Activation of aryl halides at gold(i): Practical synthesis of (P,C) cyclometalated gold(III) complexes

Article abstract of DOI:10.1021/ja412432k

Taking advantage of phosphine chelation, direct evidence for oxidative addition of Csp²-X bonds (X = I, Br) to a single gold atom is reported. NMR studies and DFT calculations provide insight into this unprecedented transformation, which gives straightforward access to stable (P,C) cyclometalated gold(III) complexes.

Full text of DOI:10.1021/ja412432k

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Communication
Activation of Aryl Halides at Gold(I): Practical
Synthesis of (P,C) Cyclometallated Gold(III) Complexes
Johannes Guenther, Sonia Mallet-Ladeira, Laura Estévez,
Karinne Miqueu, Abderrahmane Amgoune, and Didier Bourissou
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja412432k • Publication Date (Web): 16 Jan 2014
Downloaded from http://pubs.acs.org on January 17, 2014
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Activation of Aryl Halides at Gold(I): Practical Synthesis of (P,C)
Cyclometallated Gold(III) Complexes
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Johannes Guenther,‡ Sonia Mallet–Ladeira,† Laura Estevez,# Karinne Miqueu,# Abderrahmane Am-
goune,‡* and Didier Bourissou‡*
‡Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier / CNRS UMR 5069, 118 Route de Nar-
bonne, 31062 Toulouse Cedex 09, France.
†Institut de Chimie de Toulouse (FR 2599), 118 Route de Narbonne, 31062 Toulouse Cedex 09, France
#Institut Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux, Equipe Chimie Physique. Université de Pau et
des Pays de l’Adour / CNRS UMR 5254, Hélioparc, 2 Avenue du Président Angot, 64053 Pau cedex 09, France
Supporting Information Placeholder
but the putative intermediate Au(III) species have not been char-
acterized.
ABSTRACT: Taking advantage of phosphine chelation, direct
evidence for oxidative addition of Csp2–X bonds (X = I, Br) to a
Our interest for elusive elementary steps at gold7,15,16 and
single gold atom is reported. NMR studies and DFT calculations
phosphine–assisted bond activation with late transition metals17
provide insight into this unprecedented transformation, which
prompted us to investigate the reaction of aryl–halides bearing
phosphine sidearms towards gold. As reported here, this strategy
has allowed us to obtain direct evidence for oxidative addition of
Csp2–X bonds (X = I, Br). The reactions proceed at a single metal
center under relatively mild conditions. The resulting gold(III)
complexes have been authenticated crystallographically and the
CAr–X oxidative addition process has been investigated by spec-
troscopic and computational means. Such phosphine–directed
CAr–X activation reactions also possess synthetic interest, giving
straightforward access to a novel class of thermally robust cyc-
lometallated gold(III) complexes.
gives straightforward access to stable (P,C) cyclometallated
gold(III) complexes.
The activation of Csp2–halide bonds (C–X) with transition met-
als plays a pivotal role in catalytic cross–coupling reactions. This
oxidative addition process represents the first step of the catalytic
cycles and as such, it is a well–established transformation, espe-
cially with late transition metals.1 In this regard, the coinage
metals, and gold in particular, stand as striking exceptions, oxida-
tive addition of Csp2–X bonds to gold being considered highly
disfavoured, if not impossible.2,3
The study of phosphine–chelated CAr–X bond activation at gold
was initiated with 8–halo naphthyl phosphines 1.18 The naphthyl
backbone was envisioned to place the metal center and CAr–X
bond in close proximity.19 To start with, the 8–iodo naphthyl
phosphine 1a was reacted with AuI in dichloromethane at room
temperature. Surprisingly, oxidative addition of the CAr–I bond
proceeds readily under these conditions to give the
cyclometallated gold(III) complex 3a. 31P NMR monitoring re-
vealed that the coordination of the phosphorus atom to gold oc-
curs instantaneously to give the phosphine gold(I) complex 2a
(31P NMR, = 35.4 ppm). Then, complex 2a is gradually and
cleanly converted into 3a (31P NMR= 51.8 ppm). The for-
mation of the gold(III) complex is complete within 24 h at 25 °C
and follows first–order kinetics (Figure 1, left), in agreement with
an intramolecular unimolecular process.20 Upon heating, the
transformation of 2a into 3a is significantly accelerated (complete
conversion within 2–3 hours at 55 °C). The first–order rate con-
stant kobs value was determined at different temperatures and the
activation parameters for the oxidative addition of the CAr–I bond
were derived from an Eyring plot: H = 25 ± 4 kcal/mol and S
= 12 ± 10 cal/K.mol (Figure S3).
In fact, the seminal work by Corma et al. on gold–catalyzed
Sonogashira coupling reactions4 has stimulated considerable
interest and raised a lively debate5 about the ability of gold to
undergo oxidative addition of iodoarenes.6,7 Due to the supported
nature of the involved catalysts, it is hardly possible to identify
unequivocally the species that activate the Csp2–X bond and how
this proceeds.8 Nevertheless, significant progress has been
achieved thanks to advanced experimental and theoretical studies
and the ability of multinuclear gold species to activate iodoben-
zene has been demonstrated for gold nanoparticles,5c,9 small gold
clusters10 as well as gold surfaces.11 In parallel, few recent studies
have explored the reaction of well–defined mononuclear gold
complexes with Csp2–X bonds. No direct evidence for oxidative
addition of Csp2–X bonds at a single gold center has been obtained
so far,12,13 but valuable insights have been gained.2c The reaction
of iodobenzene with phosphine gold cations in the gas phase was
recently examined using mass–spectrometry experiments and
DFT calculations.10 Bisligated complexes such as [(R3P)2Au+] (R
= Me, Ph) were shown not to react with iodobenzene, while under
the same conditions, the corresponding monoligated species
[(R3P)Au+] form 1:1 adducts that subsequently fragment into the
corresponding phosphonium ion [R3PPh]+ and AuI. Reaction of
the (IMes)AuPh complex (IMes = N,N’–bis(mesityl) imidazol–2–
ylidene) with iodobenzene has also been investigated and com-
plete conversion into biphenyl and (IMes)AuI was observed after
50 hours at 110 °C in benzene solution.14 The two latter transfor-
mations may involve oxidative addition of iodobenzene to gold,
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Scheme 1. Coordination of the 8–iodo naphthyl phosphine 1a:
spontaneous oxidative addition of the CAr–I bond to gold.
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Both complexes 2a and 3a have been characterized by multi–
nuclear NMR spectroscopy. Most indicative of the oxidative
addition are the disappearance of the 13C NMR resonance signal
corresponding to the C–I atom at  92.6 ppm in 2a (d, JPC = 5.9
Scheme 2. Coordination of the 8–bromo/chloro naphthyl
phosphines 1b/1c to gold: oxidative addition of the CAr–Br bond
to gold.
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Hz) and the appearance of a new signal at  153.8 ppm (d, JPC
=
The computed values of G = 21.9 kcal/mol and H = 21.6
kcal/mol for CAr–I activation are in good agreement with the
activation parameters determined by NMR.20 The geometric
features of the transition state connecting 2a* and 3a* deserve
comment: the cleavage of the C–I1 bond is advanced (2.58 Å, vs
2.12 Å in 2a*), the Au–C1 bond formation is well–developed
(2.154 Å) and the P–Au–I2 fragment is noticeably bent (138.7°).
The P, C and I2 atoms are organized in a Y–shape arrangement
around gold, and I1 stands above this trigonal plane, rather far
away from gold (AuI1 = 3.041 Å, rcov = 2.75 Å).23
7.2 Hz) for the peri–carbon atom bond to gold in 3a. The molecu-
lar structure of 3a was confirmed by single crystal X–ray diffrac-
tion analysis (Figure 1, right). The gold atom is tetracoordinated
with the two iodine atoms and the five–membered (P,C) chelate
organized in a quasi–ideal square–planar arrangement (bond
angles deviate by less than 8°). The most noticeable distortion is
the 5–6° tilt of the C–P bond towards Au in order to accommodate
a relatively short PAu distance [2.284(1) Å].21
Figure 1. Plot of ln[2a] vs time at 40 °C, indicating first–order
behavior (left). Molecular structure of complex 3a in the solid
state (right). Ellipsoids set at 50 % probability; hydrogen atoms
omitted for clarity. Selected bond lengths [Å] and angles [°]: Au–
C1 2.070(4); Au–P 2.284(1); Au–I1 2.6288(3); Au–I2 2.6621(3);
C1–Au–P 84.4(1); C1–Au–I1 96.1(1); C1–Au–I2 172.2(1); P–
Au–I1 175.06(3); P–Au–I2 89.72(2); I1–Au–I2 90.23(1).
Figure
2.
Energy
profile
computed
at
the
B3PW91/SDD+pol(Au,I),6-31G**(other atoms) level of theory
for the oxidative addition of the CAr-I bond to gold. Free energy
ΔG at 25 °C including ZPE correction (kcal/ mol). Enthalpy
values are given in brackets.
Calculations predict a similar pathway for the oxidative addi-
tion of the C–Br and C–Cl bonds of 2b,c*, but the corresponding
energy maps differ significantly from one halogen to the other
(Figure S30 and S31). Oxidative addition of the C–Br is ender-
gonic by 7.2 kcal/mol and the associated activation barrier (G =
32.1 kcal/mol) is substantially higher than that of C–I bond activa-
tion, but remains accessible upon heating. In accordance with
experimental results, activation of the CAr–Cl bond (2c*3c*) is
slightly endergonic (G = 0.5 kcal/mol at 25 °C) and involves a
prohibitively high activation barrier (G = 39.7 kcal/mol). The
formation of complexes 3a and 3b provide the first direct evi-
dence for CAr–X (X = I, Br) oxidative addition at a single gold
center. Besides its fundamental relevance, this transformation is
interesting synthetically as it gives direct access to well–defined
stable (P,C) gold(III) complexes. Cyclometallation is known to
impart high thermal stability to gold(III) complexes by preventing
undesirable reductions. Gold(III) complexes deriving from (C,N)
ligands have recently attracted much interest,24 on their own25 as
well as for therapeutic,26 luminescent27 and catalytic applica-
tions.28 However, synthetic issues hamper further development in
this area. Direct cyclometalation of N–ligands may be achieved by
C–H activation with gold(III) precursors.29–31 But this route is far
from general and most (C,N) gold(III) complexes are in fact
prepared by a multi–step process involving transmetallation from
The formation of 3a clearly benefits from phosphine chelation,
but the oxidative addition of the CAr–I bond of 1a is unexpectedly
easy. This prompted us to explore the behavior of the related
ligands 1b and 1c featuring CAr–Br and CAr–Cl bonds. The corre-
sponding gold(I) complexes 2b and 2c were readily prepared upon
reaction with [AuX(SMe2)] (X = Br, Cl) at room temperature
(Scheme 2).22 Complex 2c (X = Cl) was heated in xylene but
oxidative addition of the CAr–Cl bond did not occur even after
several hours at 130 °C. In contrast, the CAr–Br bond of complex
2b is activated under the same conditions and the thermally stable
gold(III) dibromide complex 3b is obtained in quantitative yield.
Cyclometallation of the naphthyl phosphine is unambiguously
supported by the diagnostic NMR signals found at  31P = 66.9
ppm and  13C = 152.6 ppm (d, JPC = 6.4 Hz, C–Au).
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organomercury salts.24,32 Alternative routes to cyclometallated
gold(III) complexes are thus highly desirable and phosphine–
1
directed CAr–X oxidative addition appears attractive to this end.
With the aim to illustrate further the synthetic potential of this
approach, we became interested in reacting diphosphine ligands of
type 4 with gold(I) precursors. The scarcity of (P,C) cyclometal-
lated Au(III) species,33,34 combined with the interest for Au(III)
pincer complexes make (P,C,P)–chelated Au(III) complexes
particularly appealing targets. Gratifyingly, reaction of 4 with
[AuBr(SMe2)] in toluene at 60 °C resulted in the coordination of
the two phosphines and oxidative addition of the CAr–Br bond
(Scheme 3).34 The ensuing Au(III) complex 5 was isolated in 87%
yield. It is stable to air (no sign of decomposition detected after
several days). Its (P,C,P) pincer structure is clearly apparent from
the NMR signals at  31P = 49.8 ppm and  13C 160.8 ppm (C–Au,
t, JPC = 4.7 Hz).
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Figure 3. Molecular view of complex 5 in the solid state. Ellip-
soids set at 50 % probability; hydrogen atoms and solvate mole-
cules omitted for clarity. Selected bond lengths [Å] and angles [°]:
Au–C1 2.060(4); Au–P1 2.329(1); Au–P2 2.329(1); Au–Br1
2.5179(5); Au–Br2 2.9945(5); P1–Au–P2 160.43(4); C1–Au–Br1
171.9(1); C1–Au–Br2 92.7(1); C1–Au–P1 81.7(1); C1–Au–P2
83.5(1); P1–Au–Br1 94.08(3); P1–Au–Br2 87.93(3); P2–Au–Br1
98.98(3); P2–Au–Br2 105.48(3); Br1–Au–Br2 94.14(2).
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Scheme 3. Synthesis of the (PCP) gold(III) pincer complex 5 by
CAr–Br oxidative addition to gold.
In addition, single crystals of 5 were grown by slow evapora-
tion of a CH3CN solution at room temperature and an X–ray
diffraction study was performed (Figure 3). The gold center is
organized in a slightly distorted square–planar geometry [P1–Au–
P2 160.43(4)° and C1–Au–Br1 171.9(1)°] and the two phosphines
are tightly bound to gold [Au–P1 and Au–P2 2.329(1) Å]. The
bromide counter–anion sits in apical position and only weakly
interacts with the metal (AuBr2 = 2.9946 Å).37 Intrigued by the
influence that the two phosphine sidearms may have on the CAr–
Br oxidative addition, we examined the formation of complex 5
by DFT.21 Accordingly, bidentate coordination of the two phos-
phorus atoms of 4 (complex 4*–AuBr) was found to precede
facile CAr–Br oxidative addition to gold (G = 16.3 kcal/mol)
(Figure 4). An alternative mechanism involving chelation by only
one of the phosphine sidearm was also considered. The corre-
sponding complex 4**–AuBr is slightly more stable than the
chelate structure (3.5 kcal/mol), but the activation barrier for the
CAr–Br bond activation is much larger (G = 39.2 kcal/mol).
These calculations substantiate the beneficial effect of the second
phosphine sidearm whose coordination facilitates the oxidative
addition process leading to complex 5. The chelate system is quite
unique in that respect, since so far, increasing the coordination
number of gold ([(R3P)nAu+] with n>1) has been predicted to
disfavor oxidative addition.10
Figure 4. Energy profile computed at the B3PW91/
SDD+pol(Au,I),6-31G**(other atoms) level of theory for the
oxidative addition of the CAr-Br bond to gold upon coordination
of 4 to gold. Free energy ΔG at 25 °C including ZPE correction
(kcal/mol). Enthalpy values are given in brackets.
ASSOCIATED CONTENT
Supporting Information
Detailed experimental conditions and procedures, theoretical
details, and analytical data and crystallographic data (CIF) for
compounds 3a and 5. This material is available free of charge
via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
amgoune@chimie.ups–tlse.fr; dbouriss@chimie.ups–tlse.fr
Notes
The authors declare no competing financial interests.
In conclusion, the results described herein demonstrate that
mononuclear gold complexes can undergo oxidative addition of
aryl–iodides and –bromides. Such phosphine–directed CAr–X
bond activations provide straightforward access to hitherto un-
known (P,C) and (P,C,P) cyclometallated Au(III) complexes. The
properties and reactivity of the latter species are under active
investigation in our group. Future work will also seek to deter-
mine if oxidative addition of CAr–X bonds can be achieved
intermolecularly at gold.
ACKNOWLEDGMENT
Financial support from the Centre National de la Recherche
Scienti ique, the Université de oulouse, and the Agence
Nationale de la Recherche (ANR–10–BLAN–070901) is
acknowledged. The theoretical work was granted access to HPC
resources of Idris under Allocation 2013 (i2013080045) made by
Grand Equipement National de Calcul Intensif (GENCI). IPREM
from the Université de Pau is also acknowledged for calculation
facilities
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(31)
phosphines since gold(III) salts oxidize phosphines.
(32) Wong, K. H.; Cheung, K. K.; Chan, M. C.-W.; Che, C. M. Or-
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(8)
(9)
Crabtree, R. H. Chem. Rev. 2011, 112, 1536.
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This strategy is not applicable to the cyclometallation of
(33)
Halogenation of ortho–vinyl phenylphosphine gold(I) com-
plexes was reported to give six–membered cyclometallated gold(III)
complexes, see: Bennett, M. A.; Hoskins, K.; Kneen, W. R.; Nyholm, R.
S.; Hitchcock, P. B.; Mason, R.; Robertson, G. B.; Towl, A. D. C. J. Am.
Chem. Soc. 1971, 93, 4591.
(13)
For a computational study of Csp2–F bond activation at gold,
see: Lv, H.; Zhan, J. H.; Cai, Y. B.; Yu, Y.; Wang, B.; Zhang, J. L. J. Am.
Chem. Soc. 2012, 134, 16216.
(14)
M.; Ahlquist, M. S. G.; Wendt, O. F. Chem. Sci. 2011, 2, 2373.
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Bourissou, D. Angew. Chem. Int. Ed. 2013, 52, 7160.
(16)
hydride abstractions in gold alkyl complexes, see: Ung, G.; Bertrand, G.
Angew. Chem. Int. Ed. 2013, 52, 11388.
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Johnson, M. T.; Marthinus Janse van Rensburg, J.; Axelsson,
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For (P,C) cyclometallated polynuclear complexes, see: Ben-
nett, M. A.; Hockless, D. C. R.; Rae, A. D.; Welling, l. L.; Willis, A. C.
Organometallics 2001, 20, 79.
(35)
[AuCl(SMe2)] resulted in the formation of the corresponding three–
coordinate diphosphine–AuCl complex without activation of the CAr–Cl
bond.[20]
In contrast, the reaction of the arylchloride analogue of 4 with
Bertrand et al. have reported the first examples of – and –
(36)
The geometry of 5 is similar to that of [AuPhCl2(PPh3)2], that
(a) Derrah, E. J.; Ladeira, S.; Bouhadir, G.; Miqueu, K.; Bou-
was prepared in two steps, C–H activation of benzene with [AuCl3]2
followed by PPh3 coordination, see: Lavy, S.; Miller, J. J.; Pazicky, M.;
Rodrigues, A. S.; Rominger, F.; Jäkel, C.; Serra, D.; Vinokurov, N.;
Limbach, M. Adv. Synth. Catal. 2010, 352, 2993.
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Mallet-Ladeira, S.; Miqueu, K.; Bouhadir, G.; Bourissou, D. Organome-
tallics 2013, 32, 1121.
(18)
The coordination of 8–fluoro naphthyl phosphines to gold has
been recently studied by Togni et al. in the context of remote C–F···Au
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