Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes

Article abstract of DOI:10.1002/chem.201903058

The study of perfluoroalkyl metal complexes is key to understand and improve metal-promoted perfluoroalkylation reactions. Herein, we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between Au^I organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuR_F (L=PPh₃ or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; R_F=n-C₄F₉, n-C₆F₁₃, i-C₃F₇, c-C₆F₁₁) and [Au(R_F)(Ar)I(PPh₃)] (Ar=2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes R_FC≡CR were formed by reaction of Ph₃PAuC≡CR (R=Ph, nHex) with IR_F (R_F=n-C₄F₉, i-C₃F₇). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. Au^III complexes [Au(n-C₄F₉)(X)(Y)L] (X=Y=Cl, Br, I, Me; X=Me, Y=I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied.

Full text of DOI:10.1002/chem.201903058

A Journal of
Accepted Article
Title: Photoinitiated Reactions of Haloperfluorocarbons with Gold(I)
Organometallic Complexes. Perfluoroalkyl Gold(I) and Gold(III)
Complexes
Authors: Alejandro Portugués, Inmaculada López-García, Javier
Jiménez-Bernad, Delia Bautista, and Juan Gil-Rubio
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201903058
Link to VoR: http://dx.doi.org/10.1002/chem.201903058
Supported by

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
Photoinitiated Reactions of Haloperfluorocarbons with Gold(I)
Organometallic Complexes. Perfluoroalkyl Gold(I) and Gold(III)
Complexes
[
a]
[a]
[a]
[b]
Alejandro Portugués, Inmaculada López-García, Javier Jiménez-Bernad, Delia Bautista, and
[
a]
Juan Gil-Rubio*
Abstract: The study of perfluoroalkyl metal complexes is key to
understanding and improving metal-promoted perfluoroalkylation
reactions. Herein we report the synthesis of the first gold complexes
with primary or secondary perfluoroalkyl ligands by photoinitiated
type of compounds arise from their applications in the
[
3i, 11]
perfluoroalkylation of organic substrates,
in the synthesis of
[
12]
highly fluorinated small molecules and fluoropolymers,
or in
Likewise, whereas a relatively large
[
13]
C–F bond activation.
number of trifluoromethyl Au complexes have been reported,
[
9b,
reactions
iodoperfluoroalkanes. Complexes of the types LAuR
N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene;
i-C c-C and [Au(R )(Ar)I(PPh
between
Au(I)
organometallic
complexes
and
9
d, e, 14]
F
(L = PPh
3
or
no complexes containing heavier perfluoroalkyl groups
R
F
=
n-C
4
F
9
,
n-
bonded to Au have been isolated or fully characterized. To fill
this gap and to increase the knowledge on the chemistry of
metal perfluoroalkyls, we started a project aimed at synthesizing
and studying the reactivity of Au(I) and Au(III) complexes
containing perfluoroalkyl ligands different than trifluoromethyl.
C
6
F
13
,
3
F
7
,
6
F
11
)
F
3
)] (Ar
=
2,4,6-
trimethylphenyl) have been isolated and characterized. Alkynes
C≡CR were formed by reaction of Ph PAuC≡CR (R = Ph, nHex)
with IR (R = n-C , i-C ). Evidences of a photoinitiated radical
mechanism for these reactions have been obtained. Au(III)
complexes [Au(n-C )(X)(Y)L] (X = Y = Cl, Br, I, Me; X = Me, Y = I)
R
F
3
F
F
4
F
9
3 7
F
Perfluoroalkyl iodides (IR
F
) were chosen as perfluoroalkyl
4
F
9
sources because of their commercial availability and reactivity
[
10b, 15]
have been prepared or in situ generated, and their thermal or
photochemical decomposition reactions have been studied.
against metal complexes in low oxidation states.
Pioneering studies by Puddephatt and co-workers showed that
complexes LAuMe react with ICF to give Au(III) and/or Au(I)
3
[
16]
trifluoromethyl complexes depending on L (Scheme 1, A). To
explain the observed reaction products, they proposed that the
Introduction
initially
formed
[Au(CF
3
)(Me)I(L)]
undergoes
reductive
elimination of MeI or ligand exchange reactions to give the final
products. Evidences for a radical mechanism were obtained, but
the photochemical character of the reaction was not investigated.
[
1]
The industrial demand for fluorinated organic compounds has
boosted intensive research on metal-mediated or -catalysed
[
2]
perfluoroalkylation reactions during the last two decades. In
many of these reactions, reductive elimination is often proposed
as the final step, in which perfluoroalkylated organic products
L
Au CF3 + MeI
[
2o, 3]
are released from the metal coordination sphere.
However, it
Me
is generally accepted that perfluoroalkyl complexes present a
ICF3
[
4]
L
Au Me
L
Au CF3
I
A
pronounced inertness against reductive elimination
and,
consequently, very limited number of stoichiometric C–
a
L = PMe Ph
LAuMe
x
3-x
Me
perfluoroalkyl bond-forming reductive eliminations have been
observed. Reported examples comprise aryl-trifluoromethyl-
(x = 0–3)
L
Au CF3
Me
+
L
Au
I
[
3c, 3j, 5]
Pd(II) complexes containing purposely designed ligands,
or alkyl- and aryl-trifluoromethyl complexes of metals in high
[
6]
[7]
[3b, 8]
Ar
oxidation states, such as Pd(IV),
Ni(IV), Cu(III)
or
ICF3
[
9]
L
Au Ar
L
Au CF3
I
B
C
D
Au(III).
hν (313 nm)
In contrast to the thoroughly studied trifluoromethyl
complexes, metal complexes containing larger perfluoroalkyl
L = PPh3,
PCy3
[
3i, 10]
ligands have received much less attention.
Interest for this
Me
MeI
-
3
0 ºC
F
3
C
Au CF
I
3
[
a]
A. Portugués, I. López-García, J. Jiménez-Bernad, Dr. J. Gil-Rubio
Departamento de Química Inorgánica, Facultad de Química
Universidad de Murcia
-
F3C Au CF3
Campus de Espinardo. 30100 Murcia (Spain)
E-mail: jgr@um.es
CF3
-
[
b]
Dr. D. Bautista
ICF3
F3C Au CF3
I
ACTI. Universidad de Murcia
dark (4 days) or
sunlight (1 min)
Campus de Espinardo. 30100 Murcia (Spain)
Supporting information for this article is given via a link at the end of
the document.
3
Scheme 1. Reported oxidative addition reactions of ICF to Au(I) complexes.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
Glockling obtained Ph
PAu(CH(SiMe ) and ICF
the reactions of complexes of the type R
and ICF under UV irradiation (Scheme 1, B). These reactions
gave Au(III) complexes of the type [Au(CF )(Ar)I(PR )] by a
3
PAuCF
3
in the reaction between
Toste and co-workers studied
PAuAr (R = Ph, Cy)
intermediates were observed by NMR spectroscopy in any of
these reactions.
[
17]
Ph
3
3
)
2
3
.
3
Au(I) perfluoroalkyl complexes 1–7 (Scheme 2) were
isolated in 51–94% yield after irradiating a solution of the
3
3
3
corresponding LAuMe and IR
The only significant by-product detected was IPrAuI, which was
formed in the reaction of IPrAuMe with c-C 11I in a 10% yield
F 2 2
in CH Cl with the 402 nm LED.
radical chain mechanism. Mechanistic studies suggested that
the reaction is initiated by one electron transfer from the starting
6
F
[
9c]
Au(I) complex to a photoexcited ICF
Au(III) trifluoromethyl complexes were photostable, but they
thermally decompose to give ArI and R PAuCF . Interestingly,
the reaction of [Au(CF )(Ar)I(PR )] with Ag gave cationic
complexes which underwent fast reductive elimination of
3
molecule. The isolated
and was separated from 7 by column chromatography. The
isolated Au(I) perfluoroalkyl complexes are air and light stable
3
3
3 6
white solids, except Ph PAu(n-C F13) (3), which was obtained as
+
3
3
an air-sensitive colourless oil. To the best of our knowledge,
complexes 6 and 7 are the first metal complexes reported
containing the perfluorocyclohexyl ligand.
[
9c]
ArCF
elimination of 4-FC
FC )Cl(PCy )] with Ag . Recently, the oxidative additions of
MeI or ICF to (PPh )[Au(CF ] to give (PPh )[Au(CF (CX )I]
were reported by the groups of Toste (X = H) and Menjón (X =
3
.
Shen and co-workers observed a similar fast reductive
6
H
4
(CF H) in the reaction of [Au(CF H)(4-
2
[9a]
2
3 6 5 2
Ph PAuMe reacted with C F CF I in the dark to give 8
+
6
H
4
3
(Scheme 2), which partially decomposed upon isolation to give
an impure oil and metallic gold particles. The reaction of
3
4
3
)
2
4
9b]
3
)
2
3
[
IPrAuMe with C
IPrAu(CF
not separated.
6 5 2
F CF I gave a mixture containing IPrAuI, likely
[
14e]
F)
(Scheme 1, C and D). The latter group also observed by
2
C
6
F
5
), and several unidentified products, which were
1
9
-
F
NMR the formation of trans-[Au(CF
analogous reaction with n-C I.
In this work we report a study of the reactivity of Au(I)
organometallic complexes of the type LAuR (L = PPh , N,N-
3 2 4 9
) (n-C F )I] in the
4
F
9
IRF
3
L
Au Me
L
Au RF
+
MeI
hν
402 nm)
bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr); R = methyl,
aryl or alkynyl) with perfluoroalkyl iodides. These reactions take
place under photoactivation with a mild light source and afford
(
1–8
RF
L
Yield (%)
Au(I) or Au(III) perfluoroalkyl complexes, or R–R
F
coupling
products. These reactions have allowed the isolation and
structural characterization of the first Au(I) and Au(III) complexes
with primary and secondary perfluoroalkyl ligands. Preliminary
results on the stability and reactivity of Au(III) complexes
containing a perfluoroalkyl and an aryl or alkyl ligand are
presented.
F2
C
CF3
1
2
PPh3
94
76
C
2
C
2
F
F
IPr
F2 F2
C
C
CF3
C
PPh3
3
C
2
C
F2
90
F
F
2
CF3
CF3
4
5
PPh3
IPr
75
51
FC
Results and Discussion
F2C CF2
CF CF2
6
7
PPh3
IPr
72
Reactions
of
Au(I)
alkyl
complexes
with
iPr
IPr =
iPr
70
F2C CF2
iPr
iPr
iodoperfluorocarbons
N
N
When a solution of Ph
3
PAuMe and perfluoro-1-iodobutane in
F
F
CD
2
Cl
2
was irradiated with a 402 nm LED for 1 min, a
PAu(n-C ) (1) took
8
F2C
F
PPh3a,b
quantitative reaction to give MeI and Ph
3
4 9
F
place (Scheme 2). The same products were formed after
irradiation with a UV fluorescent lamp (λmax = 310 nm), but in this
case traces of ethane were observed, likely arising from
F
F
a
The reaction takes place in the dark.
b Unstable, not isolated.
[
18]
photolysis of Ph
3
PAuMe.
On heating at 60 ºC in the dark
(
CDCl ) the reaction was slower (the yield was 59% after 20
3
Scheme 2. Reactions of Au(I) methyl complexes with iodoperfluorocarbons.
min) and partial decomposition to give metallic gold also took
place. No reaction was observed in the dark after 30 min at
room temperature, or when the reaction mixture was irradiated
with a blue LED (λmax = 454 nm).
The crystal structures of 1 and 2 were determined by single-
crystal X-ray diffraction (Figures 1 and 2). In both complexes the
Analogously, IPrAuMe and n-C
but quantitatively gave MeI and IPrAu(n-C
irradiation at 402 nm (Scheme 2). The tertiary alkyl complex
IPrAutBu reacted similarly with n-C I, to give tBuI and 2. The
reactions of LAuMe (L Ph P, IPr) with the secondary
iodoperfluoroalkane i-C I proceeded in the same way, to give
LAu(i-C ) (L = PPh (4), IPr (5)). Remarkably, no reaction
4
F
9
I did not react in the dark,
gold atoms show
a slightly distorted linear coordination
4
9
F )
(2) upon
environment. The Au(n-C F ) unit presents an "L" conformation
4
9
in both cases, probably to allow a more efficient molecular
packing. The Au–CF2 bond is slightly shorter in 1 (2.097(2) Å)
than in 2 (2.125(3) Å), and both Au–CF2 distances are longer
than the Au–CF3 distances reported for similar Au(I)
4
F
9
=
3
3
F
7
3
F
7
3
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
trifluoromethyl complexes containing NHC or phosphine ligands
substituted perfluorocyclohexanes, which show that the axial
[
19]
[21]
(
2.01–2.08 Å).
fluorine nuclei are less shielded than the equatorial ones.
Complex 6 shows a similar behaviour and its spectra are
included in the Supporting Information (Figure S1).
Figure 1. Crystal structure of 1 in the solid state (50% thermal ellipsoids).
Selected bond lengths (Å) and angles (deg): Au-C 2.097(2), Au-P 2.2918(5);
C-Au-P 173.07(6).
Figure 2. Molecular structure of 2 in the solid state (50% thermal ellipsoids).
Selected bond lengths and angles: Au-Ccarbene 2.014(2), Au-CF 2.125(3);
C
carbene-Au-CF 175.89(10).
19
8
Figure 3. Variable-temperature F NMR spectra of 7 (D -Toluene, 564.6
MHz).
1
9
31
The F and P NMR spectra of 1, 3, 4 and 8 show the
3
1
19
3
expected P- F coupling patterns, with JPF values in the range
Reactions
iodoperfluorocarbons
Ph PAuMes (Mes = 2,4,6-trimethylphenyl) did not react with n-
I in the dark at room temperature (CD Cl ) or at 60 ºC
CDCl ). However, upon irradiation at 402 nm the starting
materials gradually transformed into the oxidative addition
product [Au(n-C )(Mes)I(PPh )] (9, Scheme 3). At short
of
Au(I)
aryl
complexes
with
3
1
19
of 12.1–26.4 Hz. In complex 6 the P- F coupling was not
resolved because of exchange broadening (see below).
3
Perfluorocyclohexyl complexes 6 and 7 exist as mixtures of
two conformers, which could be observed by NMR spectroscopy
at low temperature. Fast exchange between both conformers
C
4
F
9
2
2
(
3
1
9
31
gave rise to coalescence of their F or P NMR signals into a
4
F
9
3
1
9
single set of averaged signals. The F NMR spectrum of 7 at -
0 ºC showed two sets of signals (Figure 3). According to the
irradiation times (ca. 1–2 min), 9 was the main reaction product,
along with unreacted starting materials and smaller amounts of 1,
6
symmetry of the conformers, each of these sets was composed
by six doublets, corresponding to the unequivalent equatorial
MesI,
Ph
3
PAuI,
mesitylene
and
several
unidentified
organofluorine products. Prolonged irradiation led to
a
and axial CF
2
fluorine nuclei, and a singlet, corresponding to the
progressive decay of 9 in favour of the other reaction products,
AuCF. The large splittings of these doublets (249–317 Hz) arise
which became finally the main components of the mixture
[
20]
mainly from the geminal F-C-F coupling.
The AuCF signals
(
Figures S5–S7). Complex 9 was isolated in 63% yield after
irradiating a mixture of Ph PAuMes and n-C I for 90 seconds.
Its crystal structure was determined by X-ray diffraction (Figure
).
appear around -200 and -219 ppm as singlets. One of the two
sets of signals is more intense than the other, and therefore was
assigned to the less sterically hindered conformer, having the
LAu moiety in equatorial disposition. According to this
assignment, the AuCF appear at a higher δ value in the main
conformer (LAueq–C–Fax) than in the minor one (LAuax–C–Feq).
3
4 9
F
4
2 2
In CD Cl solution, 9 is stable at room temperature in the
dark, but decomposed upon irradiation at 402 nm to give a
mixture containing essentially the same products which were
previously observed after prolonged irradiation of the reaction
1
9
This is in agreement with previous
F NMR studies on
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
mixture (Figure S8). This suggests that these reaction products
402 nm
310 nm
arose from photodecomposition of 9. Remarkably, integration of
X
1
I–RF
the H NMR spectrum and GC-MS analysis of the obtained
IPr Au Ph
hν
mixture revealed that the mesitylene formed after
IPr Au RF + PhI
photodecomposition of 9 in CD
2
Cl
2
was partially deuterated in
RF = n-C F , i-C F
4 9 3 7
2
, 5
one of the aromatic positions.
Scheme 4. Reactions of IPrAuPh with iodoperfluoroalkanes.
I
I–RF
Ph P Au Mes
3
Ph P Au RF
3
hν (402 nm)
The crystal structures of 9, 10 and 12 (Figures 4, 5 and 6)
Mes
show slightly distorted square planar coordination geometries,
9
–12
Mes =
with the PPh
most significant distortion is a widening of the I–Au–CF angle
96.23(6) º) in 12, probably produced by the steric repulsion
3 F
and R ligands in a mutual trans disposition. The
(
RF
Isolated yield (%)
hν
402 nm)
between the iodo and perfluoroisopropyl ligands. The Au–CF2
bond distances in the perfluoro-butyl or -hexyl complexes 9
(2.110(2) Å) and 10 (2.118(3) Å) are slightly shorter than the
Au–CF bond distance in 12 (2.152(2) Å), and similar to the Au–
2
(
9
n-C4F9 63
0 + 11 n-C6F13 65 (10:11 = 81:19)
9 (pure 10)
1
CD
Cl
2 2
3
1
2
i-C3F7 9.8
CF bond distance in 1 (2.097(2) Å).
Ph P Au RF
3
+
MesI
1
, 3, 4
I
Ph P Au I + MesH(D)
3
1
1 = Ph P Au Mes
3
+
n-C6F13
unidentified fluoroorganic
compounds
Scheme 3. Reactions of Ph
3
PAuMesAu(I) with iodoperfluoroalkanes and
photodecomposition of the resulting Au(III) complexes.
3 6 13
The outcome of the reaction of Ph PAuMes with n-C F I
was similar. However, in this case a mixture of two isomeric
Au(III) complexes (10 and 11) was isolated (Scheme 3). The
main isomer (10) was obtained pure by recrystallization in a 39%
yield. Its X-ray structure showed the same configuration as for 9
Figure 4. Molecular structure of 9 in the solid state (50% thermal ellipsoids).
Selected bond lengths and angles: Au-P 2.3857(5), Au-CF
.0659(19), Au-I 2.67565(18); CMes-Au-CF 89.21(8), CMes-Au-P 88.39(6), CF
Au-P 174.74(6), CMes-Au-I 178.53(6), CF -Au-I 91.90(6), P-Au-I 90.573(13).
2
2.110(2), Au-CMes
2
2
2
-
(
Figure 5). Owing to its higher solubility, the minor isomer (11)
2
could not be isolated free of 10, and its NMR data suggest that
the PPh
below).
3
and Mes ligands are mutually placed in trans (see
Analogously, the reaction of Ph
3 3 7
PAuMes with i-C F I gave
complexes 12, 4, and Ph PAuI, along with MesI, mesitylene and
3
several unidentified organofluorine products (Scheme 3). In
contrast with 9 and 10, complex 12 was always a minor
component of the reaction mixture, even at short irradiation
times. Nevertheless, 12 could be isolated from the reaction
mixture by liquid-diffussion crystallization. Its NMR spectra and
crystal structure show that its structure is analogous to that of 9
and 10 (Figure 6). No Au(III) complexes were detected in the
reaction of Ph
irradiation at 402 nm for 1 min to give 6 and MesI.
IPrAuPh did not react with n-C I or i-C I upon 402 nm
3 6
PAuMes and c-C F11I, which reacted upon
4
F
9
3
F
7
Figure 5. Molecular structure of 10 in the solid state (50% thermal ellipsoids).
Selected bond lengths and angles: Au-P 2.3781(7), Au-CF 2.118(3), Au-
CMes 2.061(2), Au-I 2.6777(3); CMes-Au-CF 89.10(10), CMes-Au-P 90.30(7),
CF -Au-P 174.95(7), CMes-Au-I 175.60(7), CF -Au-I 91.65(7), P-Au-I
9.329(18).
irradiation, but it reacted at 310 nm to give PhI and complexes 2
or 5, respectively (Scheme 4; Figures S9 and S10). No Au(III)
intermediates were detected in this case.
2
2
2
2
8
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
1
9
In the F NMR spectra of the Au(III) perfluoro-butyl or -hexyl
complexes 9, 10 and 11, the AuCF nuclei adjacent to gold
resonate at higher δ values than those of their Au(I) counterparts
or 3 (-79.5 to -81.0 ppm vs. -104 ppm, respectively). The same
happens with the perfluoroisopropyl complexes 12 and 4 (-172.1
parameters, the main difference between them being the
conformational disorder of the perfluorobutyl chain in one of the
molecules. The Au–C distances (2.122(4) and 2.123(4) Å) are
not significantly different from those of 9 and 10.
2
1
3
1
The P NMR signal of 13 appears at a similar δ value (27.2
3
1
3
vs. -199.1 ppm, respectively). In contrast, the P signals of the
ppm) than for 9–12. The high value of JPF (53.4 Hz) is in
Au(III) perfluoroalkyls appear at lower δ values than those of the
agreement with the trans disposition of the phosphine and the
3
19
Au(I) complexes (23.3–28.3 vs. 38.4–39.6 ppm). The JPF values
perfluorobutyl ligand. In the F NMR spectra of 13–15, the δ
of the Au(III) perfluoroalkyl complexes are typically higher than
those of their Au(I) counterparts.
2
values of the AuCF appear in the region from -74.1 and -81.9
ppm, which falls in the range observed for the Au(III)
The configuration of 11 was assigned on the basis of (i) a
perfluorobutyl complexes 9–11.
3
lower JPF value (29.7 Hz) in comparison with 9 and 10 (39.6 and
3
9.5 Hz), which suggests a mutually cis disposition of the
Br2 or
PhICl2
X
triphenylphosphine and perfluorohexyl ligands, and (ii) the
3
1
5
coupling between the mesityl aromatic proton and P ( JPH = 4.1
Hz), which was not observed in the other complexes and
suggests that the triphenylphosphine and mesityl ligands are
trans to each other.
L
Au
R
F
L
L
Au R
F
dark
1,2,5
X
13–16
= n
C F )
4 9
I
(R
2
F
dark
RF
X
Yield (%)
1
3
PPh3 n-C4F9 Br
75
66
61
82
I
14 IPr
n-C4F9 Cl
n-C4F9 Br
i-C3F7 Cl
1
1
5
6
IPr
IPr
L
Au n-C4F9
I
L = PPh3 (not detected)
L = IPr (detected: 17)
dark
L
Au I + n-C F I
4 9
Scheme 5. Reactions of Au(I) perfluorobutyl complexes with halogens or
PhICl
2
.
Figure 6. Molecular structure of 12 in the solid state (50% thermal ellipsoids).
Selected bond lengths and angles: Au-P 2.3748(6), Au-CF 2.152(2), Au-CMes
2
1
.063(2), Au-I 2.6925(2); CMes-Au-CF 88.46(9), CMes-Au-P 85.91(7), CF-Au-P
72.45(6), CMes-Au-I 173.81(6), CF-Au-I 96.23(6), P-Au-I 89.750(15).
Reactions of Au(I) perfluoroalkyl complexes with halogens.
Reductive elimination reactions from complexes
Au(R )X L] (X = Cl, Br, I)
The reaction of 1 with Br
13) as the main product (Scheme 5). It was separated from the
minor reaction products Ph PAuBr and Ph PAuBr by extraction
with n-hexane and isolated in a 75% yield. Similarly, complexes
[
F
2
2
4 9 2 3
afforded trans-[Au(n-C F )Br (PPh )]
(
3
3
3
1
4, 15 and 16 were isolated in 61–82% yield by reaction of 2 or
with PhICl or Br . In contrast, 1 reacted with PhICl to give a
PAuCl , Ph PAuCl, and the expected
Au(III) perfluoroalkyl complex trans-[Au(n-C )Cl (PPh )], which
could not be separated. The reactions of 1 or 2 with I
quantitatively gave LAuI (L = PPh or IPr) and n-C I (Scheme
). The Au(III) complex 17 was observed by NMR spectroscopy
at initial stages of the reaction, along with unreacted 2, IPrAuI
and n-C I (Figures S11 and S12). The expected Au(III)
intermediate of the reaction between 1 and I was not observed.
5
2
2
2
Figure 7. Molecular structure of 13 in the solid state (50% thermal ellipsoids).
Selected bond lengths and angles: Au-P 2.4019(10), Au-C 2.122(4), Au-Br(1)
2.4237(4), Au-Br(2) 2.4179(4); C-Au-P 176.71(11), C-Au-Br(2) 90.58(11), P-
Au-Br(2) 87.13(3), C-Au-Br(1) 90.56(11), P-Au-Br(1) 91.89(3), Br(2)-Au-Br(1)
mixture containing Ph
3
3
3
4
F
9
2
3
2
1
76.191(15).
3
4 9
F
5
Complex 13 underwent reductive elimination of n-C
was exposed to ambient light or irradiated with a blue LED
Scheme 6). In contrast, 15 was stable under blue light, but
4 9
F Br when it
4
F
9
2
(
The crystal structure of 13 (Figure 7) shows a slightly
distorted square planar trans geometry. The unit cell contains
two independent molecules with very similar structural
underwent reductive elimination on irradiation with 402 nm light.
This is in agreement with the positions of the absorption bands
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
in their UV-visible spectra (Figure 8). Thus, the lowest energy
absorption maximum of 13 lies at 368 nm, but it tails up to 500
nm, showing a significant absorbance in the visible region. In
contrast, the absorption maximum of 15 is at shorter wavelength
C
4
F
9
)(Me)(I)L]. Given that these complexes are potential
F
intermediates in the reacion between LAuMe and IR , their
reactivity could provide some insight on the reaction mechanism.
First, 13 and 15 were allowed to react with MeMgBr, to obtain
(
335 nm) but presents a low absorbance at 402 nm which
complexes of the type [Au(n-C
4 9
F )(Me)(Br)L], which could
decays at longer visible wavelengths. Finally, the lowest energy
maxima of 14 and 16 lie at 293 and 294 nm, respectively. These
complexes do not significantly absorb beyond 380 nm, therefore
they are stable under 402 nm irradiation. However, they
decomposed when they were irradiated at 310 nm in an
unselective way, to give a mixture of IPrAuCl and several
subsequently be transformed into the desired iodocomplexes by
-
-
Br /I metathesis. However, the reaction of 15 with the Grignard
reagent (3.8 equiv) in the dark cleanly gave MeBr and 2
(Scheme 7; Figure S18). The analogous reaction of 13 with
MeMgBr (1.2 equiv) gave 1, MeBr, Ph
unidentified product. This suggests that complexes [Au(n-
)(Me)(Br)L] (L IPr, PPh are unstable at room
3
PAuBr and an
unidentified
fluorinated
products,
among
which
the
C
4
F
9
=
3
)
[
22]
[23]
chlorofluorocarbons n-C
4
F
9
Cl or i-C
3
F
7
Cl were not detected
temperature against reductive elimination of MeBr.
1
9
by F NMR (Figures S13–17).
In the reaction of 13 with an excess of MeMgBr, trans-[Au(n-
4 9 2 3
C F )(Me) (PPh )] (18) was the main reaction product. It was
isolated in a 52% yield as a white air-stable solid. The presence
hν
λmax
1
Br
L
Au Br
+
in its H NMR spectrum of a unique Au-Me signal integrating for
(
)
L
Au n-C4F9
six protons indicated a trans configuration. It was stable under
n-C F Br
4
9
4
02 nm irradiation but decomposed unselectively upon 310 nm
irradiation in CD Cl solution to give mainly 1, CH CH , CDH
and CH CDCl (Figure S19).
Au(n-C )(Me)I(PPh )] (19) was obtained by protonolysis of
one of the Au–Me bonds of 18 in the presence of NBu
(Scheme 7). Formation of CH was confirmed by carrying out the
reaction in an NMR tube in CD
Hz) suggested a mutual trans disposition of the PPh
Br
L
λmax(nm)
2
2
3
3
3
1
3, 15
3
2
PPh3
IPr
454
402
[
4
F
9
3
4
I
λmax(nm)
4
Cl
3
hν
2
Cl
2
. The JPF value of 19 (40.5
and n-C
IPr Au RF
Cl
402 No reaction
10 Complex mixture
3
4 9
F
3
3
1
19
ligands, and their P and F C-Au chemical shift values were
2
1
comparable to those of 9 and 10. In the H NMR spectrum the
1
4, 16
RF = n-C4F9, i-C3F7
3
methylic protons of 19 gave a doublet at 1.78 ppm ( JPH = 5.6
Hz). In the dark at room temperature, 19 progressively
transformed into 1 and MeI over a period of more than 24 h. In
contrast, photoirradiation of 19 at 402 nm for 1 min led to almost
Scheme 6. Photoreductive elimination reactions of dihalo perfluoroalkyl AuIII)
complexes.
3
complete decomposition to MeI, 1, Ph PAuI (main products),
and several unidentified products (Scheme 7; Figure S20).
Br
MgMeBr (exc)
2
+
MeBr
L
Au n-C4F9
Br
L = IPr
1
3 or 15
MgMeBr (exc)
L = PPh3
Me
HOTf
Bu N)I
I
(
4
Ph P Au n-C4F9
Ph P Au n-C4F9
3
3
-HMe
Me
-(Bu N)OTf
Me
1
8
4
19
(52%)
(20%)
hν (402 nm)
fast)
RT, dark
(slow)
(
1
+ MeI + Ph3PAuI
-
4
1
+ MeI
2 2
Figure 8.UV-vis spectra of complexes 13–16 (CH Cl , 2–2.3 × 10 M).
+
unidentified products
Scheme 7. Synthesis of Au(III) complexes containing perfluoroalkyl and
methyl ligands. Thermal- or photo-reductive elimination reactions of these
complexes.
Having Au(III) perfluoroalkyl complexes 13 and 15 in our hands,
we attempted to synthesize complexes of the type [Au(n-
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
Reactions
iodoperfluorocarbons
The reactions of Ph PAuC≡CPh with IR
quantitatively gave Ph PAuI and alkynes R
upon 402 nm irradiation. As in the previous cases, the reaction
did not take place in the dark nor at 60 ºC (CDCl , 10 min).
Under the same conditions, complex Ph PAuC≡CnHex reacted
with IR (R = n-C , i-C ) to give Ph PAuI and alkynes
C≡CnHex as the main products, but complexes 1 or 4 and
of
Au(I)
alkynyl
complexes
with
Since the reactions do not proceed in the dark, perfluoroalkyl
radicals could be generated by three possible pathways
(Scheme 10): (a) Light-promoted homolysis of the Au–R bond
3
F
(R
F 4 9 3 7
= n-C F , i-C F )
3
F
C≡CPh (Scheme 8)
followed by reaction of the generated radicals with IR
electron transfer from an excited LAuR complex to a molecule of
IR ; (c) single electron transfer from LAuR to an excited
molecule of IR ; (d) light-activated homolysis of the I–R bond.
Homolysis of the Au–R (R = Me, Ar) bond under UV
F
; (b) single
3
F
3
F
F
F
F
4
F
9
3
F
7
3
[
18, 25]
R
F
irradiation has been reported,
the formation of the hydrogen abstraction products HR when
LAuR (L = PPh , R = Me, Mes, C≡CPh; L = IPr, R = Me) and an
excess of THF were irradiated with the less energetic 402 nm
radiation in CD Cl . In contrast, decreasing the wavelength to
however we did not detect
other unidentified products were also detected by NMR
spectroscopy in the reaction mixtures.
3
2
2
Ph P Au
I
IRF
3
310 nm induced formation of HR for complexes Ph PAuR (R =
3
Me or Mes) but not for R = C≡CPh (Figures S23 and S24). Thus,
pathway (a) was discarded.
Ph P Au
3
C
CR
+
hν
402 nm)
R C CR
F
(
Pathway (b) requires previous photoexcitation of the Au(I)
complex. The emission band of the used LED has its maximum
at 402 nm and the high-energy onset at ca. 370 nm. Since the
a
R
RF
Yield (%) of R C≡CR
F
Ph
Ph
n-C4F9
>90
>90
60
i-C3F
7
absorbance of complexes LAuMe (L = PPh , IPr) at wavelengths
3
nHex n-C4F9
nHex i-C3F7
longer than 350 nm is zero, these complexes can not be excited
upon irradiation with the 402 nm LED (Figure S25). In contrast,
83
a
Determined by NMR on the reaction mixture.
Ph
in the LED emission range. Remarkably, IPrAuPh does not react
with IR (R = n-C , i-C ) upon irradiation at 402 nm, despite
3 3
PAuMes and Ph PAuC≡CPh show a significant absorbance
Scheme 8. Reactions of Au(I) alkynyl complexes with iodoperfluoroalkanes.
F
F
4
F
9
3 7
F
its absorbance at this wavelength is higher than that of IPrAuMe.
Pathways (c) and (d) require previous photoexcitation of the
Mechanistic studies
iodoperfluoroalkane. The absorption maxima of IR
= n-C ) and 272 nm (R = i-C ), but the bands tail up to
ca. 375 nm (Figure S25). Since the overlap between the LED
emission and the IR absorption bands is minimal, the number of
F
lie at 269 nm
Previous studies have shown that the photooxidative addition of
(
R
F
4
F
9
F
3 7
F
ICF
3
to Au(I) aryl complexes proceed through a radical chain
mechanism which is initiated by the transfer of one electron from
F
[
9c]
the Au(I) complex to an excited molecule of ICF
agreement with a radical mechanism, the reactions of LAuR (L =
PPh , R = Me, Mes, C≡CPh; L = IPr, R = Me) and IR were
almost completely inhibited in the presence of the radical trap
TEMPO (Scheme 9). In addition, significant amounts of n-C
3
.
In
excited molecules in these conditions should be very small.
Accordingly, attempts to trap possible perfluoroalkyl radicals
3
F
formed by I–C homolysis by irradiating CD
I in the presence of THF or norbornene at 402 nm were
unsuccessful. Neither the THF α-hydrogen abstraction product
n-C H), nor the product resulting from n-C I addition to the
2 2
Cl solutions of n-
4 9
C F
4
9
F H
were formed when the reactions were carried out in presence of
an excess of THF (Scheme 9; Figures S21 and S22). This
hydrofluorocarbon typically results from α-hydrogen atom
(
4
F
9
4 9
F
norbornene C=C bond were detected by NMR. This suggests
that in the absence of the Au(I) complexes the extent of I–C
homolysis is insignificant and disfavours pathway (d).
[
24]
abstraction from THF by a perfluorobutyl radical.
L
Au
R
+
n-C F I
4 9
hν
(a) LAuR
LAu + R
CD Cl2 hν (402 nm)
2
R
+
IRF
hν
RI + RF
X
TEMPO
THF (exc)
Products + n-C F H
IR
F
(
b) LAuR
[LAuR]*
RF
-LAuRI
4
9
hν
+ LAuR
-LAuRI
(
c) IRF
d) IRF
IRF*
RF
R
F
n
R
L
% of H C F
4
9
Me
Me
PPh3
IPr
33
7
hν
(
+
I
Mes
C≡CPh
PPh3
PPh3
N.D.
3
Scheme 10. Pathways for the generation of perfluoroalkyl radicals in the
photochemical reactions of Au(I) organometallic complexes with
iodoperfluoroalkanes.
Scheme 9. Inhibition by TEMPO and radical-trapping experiments in the
reactions of Au(I) organometallic complexes with iodoperfluorobutane.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
To get further evidence on the initiation mechanism, we
F 3
Complexes [Au(R )Me(I)L] (L = IPr or PPh ) were not observed
investigated the reactions of complexes LAuR (L = Ph
3
P, R = Me, in the reaction mixtures, but one of these potential intermediates
(19, L = PPh ) was prepared by an alternative route. As
Mes, C≡CR; L = IPr, R = Me) with Br(CF H, which absorbs at
2
)
6
3
lower wavelengths (λmax < 200 nm) and thus can not be excited
by the 402 nm LED (Scheme 11). No reaction was observed in
any case with this light source, suggesting that excitation of the
halocarbon is necessary for the initiation of the reaction. In
contrast, irradiation at 310 nm produced mixtures containing
expected, 19 is unstable against reductive elimination of MeI,
being the photochemical decomposition much faster than the
thermal one. However, photodecomposition of 19 gave MeI and
1, along with Ph
S20). Since the reaction of Ph
MeI and 1, a pathway not involving an intermediate of the type
[Au(R )(R)(I)L] could be operative. As an alternative, we propose
pathway (Scheme 12), where homolysis of the Au(II)
intermediate [Au(R )(R)L] would give LAuR and a methyl
radical, which would react with IR to generate MeI and a
perfluoroalkyl radical. A similar pathway has been previously
proposed to explain the radical reactions of LAuMe (L = PMe
3
PAuI and several unidentified products (Figure
n
3
4 9
PAuMe and I C F cleanly affords
[
26]
mainly LAu(CF
Ph PAuC≡CR, which did not react (Figures S26–S33). Since UV
light is able to promote homolysis of the Au–R (R = Me, Ar)
2
)
6
H
and RBr in all cases,
except for
3
F
B
[
18, 25]
bond,
Br(CF
under irradiation at 402 is also in line with pathway (c),
considering its lower reducing power in comparison with
Ph PAuR (R = Me, Mes or C≡CPh).
this process could trigger the reactions with
F
F
2
)
6
H. The lack of reactivity of Ph PAuC against i-C
3
6
F
5
3
F
7
27]
I
F
[
3
,
[
16]
[28]
3
PMe
2
Ph, PMePh
2
, PPh
3
) with ICF
3
or PhSH,
and the
[
29]
reaction of Ph
3
PAuMe with [OsH
2
(CO) ].
4
In agreement with
this pathway, small amounts of MeH or the adduct Me–TEMPO
were detected by NMR spectroscopy when the reactions of
L
Au
R
hν Br(CF ) H
2
6
3 4 9
Ph PAuMe and n-C F I were carried out in the presence of THF
X
or TEMPO under 402 nm irradiation (Figures S21 and S22).
These products were not detected in the absence of the
iodoperfluoroalkane.
4
02 nm
310 nm
Au (CF ) H + RBr
L
2
6
When L = PPh
the Au(III) intermediates [Au(R
to be isolated. In contrast, when R
the Au(III) intermediate was observed in low concentration (R
i-C ), or it was not detected (R = c-C 11). This suggests that
3
, R = Mes and R
)(Mes)I(PPh
is a secondary perfluoroalkyl
F
is a primary perfluoroalkyl,
L
R
+
LAuBr + RH + ...
F
3
)] are stable enough
PPh3 Me, Mes
IPr
Me
F
F
=
Scheme 11. Reactions of Au(I) organometallic complexes with 1-bromo-6-H-
3
F
7
F
6
F
perfluorohexane upon irradiation at different wavelengths.
bulkier perfluoroalkyl ligands could destabilize the Au(III)
complexes.
Complexes [Au(R
temperature but under 402 nm irradiation they decompose to
give Ph PAuR MesI, Ph PAuI, mesitylene and several
unidentified organofluorine products. Formation of n-
TEMPO or n-C H when [Au(n-C )(Mes)I(PPh )] was
F 3
)(Mes)I(PPh )] are stable at room
In summary, the available evidence points to (c) being the
dominant initiation pathway under irradiation at 402 nm. Some of
3
F
,
3
F
the excited IR molecules could accept one electron from a Au(I)
-
complex to give I and a perfluoroalkyl radical that would initiate
a radical chain reaction. Addition of the radical to a LAuR
molecule would give a perfluoroalkyl Au(II) intermediate, which
C
4
F
9
4
F
9
4
F
9
3
irradiated in the presence of TEMPO or THF (Scheme 13,
figures S34 and S35) suggests that this decomposition takes
would react with IR
perfluoroalkyl radical, which would repeat the process (Scheme
2, pathway A).
F
to give a Au(III) complex and another
place through
a
radical mechanism. Remarkably, this
photodecomposition process has not been reported for the
[
9c]
1
3 3
trifluoromethylated analogues [Au(CF )(Ar)I(PPh )].
LAuR LAuR+
IRF*
IRF
I
n-C4F9TEMPO
hν
TEMPO
+
IRF
Ph P Au n-C4F
3
9
Ph P Au
3
I
I-
-
hν
(402 nm)
MeI
Mes
+
Ph P Au Mes
3
RF
IRF
Me
R = Me)
LAuRF
+
MesI
IRF
LAuR
A
B
THF (exc) hν
+
MesH(D)
(
402 nm)
(
II)
(
[
Au(R )(R)(I)L]
[Au(R )(R)L]
F
F
Ph P Au I + n-C F H + MesH
3
4 9
LAuRF + RI + LAuI + RH(D) + ... (R = Mes)
LAuI + RRF (R = alkynyl)
Scheme 13. Perfluorobutyl radical trapping experiments in the
photodecomposition of Au(III) perfluorobutyl complex 9.
Scheme 12. Proposed radical chain mechanism for the reactions of Au(I)
organometallic complexes with iodoperfluoroalkanes.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
Conclusions
spectrometer with nujol mulls between polyethylene sheets. Melting
points were determined on a Reichert apparatus in an air atmosphere.
3
The reactions of LAuR (L = PPh , IPr; R = methyl, mesityl or
Ph
3
PAu(n-C
4
F
9
) (1). n-C
4
F
9
I (24 µL, 0.14 mmol) was added to a solution
Cl (7 mL) in a Schlenk tube.
alkynyl) with primary or secondary perfluoroalkyl iodides
proceed upon irradiation with a mild light source (402 nm) and
follow a photoinitiated radical mechanism. They afford Au(I) or
of Ph
3
PAuMe (61 mg, 0.13 mmol) in CH
2
2
The solution was irradiated at 402 nm for 5 min with stirring and
evaporated to dryness under vacuum. Addition of n-pentane (1 mL) gave
a suspension which was filtered. The white solid was washed with cold n-
pentane (2 × 1 mL, 0 ºC) and air dried. Yield: 82 mg (0.12 mmol), 94%.
Au(III) perfluoroalkyl complexes of the types LAuR
Au(R )(R)I(PPh )], or alkynes C≡CR, depending on the
nature of L, R and R
Whereas oxidative addition complexes of the type
Au(R )(R)I(PPh )] were isolated for L = PPh and R = Mes, they
were not detected in the reactions of LAuMe and IR . Evidence
for different radical pathways in these reactions was obtained.
Au(III) perfluoroalkyl complexes of the type trans-[Au(R )X
L = PPh , IPr) have been prepared by oxidation of LAuR with
PhICl or Br . These complexes are light-sensitive and undergo
reductive elimination of XR under photoirradiation. In contrast,
F
or
[
F
3
R
F
1
F
.
M.p. 104–107 ºC (dec); H NMR (300.1 MHz, CDCl ): δ=7.55–7.46 (m,
3
1
3
15H); C NMR (75.5 MHz, CDCl
3
): δ=134.3 (d, JP,C=13.6 Hz, Ph), 131.9
(
d, JP,C=2.0 Hz; Ph), 129.5 (d, JP,C=11.3 Hz; Ph), 129.2 (d, JP,C=54.6 Hz;
[
F
3
3
1
9
C-P), 120.4–109.4 (several m; C-F); F NMR (282.4 MHz, CDCl
3
): δ=-
), -120.6 (m,
P,F = 23.1 Hz,
P,F = 1.7 Hz); IR (Nujol): ν 1344, 1273, 1233, 1189, 1172, 1146, 1022,
F
8
3 2
1.3 (tt, 3F, JF,F = 9.5 and 3.2 Hz; CF ), -104.5 (m, 2F; AuCF
3
1
3
2
3
F), -125.5 (m, 2F); P (121.5 MHz, CDCl ): δ=38.8 (tt, J
F
2
L]
4
~
J
(
3
F
–1
1
3
067, 999 cm (CF); elemental analysis calcd (%) for C22
8.96, H 2.23; found: C, 38.93, H 2.16.
9
H15AuF P: C
2
2
F
their diiodo analogues (X = I) are thermally unstable and could
not be isolated.
IPrAu(n-C
4
F
9
) (2). It was prepared in the same way as for 1 from
I (67 µL, 0.38 mmol). The
IPrAuMe (191 mg, 0.318 mmol) and n-C
4 9
F
The photoinstability of Au(III) perfluoroalkyl complexes
contrasts with the reported stability of their trifluoromethyl
irradiation time was 8 min. n-Hexane (5 mL) was added to the solution
and it was concentrated under vacuum until a white solid precipitated.
The suspension was filtered and the solid was washed with n-hexane (2
[
9c]
counterparts,
and should be taken into account when
×
1 mL) and air dried. Yield: 195 mg (0.242 mmol), 76%. M.p. 185–187
designing gold-catalysed perfluoroalkylation reactions.
The first gold complexes containing perfluoroalkyl ligands
other than trifluoromethyl have been isolated and structurally
characterized. These include the first perfluorocyclohexyl
transition metal complexes reported. Studies on the reactivity
and stability of Au(III) perfluoroalkyl complexes containing
different types of ligands are underway and will be reported in
due course.
1
3
ºC; H NMR (400.9 MHz, CD
2
Cl
H,H = 7.8 Hz, 4H, m-C
H,H = 6.9 Hz, 4H, CHMe ), 1.32 (d, JH,H = 6.9 Hz, 12H, Me), 1.23 (d, JH,H
2
): δ=7.54 (t,
6 3
JH,H = 7.8 Hz, 2H, p-C H ),
3
7
.34 (d,
J
6 3
H
), 7.23 (s, 2H, HC=CH), 2.55 (sept,
J
2
1
3
3
=
6.9Hz, 12H, Me); C NMR (100.8 MHz, CD
2
Cl
2
): δ=189.0 (t, JF,C = 6.5
), 146.1 (s, Ar),
1
2
Hz, N
2
CAu), 150.0 (tt, JF,C = 285.4, JF,C = 47.0 Hz, AuCF
2
134.2 (s, Ar), 130.9 (s, Ar), 124.4 (s, Ar), 124.0 (s, CH=CH), 119.9–109.6
1
9
(
several m, C-F), 29.2 (s, CH), 24.3 (s, Me), 24.1 (s, Me); F (188.3 MHz,
CD Cl ): δ=-82.1 (tt, JF,F = 9.4 and 3.5 Hz, 3F, CF ), -106.3 (m, 2F,
AuCF ), -123.3 (q, JF,F = 9.2 Hz, 2F), -126.1 (t, JF,F = 11.2 Hz, 2F); IR
Nujol): ν 1227, 1192 cm
AuN : C 46.28, H 4.51, N 3.48; found: C 46.37, H 4.50, N 3.35.
2
2
3
2
~
–1
(
(CF); elemental analysis calcd (%) for
C
31
H
36
F
9
2
Experimental Section
Ph
3 6 6
PAu(n-C F13) (3). n-C F13I (104 µL, 0.468 mmol) was added to a
[
30]
[31]
General considerations and materials: Ph
3
PAuMe
and IPrAuMe
solution of Ph PAuMe (111 mg, 0.234 mmol) in CH Cl (7 mL) in a
3
2
2
were prepared by modified literature methods (see Supporting
Schlenk tube. The solution was irradiated at 402 nm at room temperature
for 10 min with stirring. The reaction mixture was filtered through a PTFE
syringe filter to remove a small amount of gold particles, and the filtrate
was evaporated to dryness under vacuum to give a colourless oil which
was soluble in n-pentane. Yield: 163 mg (0.209 mmol), 90%. Satisfactory
elemental analyses could not be obtained because of the air sensitivity of
[
32]
[31]
[33]
[34]
Information). Ph
and Ph PAuC≡CnHex
Reactions were carried out under a N
Schlenk techniques. Inhibitor-free CH Cl
were used as solvents in preparative or NMR-tube reactions. Both were
passed through an activated basic alumina column, degassed by N
bubbling, and stored over 4 Å molecular sieves in a N atmosphere and
3
PAuMes,
IPrAutBu,
were prepared as previously reported.
atmosphere by using standard
(Fisher) or CD Cl (Eurisotop)
IPrAuPh,
3
Ph PAuC≡CPh
[
35]
3
2
2
2
2
2
1
13
2
2 2
the oil. H NMR (200.1 MHz, CD Cl ): δ=7.59–7.46 (m, 15H); C NMR
2
2 2 P,C
(100.8 MHz, CD Cl ): δ=134.6 (d, J = 13.5 Hz, Ph), 132.2 (d, JP,C = 2
protected of light. Unless otherwise stated, the complexes were isolated
in an air atmosphere using commercial solvents (HPLC or analytical
grade). Irradiations were performed using a blacklight or blue LED stripe
P,C
Hz, Ph), 129.7 (d, JP,C = 11.2 Hz, Ph), 129.4 (d, J = 55.3 Hz, C-P),
1
9
119.2–108.5 (several m, C-F); F NMR (188.3 MHz, CDCl ): δ=-81.3 (t,
3
JF,F = 9.6 Hz, 3F, CF ), -104.3 (m, 2F, AuCF ), -119.7 (m, 2F), -121.7 (m,
3
2
3
1
(
λ
max = 402 or 454 nm, respectively; 6 W, 1 m length) or a fluorescent
2 2
2F), -123.2 (m, 2F), -126.6 (m, 2F); P (162.3 MHz, CD Cl ): δ=38.6 (t,
3
lamp (λmax = 310 nm, 36 W). The LED stripes were placed in a reflecting
JP,F = 22.6 Hz).
metal can around the reaction tube. NMR spectra were measured on
1
13
1
Bruker Avance 200, 300, 400 or 600 MHz spectrometers. H and C{ H}
Ph
3
PAu(i-C
I (16 µL, 0.11 mmol) and Ph
solid. Yield: 50 mg (0.080 mmol), 75%. M.p. 156 ºC (dec); H NMR
3
F
7
) (4). It was prepared in the same way as for 1 from i-
[
36] 19
31
1
NMR spectra were referenced on the solvent signals.
spectra were referenced against external CFCl or H
F and P{ H}
, respectively.
C
3
F
7
3
PAuMe (50 mg, 0.11 mmol). White
3
3
PO
4
1
GC-MS analyses were performed on an Agilent 6890 gas chromatograph
with a HP5 column coupled to an Agilent 5973 mass spectrometer, which
13
(
400.9 MHz, CDCl
CDCl ): δ=134.3 (d, JP,C = 13.1 Hz, Ph), 132.0 (d, JP,C = 1.9 Hz, Ph),
29.5 (d, JP,C = 11.3 Hz, Ph), 129.1 (d, JP,C = 56.1 Hz, C-P); the C-F
3
): δ=7.56–7.49 (m, 15H); C NMR (100.8 MHz,
3
4
was equipped with an electron impact or chemical ionization (CH as
1
reagent gas) ion source. Elemental analyses were carried out with a
LECO CHNS-932 microanalyzer. UV-vis absorption spectra were
recorded on a Perkin-Elmer Lambda 750S spectrometer using 10 mm
quartz cells and spectroscopic grade solvents. Infrared spectra were
19
signals were not observed; F NMR (282.4 MHz, CDCl
3
): δ=-69.3 (dd,
3
4
3
3
J
F,F = 12.4 Hz,
J
P,F = 4.5 Hz, 6F, CF
3
), -199.1 (d of septets,
J
P,F
=
J
F,F
31
3
=
12.1 Hz, 1F, CF); P (162.3 MHz, CDCl
3
): δ=39.6 (d of septets,
J
P,F
=
4
~
–1
1
2.1 Hz, JP,F = 3.9 Hz); IR (Nujol): ν 1301, 1271, 1204, 1175, 1030 cm
-
1
recorded in the range 4000–200 cm on a Perkin-Elmer 16F PC FT-IR
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
2
2
(
CF); elemental analysis calcd (%) for C21
H
15AuF
7
P: C 40.15, H 2.41;
= 283.6 Hz, 1F), -135.1 (d,
J
F,F = 275.6 Hz, 2F) -142.4 (d,
J
F,F = 281.8
found: C 40.02, H 2.43.
Hz, 1F), -201.7 (m, 1F, AuCF); (signals of the minor conformer) δ=-111.3
2
2
2
(
d, JF,F = 248.9 Hz, 2F), -112.8 (d, JF,F = 272.5 Hz, 2F), -118.8 (d, J
F,F
2
2
=
1
255 Hz, 2F), -122.8 (d, JF,F = 299.7 Hz, 1F), -140.7 (d, JF,F = 281.3 Hz,
IPrAu(i-C
3
F
7
) (5). It was prepared in the same way as for 1 from
I (29 µL, 0.21 mmol). The
2
19
F), -141.3 (d,
, 23 ºC): δ=-109.2 (d, JF,F = 279.8 Hz, 2F), -118.1 (d, JF,F
282.1 Hz, 2F), from -125 to -140 (very br m, 6F), -204.6 (very br, 1F,
JF,F = 271.8 Hz, 2F), -219.0 (s, 1F, AuCF); F (564.6
IPrAuMe (102 mg, 0.170 mmol) and i-C
3 7
F
2
2
3 6 5
MHz, CD C D
irradiation time was 8 min. The volatiles were removed under vacuum
=
and the solid was stirred with n-pentane (1 mL), separated by filtration
1
9
2
1
AuCF); F (564.6 MHz, CD C D , 95 ºC): δ=-109.0 (d, JF,F = 280.7 Hz,
and air dried. Yield: 66 mg (0.087 mmol), 51%. M.p. 243–245 ºC;
NMR (400.9 MHz, CD Cl ): δ=7.54 (t, JH,H = 7.8 Hz, 2H, p-C
H,H = 7.8 Hz, 4H, m-C ), 7.24 (s, 2H, CH=CH), 2.52 (sept, JH,H = 6.9
), 1.29 (d, JH,H = 6.9 Hz, 12H, Me), 1.23 (d, JH,H = 6.9 Hz,
Cl ): δ=188.0 (s, N CAu), 146.2 (s,
Ar), 134.2 (s, Ar), 130.8 (s, Ar), 124.3 (s, Ar), 123.8 (s, CH=CH), 29.1 (s,
H
3
6
5
2
2
2
2
F), -118.1 (d,
J
F,F = 283.4 Hz, 2F), -128.1 (m, 5F), -137.0 (d,
J
F,F
=
2
2
6 3
H ), 7.32 (d,
~
–1
74.2 Hz, 1F), -206.7 (s, 1F, AuCF); IR (Nujol): ν 1192, 1003 cm (CF);
J
6 3
H
elemental analysis calcd (%) for C33
found: C 45.79, H 4.08, N 3.10.
36 2
H F11AuN : C 45.74, H 4.19, N 3.23;
Hz, 4H, CHMe
2
1
3
1
2H, Me); C NMR (100.8 MHz, CD
2
2
2
1
9
CH), 24.2 (s, Me), 24.1 (s, Me); the C-F signals were not observed;
F
Reaction of Ph
(8). C CF I (4 µL, 0.02 mmol) was added to a solution of Ph
(9.5 mg, 0.020 mmol) in CD Cl (0.5 mL) in a NMR tube. After 40 min in
3
PAuMe with C
6
F
5
CF
2
I. NMR data of Ph
3
PAu(CF
2 6 5
C F )
3
NMR (188.3 MHz, CD
2
Cl
sept, JF,F = 12.5 Hz, 1F, CF); IR (Nujol): ν 1299, 1272, 1199, 1175 cm
CF); elemental analysis calcd (%) for C30 AuN : C 47.75, H 4.81, N
.71; found: C 47.56, H 4.74, N 3.60.
2
): δ=-70.9 (d,
J
F,F = 11.7 Hz, 6F, CF
~
3
), -203.2
6
F
5
2
3
PAuMe
3
–1
(
(
2
2
H
36
F
7
2
the dark, the NMR spectra of the mixture showed quantitative formation
3
of 8 and MeI. The same reaction was carried out in a larger scale in
2 2
CH Cl to isolate 8. However, when the reaction mixture was evaporated
under vacuum and n-pentane was added to precipitate 8, partial
decomposition to metallic gold took place and a grey oil was formed. This
oil was a mixture containing 8 and several unidentified compounds. NMR
Ph
3
PAu(c-C
6
F
11) (6). It was prepared in the same way as for 1 from c-
PAuMe (103 mg, 0.217 mmol). The
C
6
F
11I (45 µL, 0.24 mmol) and Ph
3
reaction mixture was concentrated under vacuum up to ca. 0.5 mL and
dry n-pentane (3 mL) was added with stirring. The resulting precipitate
was allowed to sediment and the mother liquor was removed with a
1
19
data of 8: H NMR (200.1 MHz, CD
NMR (188.3 MHz, CD Cl ): δ=-80.7 (qd, JF,F = JP,F = 25.4 Hz, JF,F = 3.0
Hz, 2F, CF ), -143.4 (m, 2F), -157.8 (t, JF,F = 21.1 Hz, 1F), -163.8 (m,
2
Cl
2
4
): δ=7.57–7.46 (m, 15 H);
F
3
6
2
2
pipette under a N
2
atmosphere. The white solid was washed in the same
2
3
1
3
2
2 2
F); P (81.0 MHz, CD Cl ): δ=38.4 (t, JP,F = 26.4 Hz).
way with dry n-pentane (2 × 1 mL) and dried under vacuum. Yield: 115
1
mg (0.155 mmol), 72%. M.p. 130 ºC (dec); H NMR (200.1 MHz, CD
2
Cl
, 21 ºC): δ=134.5
d, JP,C = 13.7 Hz, Ph), 132.3 (d, JP,C = 2.1 Hz, Ph), 129.7 (d, JP,C = 11.4
Hz, Ph), 129.2 (d, JP,C = 56.7 Hz, C-P); the C-F signals were not
2
):
1
3
δ=7.56–7.48 (m, 15 H, Ph); C NMR (50.3 MHz, CD
2
Cl
2
SP-4-4-[Au(n-C
4
F
9
)(Mes)I(PPh
3
)] (9). n-C
4
F
9
I (91 µL, 0.53 mmol) was
Cl
(
added to a solution of [Au(Mes)(PPh
3
)] (102 mg, 0.176 mmol) in CH
2
2
(10 mL). The solution was irradiated at 402 nm for 80 s at room
temperature with stirring. The resulting yellow solution was evaporated to
dryness under vacuum. The residue was stirred with n-pentane (10 mL)
to give a pale yellow precipitate, which was isolated by filtration, washed
1
9
2
observed; F NMR (188.3 MHz, CD
2
Cl
2 F,F
, 21 ºC): δ=-109.2 (d, J =
2
2
69.3 Hz, 2F), -118.8 (d,
JF,F = 280.5 Hz, 2F), -129.6 (br m, 5F), -138.2
1
9
(
(
(
-
(
br m, 1F), -206.0 (br s, 1F, AuCF); F (564.6 MHz, CD
2
Cl
signals of the major conformer) δ=-108.5 (d, JF,F = 292.9 Hz, 2F), -117.7
2
, -60 ºC):
2
with n-pentane (3 × 2 mL) and air dried. Yield: 102 mg (0.110 mmol),
2
2
1
d, JF,F = 293.0 Hz, 2F), -123.2 (two overlapped d, JF,F = 279.9 Hz, 3F),
63%. M.p. 160–165 ºC; H NMR (600.1 MHz, CDCl
3
): δ=7.49-7.32 (m,
2
2
13
135.7 (d,
J
F,F = 277.6 Hz, 2F), -143.0 (d,
J
F,F = 282.4 Hz, 1F), -200.0
15H, Ph), 6.34 (s, 2H, H3, Mes), 2.12 (s, 6H, Me), 2.08 (s, 3H, Me);
C
2
s, 1F, AuCF); (signals of the minor conformer) δ=-111.9 (d, JF,F = 254.7
NMR (150.9 MHz, CDCl ): δ=149.9 (m, C1, Mes), 136.5 (s, Mes), 136.2
3
2
2
Hz, 2F), -113.3 (d, JF,F = 275.8 Hz, 2F), -119.7 (d, JF,F = 255.3 Hz, 2F),
(s, Mes), 135.0 (d, JPC = 9.2 Hz, Ph), 131.8 (s, Ph), 129.5 (s, Mes), 128.5
(d, JP,C = 11.2 Hz, Ph), 127.2 (d, JP,C = 56.8 Hz, C-P), 120.8–109.6
2
2
-
2
123.7 (d, JF,F = 316.7 Hz, 1F), -140.7 (d, JF,F = 280.3 Hz, 1F), -142.1 (d,
19
19
J
F,F = 275.5 Hz, 2F), -219.7 (s, 1F, AuCF); F NMR (188.3 MHz,
(several m, C-F), 23.6 (s, Me), 20.3 (s, Me); F NMR (188.3 MHz,
2
2
3
CD
3
C
6
D
5
, 80 ºC): δ=-108.6 (d,
J
F,F = 280.4 Hz, 2F), -117.8 (d,
J
F,F
=
CD
F,F = 10.1 and 2.9 Hz, CF
(81.0 MHz, CD Cl ): δ=23.3 (t,
2
Cl
2
): δ=-80.4 (dtm, JF,F = 15.6 Hz,
J
P,C = 39.4 Hz, AuCF
2
), -81.7 (tt,
2
31
2
83.2 Hz, 2F), -128.4 (d, JF,F = 273.7 Hz, 1F) -128.7 (br s, 4F), -137.1 (d,
J
3
), -112.8 (m, 2F), -126.6 (m, 2F); P NMR
2
31
3
~
J
FF = 280.4 Hz, 1F), -204.8 (s, 1F, AuCF); P (242.9 MHz, CD
2
Cl
2
, 25
2
2
J
P,F = 39.6 Hz); IR (Nujol): ν 1190, 1175,
3
1
–1
ºC): δ=39.4 (br m); P (242.9 MHz, CD
2
Cl
2
, -60 ºC): δ=39.1 (br m, major
1097, 1059 cm (CF); elemental analysis calcd (%) for C31
40.28, H 2.84; found: C 40.06, H 2.99.
9
H26AuF IP: C
–
1
~
conformer), 37.7 (br m, minor conformer); IR (Nujol, cm ): ν 1246, 1227,
–
1
1
216, 1197, 1164, 1130, 1039, 1002, cm (CF); elemental analysis
calcd (%) for C24 15AuF11P: C 38.94, H 2.04; found: C 39.03, H 2.03.
H
SP-4-4- and SP-4-3-[Au(n-C
prepared in the same way as for 9 from n-C
and [Au(Mes)(PPh )] (107 mg, 0.185 mmol). The obtained pale yellow
solid was a mixture of 10 (81%) and its isomer 11 (19%). Yield: 126 mg
(0.120 mmol), 65%. Recrystallization from CH Cl /n-hexane at 5 ºC gave
pale yellow crystals of pure 10. Yield: 73 mg, 39%. M.p. 170–175 ºC
6
F
13)(Mes)I(PPh
3
)] (10) and (11). It was
6
F13I (124 µL, 0.556 mmol)
IPrAu(c-C
6
F
11) (7). It was prepared in the same way as for 1 from
11I (46 µL, 0.24 mmol). The
3
IPrPAuMe (130 mg, 0.216 mmol) and c-C
6
F
irradiation time was 15 min. The reaction mixture was evaporated to
dryness. The residue was extracted with n-hexane (20 mL). The extract
was concentrated and chromatographed in a silicagel column. Elution
2
2
1
(dec); H NMR (600.1 MHz, CD
2H, H3, Mes), 2.13 (s, 6H, Me), 2.09 (s, 3H, Me); C NMR (150.9 MHz,
CD Cl ): δ=150.3 (m, C1, Mes), 136.68 (s, Mes), 136.64 (s, Mes), 135.3
2 2
Cl ): δ=7.51-7.35 (m, 15H, Ph), 6.36 (s,
1
3
with CH
2 2 f
Cl /n-hexane (1:1) gave pure 7 (R = 0.6), which was obtained
after evaporation as a white solid. Yield: 112 mg (0.151 mmol), 70.0%.
2
2
1
M.p. 225–226 ºC; H NMR (200.1 MHz, CD
.8 Hz, 2H, p-C ), 7.33 (d, JH,H = 7.8 Hz, 4H, m-C
CH=CH), 2.55 (sept, JH,H = 6.9 Hz, 4H, CHMe ), 1.31 (d, JH,H = 6.9 Hz,
2
Cl
2
, 21 ºC): δ=7.54 (t, JH,H
=
(d, JP,C = 7.8 Hz, C3, Ph), 132.2 (s, Ph), 129.8 (s, C3, Mes), 128.7 (d, JP,C
= 11.2 Hz, C2, Ph), 127.2 (d, JP,C = 57.5 Hz, C1, Ph), 120.6–107.1
7
6
H
3
6 3
H
), 7.26 (s, 2H,
1
9
2
(several m, C-F) 23.7 (s, Me), 20.2 (s, Me); F NMR (188.3 MHz,
1
3
3
1
2H, Me), 1.24 (d, JH,H = 6.9 Hz, 12H, Me); C (150.9 MHz, CD
ºC): δ=188.1 (s, N CAu), 146.2 (s, Ar), 134.2 (s, Ar), 130.9 (s, Ar), 124.4
s, Ar), 123.9 (s, CH=CH), 29.22 (s, CH), 24.21 (s, Me), 24.17 (s, Me);
2
Cl
2
, 25
CD
2
Cl
2
): δ=-79.5 (dtm, JP,F= 39.7 Hz, JF,F = 16.3 Hz, 2F, AuCF
2
), -81.1 (t,
2
J
F,F = 10.1 Hz, 3F, CF
3
), -111.3 (m, 2F), -122.0 (m, 2F), -122.8 (m, 2F), -
3
1
3
(
126.3 (m, 2F); P NMR (81.0 MHz, CD
2
Cl
IR (Nujol): ν 1235, 1195 cm (CF); elemental analysis calcd (%) for
26AuF13IP: C 38.69, H 2.56; found: C 38.61, H 2.58. NMR data of 11:
H NMR (200.1 MHz, CDCl ): δ=7.68-7.46 (m, 15H, Ph), 6.74 (d, 2H,
2
): δ=23.9 (t, JP,F = 39.5 Hz);
1
9
~
–1
the C-F signals were not observed; F (564.6 MHz, CD
3
C
6
D
5
, -60 ºC):
2
(
signals of the major conformer) δ=-108.4 (d, JF,F = 293.1 Hz, 2F), -117.3
33
C H
1
2
2
2
(
d,
J
F,F = 292.7 Hz, 2F), -122.1 (d,
J
F,F = 276.4 Hz, 2F), -122.3 (d,
J
F,F
3
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
5
19
J
P,H = 4.1 Hz, H3, Mes), 2.44 (s, 3H, Me), 2.25 (s, 6H, Me); F NMR
188.3 MHz, CD Cl ): δ=-81.1 (m, 2F, AuCF ), -81.2 (m, 3F, CF ), -113.8
m, 2F), -122.5 (m, 2F), -123.1 (m, 2F), -126.6 (m, 2F); P NMR (81.0
trans-[Au(n-C
14 from Br
Yield: 75 mg (0.078 mmol), 61%. M.p. 157–161 ºC (d); H NMR (200.1
4
F
9
)Br
2
(IPr)] (15). It was prepared in the same way as for
(
2
2
2
3
2
(0.13 mmol) and 2 (102 mg, 0.127 mmol). Orange solid.
3
1
1
(
3
4
3
3
MHz, CD
2
Cl
2
): δ=28.3 (tt, JP,F = 29.7 Hz, JP,F = 5.3 Hz).
MHz, CD
Hz, 4H, m-C
CHMe ), 1.38 (d, JH,H = 6.6 Hz, 12H, Me), 1.12 (d, J
2
Cl
2
): δ=7.56 (t,
J
H,H = 7.2 Hz, 2H, p-C
6
H
3
), 7.37 (d,
J
H,H = 7.7
H,H = 6.8 Hz, 4H,
H,H = 6.8 Hz, 12H,
): δ=163.5 (t, JC,F = 16.6 Hz, N CAu),
46.5 (Ar), 133.7 (Ar), 131.6 (Ar), 126.6 (CH=CH), 124.8 (Ar), 122.9–
3
6
H
3
), 7.35 (s, 2H, CH=CH), 2.99 (sept, J
3
3
SP-4-4-[Au(i-C
3
F
7
)(Mes)I(PPh
Cl
3
)] (12). To a solution of [Au(Mes)(PPh
3
)]
2
3
1
3
Me); C NMR (150.9 MHz, CD
2
Cl
2
2
(
79 mg, 0.14 mmol) in CH
2
2
(6 mL) i-C I (60 µL, 0.41 mmol) was
3 7
F
1
1
added. The mixture was irradiated at 402 nm for 15 s with stirring to give
a yellow solution, which was concentrated to ca. 0.5 mL under vacuum,
layered with n-hexane (10 mL) and allowed to stand in the dark until
yellow crystals grew (2 days). The crystals were separated from the
1
9
09.2 (several m, C-F), 29.4 (CHMe
Cl ): δ=-81.9 (tt, JF,F = 9.8 and 2.7 Hz, 3F, CF
F,F = 13.6 Hz, 2F, AuCF ), -114.7 (m, 2F), -126.6 (m, 2F); IR (Nujol,): ν
2
), 26.7 (Me), 23.0 (Me); F NMR
(
188.3 MHz, CD
2
2
3
), -83.3 (t,
~
J
2
-
1
1
232, 1197, 1129 cm
(CF); elemental analysis calcd (%) for
mother liquor and dried under vacuum. Yield: 12 mg (0.014 mmol), 9.8%;
1
C
31
H
36Br
2
F
9
AuN : C 38.61, H 3.76, N 2.90; found: C 38.35, H 3.76, N
2
2 2
H NMR (300.1 MHz, CD Cl ): δ=7.53–7.35 (m, 15H, Ph), 6.32 (s, 2H, H3,
1
9
2.86.
Mes), 2.13 (s, 6H, Me), 2.06 (s, 3H, Me); F NMR (282.4 MHz, CD
2
Cl
2
):
3
3
31
δ=-65.6 (t,
J
P,F
=
JF,F = 7.8 Hz, 3F, CF ), -173.1 (m, 1F, CF); P NMR
3
3
4
(
81.0 MHz, CD
2
Cl
2
): δ=26.5 (d of septets, JP,F = 22.4 Hz, JP,F = 7.1 Hz);
trans-[Au(i-C )Cl
3
F
7
2
(IPr)] (16). It was prepared in the same way as for
1
3
The available amount of sample was too small to obtain an useful
C
14, from PhICl (61 mg, 0.22 mmol) and 5 (110 mg, 0.183 mmol). The
2
NMR spectrum; elemental analysis calcd (%) for C30
H 3.00; found: C 41.33, H 3.12.
H
26AuF
7
IP: C 41.21,
mixture was stirred for 12 h at room temperature and worked-up in the
same way to give a yellow solid. Yield: 124 mg (0.150 mmol), 82%. M.p.
1
3
1
87–190 ºC (dec); H NMR (200.1 MHz, CD
2
Cl
2
): δ=7.57 (t,
JH,H = 7.8
3
Hz, 2H, p-C
6
H
3
), 7.37 (d,
J
H,H = 7.4 Hz, 4H, m-C
6 3
H
), 7.36 (s, 2H,
trans-[AuBr
added to a solution of [Au(Me)(PPh
20 mL). The mixture was irradiated with a 402 nm LED for 5 min and
evaporated to dryness under vacuum. The resulting white solid
containing complex 1 was redissolved in CH Cl (20 mL) and the solution
was cooled at –70 ºC and protected from light. Then, a solution of Br in
CH Cl (2.8 mL, 0.26 M, 0.73 mmol of Br ) was added with stirring. The
2
(n-C
4
F
9
)(PPh
3
)] (13). n-C
4
F
9
I (137 µL, 0.796 mmol) was
3
3
CH=CH), 2.86 (sept,
J
H,H = 6.8 Hz, 4H, CHMe
2
), 1.36 (d,
J
H,H = 6.7 Hz,
H,H = 6.8 Hz, 12H, Me); C NMR (150.9 MHz,
): δ=163.0 (m, N CAu), 146.6 (s, Ar), 133.1 (s, Ar), 131.7 (s, Ar),
26.4 (s, CH=CH), 124.7 (s, Ar), 122.6 (qdq,
3
)] (342 mg, 0.721 mmol) in CH
2
Cl
2
3
13
1
2H, Me), 1.12 (d,
J
(
CD Cl
2
2
2
1
2
1
2
3
JF,C = 310.8 Hz,
1
J
F,C
=
=
2
2
3
2
6.4 Hz,
3 F,C
JF,C = 4.5 Hz, CF ), 96.2 (d of septets, JF,C = 233.6 Hz, J
2
1
9
5.9 Hz, CF), 29.3 (CHMe
2
), 26.7 (Me), 22.5 (Me); F NMR (188.3 MHz,
2
2
2
3
3
CD
2 2 3
Cl ): δ=-68.5 (d, JF,F = 8.5 Hz, 6F, CF ), -177.9 (sept, JF,F = 8.5 Hz,
reaction mixture was slowly warmed to room temperature over 40 min
then it was evaporated to dryness under vacuum. The orange residue
was extracted with warm n-hexane (50 mL) to give a yellow extract. The
residue was extracted with more warm n-hexane until the extract was
almost colourless (2 × 20 mL). The extracts were filtered through a cotton
plug while protecting from light and evaporated to dryness. The residue
was stirred with cold n-pentane (0º C, 3 mL) to give a yellow solid, which
was filtered, washed with cold n-pentane (3 mL) and air dried. Yield: 452
~
-1
1
F, CF); IR (Nujol,): ν 1292, 1275, 1210, 1191 cm (CF); elemental
analysis calcd (%) for C30
C 43.50, H 4.38, N 3.29.
2 7 2
H36Cl F AuN : C 43.65, H 4.40, N 3.39; found:
4 9 2 3 2
trans-[Au(n-C F )Me (PPh )] (18). MgMeBr (2.8 M solution in Et O, 1.05
mmol) was added to a solution of 13 (293 mg, 0.350 mmol) in THF (20
mL) at -70 ºC protected from light. The mixture was allowed to warm at
1
mg (0.539 mmol), 75%. M.p. 98–100 ºC (dec); H NMR (600.1 MHz,
room temperature and stirred for 30 min in the dark. Then, H
was added and the mixture was stirred for 15 min and evaporated to
dryness under vacuum. The residue was stirred with CH Cl (20 mL) and
excess of MgSO for 40 min. The suspension was filtered over celite. The
solid material was extracted with more CH Cl (30 mL) and the combined
CH Cl solutions were evaporated to dryness. The resulting residue was
2
O (0.1 mL)
1
3
CD
2 2 2 2
Cl ): δ=7.65–7.51 (m, 15H, Ph); C NMR (100.8 MHz, CD Cl ):
δ=135.4 (d, JP,C = 9.6 Hz, Ph), 132.9 (d, JP,C = 2.6 Hz, Ph), 129.2 (d, JP,C
2
2
1
=
11.7 Hz, Ph), 126.5 (d,
J
P,C = 58.1 Hz, C-P), 119.5–109.2 (several m,
); F NMR (188.3 MHz, CDCl ): δ=-72.6 (dt, JP,F = 54.3 Hz, JF,F
), -80.8 (tt, JF,F = 10.0 and 2.2 Hz, 3F, CF ), -112.5 (m,
4
1
9
n-C
4
F
9
3
=
2
2
1
2
3.4 Hz, 2F, AuCF
F), -125.8 (m, 2F); P NMR (81.0 MHz, CDCl
2
3
2
2
3
1
3
3
): δ=27.4 (t,
J
P,F = 54.2
extracted with n-pentane (3 × 3 mL). The extract was filtered and
~
-1
Hz); IR (Nujol): ν 1237, 1197, 1093, 1075 cm (CF); elemental analysis
calcd (%) for C22 PAu: C 31.53, H 1.80; found: C 31.57, H 1.82.
concentrated under vacuum to give a white solid. Yield: 128 mg (0.181
1
H
15Br
2
F
9
mmol), 52%. M.p. 128–130 ºC (dec); H NMR (600.1 MHz, CD
2
Cl
2
):
3
13
δ=7.58–7.50 (m, 15H, Ph), 0.11 (d,
150.9 MHz, CD Cl ): δ=134.7 (d, JP,C = 10.8 Hz, C3, Ph), 132.2 (s, Ph),
29.3 (d, JP,C = 11.2 Hz, C2, Ph), 126.9 (d, JP,C = 57.3 Hz, C1, Ph),
JP,H = 5.3 Hz, 6H, Me); C NMR
(
2
2
trans-[Au(n-C
in CH Cl (2.5 mL) was added to a light-protected solution of 2 (105 mg,
.131 mmol) in CH Cl (5 mL) at -70 ºC with stirring. The mixture was
4 9 2 2
F )Cl (IPr)] (14). A solution of PhICl (36 mg, 0.13 mmol)
1
1
2
2
1
9
21.2–108.4 (several m, C-F), 13.7 (m, Me); F NMR (188.3 MHz,
Cl ): δ=-81.3 (tt, JF,F = 10.1 and 3.2 Hz, 3F, CF ), -96.9 (dt, JP,F
8.6 Hz and JF,F = 13.9 Hz, 2F, AuCF ), -116.9 (m, 2F), -126.0 (m, 2F);
0
2
2
CD
2
2
3
=
allowed to warm at room temperature and then stirred for 45 min. The
3
2
volatiles were removed under vacuum and the residue was stirred with n-
3
1
3
~
P NMR (81.0 MHz, CD
1346, 1233, 1190, 1100, 1073 cm (CF); elemental analysis calcd (%)
for C24 PAu: C 40.69, H 2.99; found: C 40.93, H 2.74.
2 2
Cl ): δ=30.0 (t, JP,F = 38.4 Hz); IR (Nujol): ν
pentane (5 mL) to give a yellow solid, which was isolated by filtration and
-
1
1
air dried. Yield: 76 mg (0.87 mmol), 66%. M.p. 149–151 ºC (dec);
NMR (600.1 MHz, CD Cl ): δ=7.57 (t, JH,H = 7.2 Hz, 2H, p-C
H,H = 7.8 Hz, 4H, m-C ), 7.33 (s, 2H, CH=CH), 2.86 (sept, JH,H = 6.6
), 1.38 (d, JH,H = 6.6 Hz, 12H, Me), 1.13 (d, JH,H = 7.2 Hz,
H
21 9
H F
2
2
6 3
H ), 7.38 (d,
J
6 3
H
Hz, 4H, CHMe
2
SP-4-4-[Au(n-C
mmol) in CH Cl
0.85 M solution in Et
4
F
9
)(Me)I(PPh
(20 mL) was sequentially treated with HOTf (140 µL of a
O, 0.119 mmol) and NBu I (45 mg, 0.12 mmol) at
3
)] (19). A solution of 18 (84 mg, 0.119
1
3
3
1
2H, Me); C NMR (150.9 MHz, CD
2
Cl
2
): δ=166.3 (t,
J
C,F = 16.6 Hz,
2
2
N
2
CAu), 146.6 (Ar), 133.3 (Ar), 131.6 (Ar), 126.3 (CH=CH), 124.8 (Ar),
2
4
1
9
1
23.3–109.3 (several m, C-F), 29.3 (CHMe
NMR (188.3 MHz, CD Cl ): δ=-81.9 (tt, JF,F = 9.8 and 2.6 Hz, 3F, CF
1.6 (t, JF,F = 16.7 Hz, 2F, AuCF ), -117.0 (m, 2F), -126.6 (m, 2F); IR
2
), 26.6 (Me), 22.7 (Me);
F
room temperature in the dark. The mixture was stirred for 2 min and
2
2
3
), -
evaporated to dryness under vacuum. The residue was stirred with 4:1 n-
9
2
2
pentane:Et O (30 mL) in the dark. The suspension was filtered with a
~
-1
(
(
Nujol): ν 1228, 1194, 1131, 1086 cm (CF); elemental analysis calcd
%) for C31 AuN : C 42.53, H 4.14, N 3.20; found: C 42.56, H 4.20,
cannula equipped with a cotton filter, and the filtrate was transferred to a
light-protected flask and evaporated to dryness. The resulting residue
was stirred with n-pentane (3 mL). The suspension was filtered and the
white solid was washed with n-pentane (3 × 2 mL) and air dried. Yield: 20
H
36Cl
2
F
9
2
N 3.04.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
1
mg (0.025 mmol), 20%. M.p. 89–92 ºC (dec); H NMR (300.1 MHz,
Poisson, X. Pannecoucke, Chem. Eur. J. 2014, 20, 16830-16845; i) T.
Liang, C. N. Neumann, T. Ritter, Angew. Chem., Int. Ed. 2013, 52,
8214-8264; j) J. Xu, X. Liu, Y. Fu, Tetrahedron Lett. 2014, 55, 585-594;
k) O. A. Tomashenko, V. V. Grushin, Chem. Rev. 2011, 111, 4475-
4521; l) Y. Ye, M. Sandford, Synlett 2012, 23, 2005-2013; m) V. V.
Grushin, Acc. Chem. Res. 2009, 43, 160-171; n) T. Koike, M. Akita, Acc.
Chem. Res. 2016, 49, 1937-1945; o) C. Le, T. Q. Chen, T. Liang, P.
Zhang, D. W. C. MacMillan, Science 2018, 360, 1010.
3
19
CD
2
Cl
2
): δ=7.65–7.51 (m, 15H, Ph), 1.41 (d,
): δ=-80.8 (tt, JF,F = 9.7 and 2.4 Hz, 3F, CF
3.5 (dt, JP,F = 40.7 Hz and JF,F = 13.1 Hz, 2F, AuCF ), -113.3 (m, 2F), -
J
P,H = 5.6 Hz, 3H, Me);
F
NMR (282.4 MHz, CDCl
3
3
), -
8
1
2
3
1
3
2 2
25.8 (m, 2F); P NMR (121.5 MHz, CD Cl ): δ=27.0 (t, JP,F = 40.5 Hz);
1
3
an useful C NMR spectrum was not obtained because complex 19
~
partially decomposed during the measurement; IR (Nujol): ν 1346, 1223,
-
1
1
127, 1097, 1073 cm
(CF); elemental analysis calcd (%) for
C
23
H
18IF
9
PAu: C 33.68, H 2.21; found: C 33.70, H 2.04.
[3]
a) X. Bao, L. Liu, J. Li, S. Fan, J. Org. Chem. 2018, 83, 463-468; b) X.
Tan, Z. Liu, H. Shen, P. Zhang, Z. Zhang, C. Li, J. Am. Chem. Soc.
2
017, 139, 12430-12433; c) E. J. Cho, T. D. Senecal, T. Kinzel, Y.
Crystal Structure Determinations. Single crystals of 1 and 2 were
obtained by slow evaporation of a CH Cl /n-hexane solution. Single
crystals of 9, 10, 12 and 13 were obtained by liquid diffusion between a
CH Cl solution and n-hexane. The compounds were measured on a
Zhang, D. A. Watson, S. L. Buchwald, Science 2010, 328, 1679-1681;
d) S. T. Keaveney, F. Schoenebeck, Angew. Chem., Int. Ed. 2018, 57,
2
2
4
9
073-4077; e) Y. Ye, M. S. Sanford, J. Am. Chem. Soc. 2012, 134,
2
2
034-9037; f) X. Wang, Y. Xu, F. Mo, G. Ji, D. Qiu, J. Feng, Y. Ye, S.
Bruker D8 SMART diffractometer at 100K. Data were collected using a
high brilliance microfocus sealed tube with Mo-Kα radiation (0.71073 Å)
in omega and phi-scans. The structures were solved by dual methods. All
Zhang, Y. Zhang, J. Wang, J. Am. Chem. Soc. 2013, 135, 10330-
0333; g) L. Chu, F.-L. Qing, J. Am. Chem. Soc. 2012, 134, 1298-1304;
1
2
h) C. Feng, T.-P. Loh, Angew. Chem., Int. Ed. 2013, 52, 12414-12417;
i) D. M. Ferguson, J. R. Bour, A. J. Canty, J. W. Kampf, M. S. Sanford,
J. Am. Chem. Soc. 2017, 139, 11662-11665; j) Y. Gu, X. Leng, Q. Shen,
Nat. Commun. 2014, 5, 5405; k) X. Mu, S. Chen, X. Zhen, G. Liu,
Chem. Eur. J. 2011, 17, 6039-6042; l) X. Mu, T. Wu, H.-y. Wang, Y.-l.
Guo, G. Liu, J. Am. Chem. Soc. 2012, 134, 878-881.
were refined anisotropically on F . The methyl groups were refined using
rigid groups and the other hydrogens were refined using a riding mode.
Special features of refinement: (a) In 1 there was a poorly-resolved
region of residual electron density that was interpreted as a disorder over
2
two positions of the AuCF carbon atom (97%) and an iodine atom (3%).
Different sets of data were measured all of them showing the same
[
[
[
4]
5]
6]
a) A. G. Algarra, V. V. Grushin, S. A. MacGregor, Organometallics 2012,
problem. (b) In 2 the perfluorobutyl ligand was disordered over two
3
3
1
1, 1467-1476; b) D. A. Culkin, J. F. Hartwig, Organometallics 2004, 23,
398-3416; c) V. V. Grushin, W. J. Marshall, J. Am. Chem. Soc. 2006,
28, 4632-4641; d) G. G. Dubinina, W. W. Brennessel, J. L. Miller, D. A.
positions with
a ca. 51:49 occupancy distribution. (c) In 13 the
perfluorobutyl ligand of one of the two independent molecules was
disordered over two positions with a ca. 88:12 occupancy distribution. In
this case the atoms of the minor positions were refined as isotropic.
Crystal data and details about data acquisition and structure refinement
are included in the Supporting Information. CCDC 1913442 (1), 1913443
Vicic, Organometallics 2008, 27, 3933-3938; e) J. Jover, F. M.
Miloserdov, J. Benet-Buchholz, V. V. Grushin, F. Maseras,
Organometallics 2014, 33, 6531-6543; f) P. Anstaett, F. Schoenebeck,
Chem. Eur. J. 2011, 17, 12340-12346; g) S.-L. Zhang, L. Huang, L.-J.
Sun, Dalton Trans. 2015, 44, 4613-4622.
(
13), 1913444 (2), 1913445 (12), 1913446 (9), 1913447 (10), contain the
supplementary crystallographic data for this paper. These data are
provided free of charge by the Cambridge Crystallographic Data Centre.
a) V. V. Grushin, W. J. Marshall, J. Am. Chem. Soc. 2006, 128, 12644-
1
1
2645; b) S. I. Arlow, J. F. Hartwig, J. Am. Chem. Soc. 2017, 139,
6088-16091; c) D. M. Ferguson, J. R. Bour, A. J. Canty, J. W. Kampf,
M. S. Sanford, Organometallics 2019, 38, 519-526; d) V. I. Bakhmutov,
F. Bozoglian, K. Gómez, G. González, V. V. Grushin, S. A. Macgregor,
E. Martin, F. M. Miloserdov, M. A. Novikov, J. A. Panetier, L. V.
Romashov, Organometallics 2012, 31, 1315-1328; e) M. C. Nielsen, K.
J. Bonney, F. Schoenebeck, Angew. Chem., Int. Ed. 2014, 53, 5903-
Acknowledgements
Finantial support from Spanish Ministry of Science, Innovation
and Universities (Grant CTQ2015-69568-P, with FEDER
support) and Seneca Foundation of the Region of Murcia (Grant
5
906.
a) N. D. Ball, J. B. Gary, Y. Ye, M. S. Sanford, J. Am. Chem. Soc. 2011,
33, 7577-7584; b) N. D. Ball, J. W. Kampf, M. S. Sanford, J. Am.
1
9890/GERM/15, Programa de Ayudas a Grupos de Excelencia)
1
is gratefully acknowledged.
Chem. Soc. 2010, 132, 2878-2879; c) Y. Ye, N. D. Ball, J. W. Kampf, M.
S. Sanford, J. Am. Chem. Soc. 2010, 132, 14682-14687.
Keywords: fluorinated ligands • Gold • oxidative addition •
[7]
a) J. R. Bour, N. M. Camasso, E. A. Meucci, J. W. Kampf, A. J. Canty,
M. S. Sanford, J. Am. Chem. Soc. 2016, 138, 16105-16111; b) J. R.
Bour, N. M. Camasso, M. S. Sanford, J. Am. Chem. Soc. 2015, 137,
photochemical reactions • radicals
8
1
2
034-8037; c) N. M. Camasso, M. S. Sanford, Science 2015, 347,
218; d) E. A. Meucci, N. M. Camasso, M. S. Sanford, Organometallics
017, 36, 247-250.
[
1]
a) E. P. Gillis, K. J. Eastman, M. D. Hill, D. J. Donnelly, N. A. Meanwell,
J. Med. Chem. 2015, 58, 8315-8359; b) S. Purser, P. R. Moore, S.
Swallow, V. Gouverneur, Chem. Soc. Rev. 2008, 37, 320-330; c) Y.
Zhou, J. Wang, Z. Gu, S. Wang, W. Zhu, J. L. Aceña, V. A. Soloshonok,
K. Izawa, H. Liu, Chem. Rev. 2016, 116, 422-518; d) T. Fujiwara, D.
O’Hagan, J. Fluorine Chem. 2014, 167, 16-29; e) M. Hird, Chem. Soc.
Rev. 2007, 36, 2070-2095; f) P. Jeschke, Pest Manage. Sci. 2010, 66,
[
[
8]
9]
M. Paeth, S. B. Tyndall, L.-Y. Chen, J.-C. Hong, W. P. Carson, X. Liu, X.
Sun, J. Liu, K. Yang, E. M. Hale, D. L. Tierney, B. Liu, Z. Cao, M.-J.
Cheng, W. A. Goddard, W. Liu, J. Am. Chem. Soc. 2019, 141, 3153-
3
159.
a) S. Liu, K. Kang, S. Liu, D. Wang, P. Wei, Y. Lan, Q. Shen,
Organometallics 2018, 37, 3901-3908; b) M. D. Levin, T. Q. Chen, M. E.
Neubig, C. M. Hong, C. A. Theulier, I. J. Kobylianskii, M. Janabi, J. P.
O’Neil, F. D. Toste, Science 2017, 356, 1272; c) M. S. Winston, W. J.
Wolf, F. D. Toste, J. Am. Chem. Soc. 2014, 136, 7777-7782; d) M. S.
Winston, W. J. Wolf, F. D. Toste, J. Am. Chem. Soc. 2015, 137, 7921-
1
0-27.
[
2]
a) H. Wang, D. A. Vicic, Synlett 2013, 24, 1887-1898; b) S. Barata-
Vallejo, A. Postigo, Coord. Chem. Rev. 2013, 257, 3051-3069; c) T.
Furuya, A. S. Kamlet, T. Ritter, Nature 2011, 473, 470-477; d) T. Koike,
M. Akita, J. Fluorine Chem. 2014, 167, 30-36; e) B. Lantaño, M. R.
Torviso, S. M. Bonesi, S. Barata-Vallejo, A. Postigo, Coord. Chem. Rev.
7
928; e) S. Kim, F. D. Toste, J. Am. Chem. Soc. 2019, 141, 4308-4315.
2
015, 285, 76-108; f) C. Alonso, E. Martínez de Marigorta, G. Rubiales,
[
10] a) D. J. Burton, L. Lu, Top. Curr. Chem. 1997, 193, 45-89; b) R. P.
Hughes, Adv. Organomet. Chem. 1990, 31, 183-267; c) R. R. Burch, J.
C. Calabrese, J. Am. Chem. Soc. 1986, 108, 5359-5360; d) W. Tyrra, D.
F. Palacios, Chem. Rev. 2015, 115, 1847-1935; g) H. Egami, M.
Sodeoka, Angew. Chem., Int. Ed. 2014, 53, 8294-8308; h) T. Besset, T.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
Naumann, J. Fluorine Chem. 2004, 125, 823-830; e) H. Lange, D.
Naumann, J. Fluorine Chem. 1984, 26, 1-18; f) R. P. Hughes, T. Le
Husebo, B. J. Holliday, A. L. Rheingold, L. M. Liable-Sands, J.
Organomet. Chem. 1997, 548, 109-112; g) P. Liebing, F. Oehler, M.
Wagner, P. F. Tripet, A. Togni, Organometallics 2018, 37, 570-583; h)
P. J. Toscano, H. Brand, S. Liu, J. Zubieta, Inorg. Chem. 1990, 29,
[14] a) J. Gil-Rubio, J. Vicente, Dalton Trans. 2015, 44, 19432-19442; b) M.
Baya, A. Pérez-Bitrián, S. Martínez-Salvador, J. M. Casas, B. Menjón, J.
Orduna, Chem. Eur. J. 2017, 23, 1512-1515; c) A. Pérez-Bitrián, M.
Baya, J. M. Casas, L. R. Falvello, A. Martín, B. Menjón, Chem. Eur. J.
2017, 23, 14918-14930; d) A. Pérez-Bitrián, M. Baya, J. M. Casas, A.
Martín, B. Menjón, J. Orduña, Angew. Chem., Int. Ed. 2018, 57, 6517-
6521; e) A. Pérez-Bitrián, S. Martínez-Salvador, M. Baya, J. M. Casas,
A. Martín, B. Menjón, J. Orduna, Chem. Eur. J. 2017, 23, 6919-6929.
[15] a) N. O. Brace, J. Org. Chem. 1962, 27, 3027-3032; b) N. O. Brace, J.
Fluorine Chem. 1999, 93, 1-25.
2
101-2105; i) H. Huang, R. P. Hughes, A. L. Rheingold,
Organometallics 2010, 29, 1948-1955; j) R. P. Hughes, S. M. Maddock,
I. A. Guzei, L. M. Liable-Sands, A. L. Rheingold, J. Am. Chem. Soc.
2
001, 123, 3279-3288; k) B. L. Dyatkin, S. R. Sterlin, B. I. Martynov, E.
I. Mysov, I. L. Knunyants, Tetrahedron 1971, 27, 2843-2849; l) M. I.
Bruce, F. G. A. Stone in Fluorocarbon Complexes of Transition Metals,
Vol. 4 (Ed. W. L. Jolly), Interscience Publishers, Bristol, 1968, pp. 177-
[16] A. Johnson, R. J. Puddephatt, J. Chem. Soc., Dalton Trans. 1976,
1360-1363.
[17] F. Glockling, V. B. Mahale, J. Chem. Res., Synop. 1978, 170.
[18] P. W. N. M. Van Leeuwen, R. Kaftein, R. Huis, C. F. Roobeek, J.
Organomet. Chem. 1976, 104, C44-C46.
2
1
35; m) P. M. Treichel, F. G. A. Stone, Adv. Organomet. Chem. 1964, 1,
43-220; n) R. P. Hughes, J. S. Overby, A. Williamson, K.-C. Lam, T. E.
Concolino, A. L. Rheingold, Organometallics 2000, 19, 5190-5201; o) A.
Maleckis, M. S. Sanford, Organometallics 2014, 33, 3831-3839; p) R. P.
Hughes, J. T. Sweetser, M. D. Tawa, A. Williamson, C. D. Incarvito, B.
Rhatigan, A. L. Rheingold, G. Rossi, Organometallics 2001, 20, 3800-
[19] a) M. Blaya, D. Bautista, J. Gil-Rubio, J. Vicente, Organometallics 2014,
33, 6358-6368; b) U. Flörke, H.-J. Haupt, P. G. Jones, Acta Cryst. 1996,
C52, 611-613.
1
9
6
[20] The F nuclei of a c-C F11 group constitute a complex second order
3
810; q) R. P. Hughes, A. Williamson, C. D. Incarvito, A. L. Rheingold,
spin system (ADD'GG'JJ'MM'QX). However, owing to the broadening of
the signals, the three-, four- and five-bonds couplings were not resolved.
Organometallics 2001, 20, 4741-4744; r) P. Sgarbossa, A. Scarso, G.
Strukul, R. A. Michelin, Organometallics 2012, 31, 1257-1270; s) Y.
Suzaki, M. Kiho, K. Osakada, Organometallics 2017, 36, 1391-1397; t)
J. Gil-Rubio, J. Guerrero-Leal, M. Blaya, J. Vicente, D. Bautista, P. G.
Jones, Organometallics 2012, 31, 1287-1299; u) C. J. Bourgeois, S. A.
Garratt, R. P. Hughes, R. B. Larichev, J. M. Smith, A. J. Ward, S.
Willemsen, D. Zhang, A. G. DiPasquale, L. N. Zakharov, A. L.
Rheingold, Organometallics 2006, 25, 3474-3480.
Therefore, the CF
2
signals are simplified into broad doublets whose
2
splittings are approximately equal to the
J
F,F values.
[21] a) A. Dimitrov, U. Groß, S. Rüdiger, W. Storek, J. Burdon, J. Fluorine
Chem. 1996, 78, 1-5; b) J. Homer, L. F. Thomas, Trans. Faraday Soc.
1963, 59, 2431-2444.
[22] A. Foris, Magn. Reson. Chem. 2004, 42, 534-555.
[23] C. L. Bumgardner, J. C. Wozny, J. Fluorine Chem. 1978, 11, 527-535.
[24] A. B. Shtarev, F. Tian, W. R. Dolbier, B. E. Smart, J. Am. Chem. Soc.
1999, 121, 7335-7341.
[
11] a) M. M. Kremlev, A. I. Mushta, W. Tyrra, Y. L. Yagupolskii, D.
Naumann, M. Schäfer, Dalton Trans. 2015, 44, 19693-19699; b) A.
Lishchynskyi, V. V. Grushin, J. Am. Chem. Soc. 2013, 135, 12584-
[25] M. Osawa, M. Hoshino, D. Hashizume, Chem. Phys. Lett. 2007, 436,
89-93.
1
2587; c) N. D. Litvinas, P. S. Fier, J. F. Hartwig, Angew. Chem., Int.
Ed. 2012, 51, 536-539; d) M. Ohashi, N. Ishida, K. Ando, Y. Hashimoto,
A. Shigaki, K. Kikushima, S. Ogoshi, Chem. Eur. J. 2018, 24, 9794-
[26] RH, LAuX (X = Br, Cl) and other minor unidentified products were also
detected by NMR.
9
798; e) L. I. Panferova, F. M. Miloserdov, A. Lishchynskyi, M.
[27] Irradiation at 310 nm led to small amounts of LAuI (< 15%) and
unidentified fluoroorganic products, but most of the starting materials
remained unreacted.
Martínez-Belmonte, J. Benet-Buchholz, V. V. Grushin, Angew. Chem.,
Int. Ed. 2015, 54, 5218-5222; f) H. Serizawa, K. Aikawa, K. Mikami, Org.
Lett. 2014, 16, 3456-3459; g) K. Mikami, T. Murase, Y. Itoh, J. Am.
Chem. Soc. 2007, 129, 11686-11687; h) K. Aikawa, Y. Nakamura, Y.
Yokota, W. Toya, K. Mikami, Chem. Eur. J. 2015, 21, 96-100; i) P. T.
Kaplan, L. Xu, B. Chen, K. R. McGarry, S. Yu, H. Wang, D. A. Vicic,
Organometallics 2013, 32, 7552-7558; j) T. Kitazume, N. Ishikawa, J.
Am. Chem. Soc. 1985, 107, 5186-5191; k) X. Wang, K. Hirano, D.
Kurauchi, H. Kato, N. Toriumi, R. Takita, M. Uchiyama, Chem. Eur. J.
[28] A. Johnson, R. J. Puddephatt, J. Chem. Soc., Dalton Trans. 1975, 115-
120.
[29] R. T. Edidin, J. R. Norton, J. Am. Chem. Soc. 1986, 108, 948-953.
[30] a) A. Tamaki, J. K. Kochi, J. Organomet. Chem. 1973, 64, 411-425; b)
E. Mizushima, D. M. Cui, D. C. D. Nath, T. Hayashi, M. Tanaka, Org.
Synth. 2012, 89, 126.
[31] N. P. Mankad, F. D. Toste, Chem. Sci. 2012, 3, 72-76.
[32] C. Croix, A. Balland-Longeau, H. Allouchi, M. Giorgi, A. Duchêne, J.
Thibonnet, J. Organomet. Chem. 2005, 690, 4835-4843.
[33] D. V. Partyka, M. Zeller, A. D. Hunter, T. G. Gray, Inorg. Chem. 2012,
51, 8394-8401.
2
015, 21, 10993-10996; l) D. J. Burton, Z.-Y. Yang, Tetrahedron 1992,
8, 189-275.
4
[
[
12] a) M. C. Leclerc, J. M. Bayne, G. M. Lee, S. I. Gorelsky, M. Vasiliu, I.
Korobkov, D. J. Harrison, D. A. Dixon, R. T. Baker, J. Am. Chem. Soc.
2
015, 137, 16064-16073; b) R. Morales-Cerrada, C. Fliedel, J.-C.
Daran, F. Gayet, V. Ladmiral, B. Améduri, R. Poli, Chem. Eur. J. 2019,
5, 296-308.
13] a) R. P. Hughes, D. C. Lindner, J. Am. Chem. Soc. 1997, 119, 11544-
1545; b) R. P. Hughes, R. B. Larichev, L. N. Zakharov, A. L.
[34] R. J. Cross, M. F. Davidson, J. Chem. Soc., Dalton Trans. 1986, 411-
414.
2
[35] A. Toledo, I. Meana, A. C. Albéniz, Chem. Eur. J. 2015, 21, 13216-
13220.
1
[36] G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb, A.
Nudelman, B. M. Stoltz, J. E. Bercaw, K. I. Goldberg, Organometallics
2010, 29, 2176-2179.
Rheingold, Organometallics 2006, 25, 3943-3947; c) R. P. Hughes, R.
B. Laritchev, L. N. Zakharov, A. L. Rheingold, J. Am. Chem. Soc. 2004,
1
26, 2308-2309; d) R. P. Hughes, R. B. Laritchev, L. N. Zakharov, A. L.
Rheingold, J. Am. Chem. Soc. 2005, 127, 6325-6334.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201903058
FULL PAPER
Entry for the Table of Contents
FULL PAPER
Irradiation with a mild light source
Alejandro Portugués, Inmaculada
(
402 nm LED) can activate reactions
López-García, Javier Jiménez-Bernad,
Delia Bautista, and Juan Gil-Rubio*
between iodoperfluoroalkanes and
Au(I) organometallic complexes.
These reactions proceed through a
radical mechanism and have afforded
the first isolated of Au(I) or Au(III)
complexes containing perfluoroalkyl
chains, including rare
L
Au R + I RF
Page No. – Page No.
F
L
L
Au CF2
F
F
F
F
Photoinitiated Reactions of
Haloperfluorocarbons with Gold(I)
Organometallic Complexes.
Perfluoroalkyl Gold(I) and Gold(III)
Complexes
Au
F
F2C CF2
CF3
F
I
F
F F
L
Au CF2
Ar F2C CF2
CF3
F
perfluorocyclohexyl metal complexes.
R'C≡C RF
This article is protected by copyright. All rights reserved.