL) and dried under
vacuum. Yield: 33 mg, 88%. mp: 268 °C (d). Anal. Calcd for
C H Br F AuN : C, 41.30; H, 4.46; N, 3.44. Found: C, 41.46; H,
hexane and measured on a Bruker D8 QUEST machine at 100 K. Data
were collected using a high brilliance microfocus sealed tube with
Mo−Kα radiation (0.71073 Å) in ω-scan. The structures were solved
2
by direct methods. All were refined anisotropically on F . The
hydrogen in the NH units of 16 was refined freely with DFIX. The
ordered methyl groups were refined using rigid groups and the other
hydrogens were refined using a riding mode. Special features: In
complexes 3, PPN[Au(CF )(C F )]·(CH Cl ) , and 17, the CF
3
2
8
36
2
3
2
−
1
1
4
.36; N, 3.65. IR (Nujol, cm ): 1109, 1075, 1054, 1019 ν(C−F). H
NMR (400.9 MHz, CD Cl ): δ 7.58 (t, J = 7.8 Hz, 2H, p-C H ),
.37 (d, J = 7.8 Hz, 4H, m-C H ), 7.33 (s, 2H, imidazole), 2.95
sept, J = 6.6 Hz, 4H, CHMe ), 1.40 (d, J = 6.9 Hz, 12H,
CHMe ), 1.12 (d, J = 6.9 Hz, 12H, CHMe ). C{ H} NMR (75.5
MHz, CD Cl ): δ 163.0 (q, J = 28.5 Hz, N CAu), 146.4 (o-C H ),
3
2
2
HH
6
3
3
7
(
HH 6 3
3
6
5
2
2
0.5
3
3
group is disordered over two positions. The relative occupances of
each position are 53:47, 57:43, and 55:45, respectively. In 7, two
HH
2
HH
13
3
1
2
HH
2
3
fluorine atoms of the CF group are disordered over two positions
2
2
CF
2
6
3
3
1
33.6 (i-C H ), 131.5 (p-C H ), 126.4 (CH imidazole), 124.9 (m-
with a relative occupance of 50:50. In 14·(CH Cl ) , the CH Cl
6
3
6
3
2
2
0.5
2
2
1
C H ), 123.9 (q, JFC = 356.6 Hz, CF ), 29.3 (CHMe ), 26.6
molecule is disordered over an inversion center and its hydrogen
6
3
3
2
19
(
(
(
CHMe ), 23.2 (CHMe ). F NMR (188.3 MHz, CD Cl ): −24.5 (s).
atoms were not included in the refinement. In compound 16, the
2
2
2
2
+
3
+)ESI-MS (condiciones) m/z: 602 ([Au(NH )(IPr)] ), 613 ([Au-
highest residual electron density is a peak of 5.44 e/Å at 0.92 Å from
3
+
+
CO)(IPr)] ), 832 ([M + NH ] ).
C33. Different crystals were measured, and all of them gave the same
peak at the same position, which suggest that this peak could be
originated by a small amount of twinning that could not be solved.
4
Reaction of 1 with I . A solution of 1 (8 mg, 0.01 mmol) in
2
CD Cl (0.5 mL) in an NMR tube was cooled to −90 °C. Then, a
solution of I (0.04 mmol) in CD Cl (0.15 mL) was added slowly to
2
2
2
2
2
avoid a temperature increase. After 5 min, the tube was inserted into
ASSOCIATED CONTENT
Supporting Information
1
19
■
the precooled (−80 °C) NMR probe. The H and F NMR spectra
*
S
showed a 1.7:0.9:1:1 mixture of 1, [AuI (CF )(IPr)], ICF , and
2
3
3
Additional spectroscopic data, tables with relevant crystallo-
graphic data, and CIF files are supplied as Supporting
Information. This material is available free of charge via the
Internet at http://pubs.acs.org.
[
AuI(IPr)]. The temperature was gradually increased, and the
1
19
composition of the reaction mixture was monitored by H and
NMR spectroscopy. After 2 h at room temperature, only [AuI(IPr)]
and ICF were observed. NMR data of the reaction products: (a)
F
3
1
trans-[AuI (CF )(IPr)], H NMR (300.1 MHz, CD Cl ): δ 7.56 (t,
2
3
2
2
3
3
JHH = 7.6 Hz, 2H, p-C H ), 7.38 (s, 2H, imidazole), 7.37 (d, J
=
6
3
HH
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jgr@um.es (J.G.-R.).
3
■
8
.1 Hz, 4H, m-C H ), 3.13 (sept, J = 6.7 Hz, 4H, CHMe ), 1.43 (d,
6 3 HH 2
3
3
J
= 6.6 Hz, 12H, CHMe ), 1.13 (d, J = 6.8 Hz, 12H, CHMe ).
2 HH 2
HH
1
9
51
1
F NMR (282.4 MHz, CD Cl ): −9.5 (s). (b) [AuI(IPr)],
H
2
2
3
*E-mail: jvs1@um.es. http://www.um.es/gqo/ (J.V.).
Notes
The authors declare no competing financial interest.
NMR (300.1 MHz, CD Cl ): δ 7.58 (t, J = 7.8 Hz, 2H, p-C H ),
7
2
2
HH
6
3
3
.35 (d, J = 7.8 Hz, 4H, m-C H ), 7.25 (s, 2H, imidazole), 2.56
sept, J = 6.9 Hz, 4H, CHMe ), 1.33 (d, J = 6.9 Hz, 12H,
HH
6
3
3
3
(
HH 2 HH
3
CHMe ), 1.23 (d, J = 6.9 Hz, 12H, CHMe ). ICF (see below).
2
HH
2
3
(
SP-4-2)-[Au(Cl)(I)(CF )(IPr)] (18). A solution of ICl in CH Cl
3
2
2
ACKNOWLEDGMENTS
We thank the Spanish Ministerio de Economı
titividad (grant CTQ2011-24016 with FEDER support) and
■
(
[
°
67 μL, 0.048 mmol of ICl) was added to a solution of
Au(CF )(IPr)] (31 mg, 0.047 mmol) in CH Cl (3 mL) at −70
C. After 2 min, a layer of cold n-hexane (15 mL) was added carefully
over the CH Cl solution. Orange crystals formed after storing the
two-layer solution at −32 °C for 3 days. The solvents were removed,
and the crystals were dried under vacuum. Yield: 24 mg, 62%. mp: 183
a
́
y Compe-
3
2
2
2
2
Fundacion
support.
́
́
Seneca (grant 04539/GERM/06) for financial
°
C (d). Anal. Calcd for C H ClF IAuN : C, 41.16; H, 4.44; N, 3.43.
Found: C, 41.20; H, 4.32; N, 3.49. IR (Nujol, cm ): 1121, 1106,
28 36 3 2
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1
3
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4
Thermal and Photochemical Reactions of Complexes 16, 17,
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