C(sp2)-C(sp2) Reductive Elimination from Well-Defined Diarylgold(III) Complexes

Article abstract of DOI:10.1021/acs.organomet.7b00588

A series of well-defined phosphine-ligated diarylgold(III) complexes cis-[Au(L)(Ar_F)(Ar′)(Cl)] were prepared, and detailed kinetics of the C(sp²)-C(sp²) reductive elimination from these complexes were studied. The mechanism of the reductive elimination from the complexes cis-[Au(L)(Ar_F)(Ar′)(Cl)] was further studied by theoretical calculations. The combination of experimental and theoretical results suggests that the biaryl reductive elimination from organogold(III) complexes cis-[Au(L)(Ar_F)(Ar′)(Cl)] proceeds through a concerted biaryl-forming pathway from the four-coordinated Au(III) metal center. These studies also disclose that the steric hindrance of the phosphine ligands plays a major role in promoting the biaryl-forming reductive elimination from diarylgold(III) complexes cis-[Au(L)(Ar_F)(Ar′)(Cl)], while electronic properties of these ligands have a much smaller effect. Futhermore, it was found that the complexes with more weakly electron withdrawing aryl ligands undergo reductive elimination more quickly and the elimination rate is not sensitive to the polarity of the solvents.

Full text of DOI:10.1021/acs.organomet.7b00588

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Cite This: Organometallics XXXX, XXX, XXX-XXX
C(sp2)−C(sp2) Reductive Elimination from Well-Defined Diarylgold(III)
Complexes
Kai Kang,† Shuanshuan Liu,‡ Ting Xu,§ Decai Wang,‡ Xuebing Leng,† Ruopeng Bai,§ Yu Lan,*,§
and Qilong Shen*,†
†Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences,
Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People’s Republic of China
‡Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing, Jiangsu Province 210009, People’s Republic of
China
§School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, People’s Republic of China
S
* Supporting Information
ABSTRACT: A series of well-defined phosphine-ligated diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)] were prepared,
and detailed kinetics of the C(sp2)−C(sp2) reductive elimination from these complexes were studied. The mechanism of the
reductive elimination from the complexes cis-[Au(L)(ArF)(Ar′)(Cl)] was further studied by theoretical calculations. The
combination of experimental and theoretical results suggests that the biaryl reductive elimination from organogold(III)
complexes cis-[Au(L)(ArF)(Ar′)(Cl)] proceeds through a concerted biaryl-forming pathway from the four-coordinated Au(III)
metal center. These studies also disclose that the steric hindrance of the phosphine ligands plays a major role in promoting the
biaryl-forming reductive elimination from diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)], while electronic properties of
these ligands have a much smaller effect. Futhermore, it was found that the complexes with more weakly electron withdrawing
aryl ligands undergo reductive elimination more quickly and the elimination rate is not sensitive to the polarity of the solvents.
bonds.7,8 However, unlike other d8 transition-metal catalysts,
INTRODUCTION
Reductive elimination that forms new C−H, C−C, or C−X
■
fundamental studies on reductive elimination from analogous
square-planar d8 Au(III) centers lag far behind,9 even though
bonds from two covalent ligands at a transition-metal center is
the seminal mechanistic studies on C(sp3)−C(sp3) reductive
generally considered as a key product-forming elementary
reaction in homogeneously catalyzed organic reactions and
elimination from well-defined trialkylgold(III) complexes by
Kochi and co-workers10 date back to the early 1970s. Only
recently, organogold(III) complexes that are able to undergo
reductive elimination to form C(sp2)−C(sp2),11 C(sp2)−N,12
C(sp3)−X, and C(sp2)−X (X = halogen)13 bonds were
identified and the underlying factors that facilitate the reductive
elimination started to be uncovered. More specifically, studies
on biaryl-forming reductive elimination from organogold(III)
complexes remain rather limited. In 1991, Vicente and co-
workers reported that, in the presence of PPh3 or a
combination of PPh3/NaClO4, the complexes [Au(Ar′)(Ar)-
metal-mediated stoichiometric transformations.1−3 Over the
past 40 years, extensive studies on the reductive elimination of
biaryls from square-planar d8 metal centers such as nickel(II),4
palladium(II),5 and platinum(II)6 have been conducted, and it
is well-established that the rates of the reductive elimination
reactions are dramatically affected by the steric hindrance and
electronic effects of both the ancillary ligands and reactive
ligands. These fundamental mechanistic insights have, in turn,
enabled the development of high-performance catalytic cross-
coupling reactions.1
Recently, gold-catalyzed cross-coupling reactions through
AuI/AuIII redox cycles have emerged as a new and
complementary tool for the construction of carbon−carbon
Received: August 1, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.7b00588
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Article
(Cl)] underwent facile biaryl reductive elimination at room
temperature.11a The addition of 2 equiv of PPh3 did not inhibit
the reaction. On the basis of these observations, a concerted
C(sp2)−C(sp2) reductive elimination mechanism from a four-
coordinated gold(III) complex was proposed. A similar example
of a C(sp2)−C(sp3) mechanism was also reported by this
group.11b In 2014, Nevado and co-workers showed that the
diarylgold(III) complex cis-[Au(PPh3)(C6F5)2(Cl)] was rather
stable and forcing conditions (150 °C) were required to
promote the biaryl reductive elimination.11c Likewise, You and
co-workers demonstrated that biaryl reductive elimination from
[Au(tpy)(Ph)(Br)] (tpy = 2-o-tolylpyridine) in tBuOH
occurred smoothly at 80 °C in 98% yield.11d In both cases,
the detailed mechanism for the elemental reaction was not
studied. Toste and co-workers reported, on the basis of kinetic
experiments at −52 °C, that biaryl reductive elimination from
the in situ formed diarylgold(III) species cis-[Au(Ph3P)(4-F-
C6H4)2(Cl)] proceeds through a concerted pathway, while the
reaction rate increased significantly from the ionic four-
coordinated diarylgold(III) species [cis-(Ph3P)2Au(4-F-
C6H4)2]+Cl− which formed upon the addition of excess
PPh3.11e This mechanistic rationale was further supported by
DFT calculations.11f More recently, Lloyd-Jones and co-
workers revealed that the rates of the intramolecular biaryl
reductive elimination from the putative organogold(III)
intermediates were accelerated by electron-donating substitu-
ents on the aryl rings, while longer and more flexible tethers
between two aryl rings also resulted in faster eliminations.14
Nevertheless, these studies mainly focused on identifying the
appropriate conditions to promote biaryl-forming reductive
elimination from the Au(III) complexes or kinetic studies of
reductive elimination from the in situ formed Au(III)
complexes that were identified by 31P and 19F NMR
spectroscopy. Fundamental studies to probe the steric and
electronic effects of the ancillary ligand on the biaryl-forming
reductive elimination from well-defined organogold(III)
complexes remain unexplored.
Thus, studies to understand the relative effects of ligand
steric and electronic properties on the rates of the C(sp2)−
C(sp2) bond-forming reductive elimination from well-defined
organogold(III) complexes not only will provide fundamental
insights into factors that govern the bond-forming process but
also could help to reduce experimental efforts during the
development of new transition-metal-catalyzed reactions. In
this paper, we report crystallographic, kinetic, and theoretical
data that illuminate the steric and electronic factors of the
ligands on the C(sp2)−C(sp2) bond-forming reductive
elimination from a series of well-defined diarylgold(III)
complexes cis-[Au(L)(ArF)(Ar′)(Cl)]. Our studies showed:
(1) Biaryl reductive elimination from organogold(III) com-
plexes cis-[Au(L)(ArF)(Ar′)(Cl)] proceeds through a con-
certed pathway from the four-coordinate Au(III) metal center.
(2) Steric hindrance of the phosphine ligand plays a major role
in promoting the biaryl reductive elimination from organogold-
(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)], while electronic
properties of these ligands have a much smaller effect. (3) The
rates of biaryl reductive elimination from organogold(III)
complexes cis-[Au(L)(ArF)(Ar′)(Cl)] were not sensitive to the
polarity of the solvents. (4) Diarylgold(III) complexes with
more electron withdrawing aryl ligands undergo reductive
elimination more quickly.
RESULTS
■
Synthesis and Characterization of Phosphine-Ligated
Diarylgold(III) Complexes cis-[Au(L)(ArF)(Ar′)(Cl)] (3a−j).
To study the biaryl reductive elimination from organogold(III)
complexes, we were facing a considerable challenge that
requires the generation of the organogold(III) complexes
with two cis aryl groups. We thus first developed a method for
the preparation of these complexes, as summarized in Table 1.
Table 1. Synthesis of Phosphine-Ligated Diarylgold(III)
Complexes cis-[Au(L)(ArF)(Ar′)(Cl)] (3a−j)
a
complex, yield (%)
entry
ligand
Ar′
C6F5
2
3
1
2
3
L = PCy3
2a, 23
2b, 80
2c, 63
3a, 56
3b, 54
3c, 62
t
L = PCy2 Bu
L = PCytBu2
L = P(p-X-C6H4)tBu2
X = OMe
C6F5
C6F5
4
5
6
7
8
C6F5
C6F5
C6F5
C6F5
C6F5
2d, 62
2e, 99
2f, 70
2g, 71
2h, 47
3d, 54
3e, 68
3f, 45
3g, 53
3h, 53
X = Me
X = H
X = Cl
X = CF3
L = PPhtBu2
L = PPhtBu2
L = PPhtBu2
9
p-H-C6F4
3i, 55
3j, 67
10
p-CF3-C6F4
a
Treatment of [Au(L)(Cl)] with 2,2′,3,3′,5,5′,6,6′-octafluoro-
1,1′-biphenyl in the presence of Ag2O, K2CO3, and tBuCO2H,15
followed by oxidation of the resulting [Au(L)(ArF)] (1a−h)
13d,16
with PhICl2
in CHCl3 generated the Au(III) complexes
cis-[Au(L)(ArF)Cl2] (2a−h) in 23−99% yields. Phosphine-
ligated diarylgold(III) complexes 3a−h were then obtained by
reaction of complexes 2a−h with in situ formed C6F5Ag17 by
mixing C6F5TMS with AgF in anhydrous acetonitrile. The
phosphine-ligated diarylgold(III) complexes were isolated as
white solids in 45−68% yields, respectively. Likewise,
complexes 3i,j were synthesized using the corresponding
TMS(p-H-C6F4) or TMS(p-CF3-C6F4) as the aryl sources.
Complexes 3a−j were fully characterized by H, 19F, and 31P
1
NMR, as well as elemental analysis. The structures of these
complexes were determined to have a cis-biaryl configuration.
The formation of cis-diarylgold(III) complexes was mainly due
to the stronger trans effect of the phosphine group in
comparison to that of the polyfluorinated aryl group and the
Au−Cl bond trans to the phosphine ligand is weaker than the
Au−Cl bond trans to the polyfluorinated aryl group. For
example, the bond distance (2.3222(17) Å) of the Au−Cl bond
trans to the phosphine ligand in cis-[Au(PPh3)(ArF)(Cl)2] (2i)
is slightly longer than that of the Au−Cl bond trans to the
polyfluorinated aryl group (2.3179(16) Å). Complexes 3a−j
are not air and moisture sensitive. No detectable decomposition
was observed after more than 2 months of storage on the shelf
B
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Figure 1. ORTEP diagrams of diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)] (3b,d,f). Ellipsoids are shown at the 50% probability level.
at ambient temperature. These complexes are also stable in
solution at room temperature. For example, no decomposition
was observed even after 24 h at room temperature when
complex 3f was dissolved in CCl4, CDCl3, THF, toluene,
nitrobenzene, DMF, or CH3CN, as determined by 19F NMR
spectroscopy.
X-ray Structures of Phosphine-Ligated Diarylgold(III)
Complexes cis-[Au(L)(ArF)(Ar′)(Cl)]. Recrystallization of
complexes 3a−f,h−j by slow diffusion of n-pentane into a
CH2Cl2 solution of diarylgold(III) complexes at room temper-
ature gave single crystals that were suitable for analysis by X-ray
diffraction. The ORTEP diagrams of phosphine-ligated
diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)] (3b,d,f)
are shown in Figure 1, and the structures of complexes
(3a,c,e,h−j) are included in the Supporting Information.
Selected bond distances and angles of complexes 3a−f,h−j
are collected in Table 2. In general, the Au−P bond distance in
indicating that the gold−aryl covalent bonds tend to be
stronger for aryl ligands that are less electron donating.
As summarized in Table 3, the sums of the four angles
around the Au(III) center in these complexes are between
359.98 and 360.71°, demonstrating the square-planar config-
uration of the gold metal center. The C(ArF)−Au−P bond
angles in complexes 3a−c (95.36(15)/93.46(16), 97.06(11),
and 99.1(8)/98.9(7)°, respectively) increased with the growth
in the steric hindrance of the corresponding phosphine ligand
t
(PCy3, PCy2 Bu, and PCytBu2). To compare the steric
hindrance of the phosphine ligands in complexes 3a−f,h−j
quantitatively and more accurately, we use the Cl−Au−C(ArF)
bond angle to reveal the steric effects of the phosphine ligands
in these Au(III) complexes. A smaller Cl−Au−C(ArF) bond
angle suggests greater steric hindrance of the corresponding
ligand. As illustrated in Table 2, the Cl−Au−C(ArF) bond
angles in complexes 3a−c (173.89/174.31, 171.27, and 170.5/
169.4°, respectively) decrease with an increase in the steric
hindrance of the corresponding phosphine ligands of PCy3,
Table 2. Selected Intramolecular Bond Distances Involving
the Non-Hydrogen Atoms of cis-[Au(L)(ArF)(Ar′)(Cl)]
(3a−f,h−j)
PCy2 Bu, and PCytBu2.
t
C(sp2)−C(sp2) Reductive Elimination from cis-[Au(L)-
(ArF)(Ar′)(Cl)] (3a−j). No decomposition of cis-[Au(PCy3)-
(ArF)(C6F5)(Cl)] (3a) was observed when it was heated in
CDCl3 at 120 °C for 2 h (Table 4, entry 1). The same reaction
conducted at 150 °C for 4 h generated the corresponding
reductive elimination product biaryl 4 in quantitative yield
bond distance (Å)
complex
Au−P
Au−Cl
Au−C(ArF)
Au−C(Ar′)
3a
2.3873(14)
2.3878(15)
2.4083(10)
2.446(8)
2.3291(16)
2.3271(15)
2.3151(11)
2.304(7)
2.025(5)
2.023(5)
2.026(4)
2.04(3)
2.077(5)
2.062(5)
2.059(4)
2.07(3)
t
3b
3c
(Table 4, entry 2). Thermolysis of cis-[Au(PCy2 Bu)(ArF)-
(C6F5)(Cl)] (3b) in CDCl3 at 100 °C for 2 h gave biaryl 4 in
23% yield, while heating at 120 °C for 2 h led to 86%
conversion of complex 3b and 82% yield of biaryl 4 (Table 4,
entry 3). Reductive elimination from a diarylgold(III) complex
ligated with a more sterically hindered phosphine ligand such as
PCytBu2 was much faster in comparison to those ligated with
2.426(8)
2.320(7)
2.06(3)
2.11(3)
3d
3e
3f
2.4162(15)
2.4169(12)
2.431(2)
2.3148(13)
2.3344(11)
2.327(2)
2.022(4)
2.070(4)
2.049(9)
2.048(5)
2.058(6)
2.053(5)
2.068(5)
2.046(4)
2.030(9)
2.062(5)
2.042(6)
2.030(5)
3h
3i
2.4155(15)
2.4385(17)
2.4326(13)
2.3205(15)
2.3302(16)
2.3325(12)
t
PCy3 or PCy2 Bu. Thermolysis of the complex cis-[Au-
3j
(PCytBu2)(ArF)(C6F5)(Cl)] (3c) in CDCl3 at 85 °C occurred
with full conversion after 2 h to give the reductive elimination
product biaryl 4 in over 95% yield, as determined by 19F NMR
spectroscopy (Table 4, entry 4). Likewise, thermolysis of di-
tert-butyl(aryl)phosphine-ligated organogold(III) complexes
cis-[Au(P(p-X-C6H4)tBu2)(ArF)(C6F5)(Cl)] (3d−h) in CDCl3
at 85 °C generated biaryl 4 in quantitive yields as well (Table 4,
entries 5−9). Reductive elimination from a diarylgold(III)
complex ligated with PtBu3 was much faster. The formation of
biaryl 4 was observed in 81% yield after 8 h at room
temperature when cis-[Au(PtBu3)(ArF)Cl2] was treated with a
complexes 3a−c (2.3873(10)/2.3878(15), 2.4083(10), and
2.446(8)/2.426(8) Å, respectively) showed an increasing trend
because of the increased steric hindrance of the corresponding
t
phosphine ligands (PCy3, PCy2 Bu, and PCytBu2) in these
complexes. Complexes 3f,i,j were ligated by the same
phosphine ligand (PhPtBu2), wherein the Au−C(Ar′) bond
distances in complex 3f (Ar′ = C6F5) and 3j (Ar′ = p-CF3-
C6F4) (2.030(5) and 2.030(9) Å, respectively) are slightly
shorter than that in complex 3i (2.042(6) Å, Ar′ = p-H-C6F4),
C
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Table 3. Selected Intramolecular Bond Angles Involving the Non-Hydrogen Atoms of cis-[Au(L)(ArF)(Ar′)(Cl)] (3a−f,h−j)
bond angle (deg)
complex
P−Au−C(Ar′)
C(ArF)−Au−P
C(ArF)−Au−C(Ar′)
Cl−Au−C(ArF)
3a
174.21(17)
172.72(17)
177.09(11)
175.2(7)
95.36(15)
93.46(16)
97.06(11)
99.1(8)
86.6(2)
173.89(14)
174.31(16)
171.27(11)
170.5(8)
86.4(2)
3b
3c
85.28(15)
85.7(10)
85.3(10)
86.45(19)
84.13(16)
85.0(4)
175.4(7)
98.9(7)
169.4(8)
3d
3e
3f
178.87(14)
174.68(12)
173.4(3)
94.29(14)
96.03(12)
99.8(3)
172.29(14)
169.03(12)
170.0(3)
3h
3i
173.69(17)
176.52(16)
175.79(13)
96.40(15)
98.71(17)
100.98(14)
84.8(2)
169.22(16)
170.82(17)
168.35(14)
84.7(2)
3j
82.72(19)
Table 4. C(sp2)−C(sp2) Reductive Elimination Reactions from Complexes 3a−j
entry
complex 3
L = PCy3, 3a
Ar′
C6F5
solvent
CDCl3
temp (°C)
time (h)
yield of 4 (%)
1
2
3
4
120
150
120
85
2
4
2
2
0
>95
82
C6F5
C6F5
C6F5
ClCH2CH2Cl
CDCl3
t
L = PCy2 Bu, 3b
L = PCytBu2, 3c
L = P(C6H4-p-X)tBu2
X = OMe, 3d
X = Me, 3e
CDCl3
>95
5
6
7
8
9
C6F5
C6F5
C6F5
C6F5
C6F5
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
85
85
85
85
85
2
2
2
2
2
>95
>95
>95
>95
>95
X = H, 3f
X = Cl, 3g
X = CF3, 3h
L = PPhtBu2
10
11
L = PPhtBu2, 3i
L = PPhtBu2, 3j
p-H-C6F4
CDCl3
CDCl3
85
85
2
2
>95
>95
p-CF3-C6F4
combination of 4.0 equiv of C6F5TMS and 2.0 equiv of AgF in
MeCN. Presumably, biaryl 4 was generated from in situ formed
complex cis-[Au(PtBu3)(ArF)(C6F5)(Cl)], which was unstable
at room temperature and underwent fast reductive elimination
to give 4 in high yield.
Table 5. First-Order Kinetics for Thermal Decomposition of
Diarylgold(III) Complexes 3d−h at 80 °C
Kinetics of the C(sp2)−C(sp2) Reductive Elimination
from cis-[Au(L)(ArF)(Ar′)(Cl)] (3c−j). Since the reductive
elimination from complexes cis-[Au(L)(ArF)(Ar′)(Cl)] 3c−j
were clean and high yielding, we studied the kinetics of these
reactions in detail. The rates of the C(sp2)−C(sp2) reductive
elimination reactions from cis-[Au(L)(ArF)(Ar′)(Cl)] (3c−j)
were measured by monitoring of the 19F NMR spectroscopy for
greater than 3 half-lives. The rate constants were then
calculated from plots of the decay of the diarylgold(III)
complexes vs time. More specifically, the diarylgold(III)
complexes in CDCl3 in a sealed NMR tube were completely
immersed in an oil bath maintained at 65 0.1 to 90 0.1 °C
and 19F NMR spectra were obtained periodically at room
temperature.
Electronic Effects of the Phosphine Ligands on
C(sp2)−C(sp2) Reductive Elimination from cis-[Au(L)-
(ArF)(Ar′)(Cl)] (3d−h). The rates of the C(sp2)−C(sp2)
reductive elimination reactions from cis-[Au(L)(ArF)(Ar′)(Cl)]
(3d−h) were measured at 80 °C, and the results are
summarized in Table 5. The disappearance of complexes 3d−
entry
Ar
complex
kobs (10−4 s−1
)
t1/2 (s)
1
2
3
4
5
p-MeO-C6H4
p-Me-C6H4
C6H5
3d
3e
3f
4.13
2.62
4.95
5.29
6.72
1676.6
2647.6
1401.4
1309.7
1031.3
p-Cl-C6H4
p-CF3-C6H4
3g
3h
h followed first-order kinetics over more than 3 half-lives. In
general, the rate constants for the C(sp2)−C(sp2) reductive
eliminations from the more electron-poor di-tert-butyl(aryl)-
phosphine ligated diarylgold(III) complexes were higher than
those from the more electron-rich di-tert-butyl(aryl)phosphine
ligated complexes, while reductive elimination from the
complex cis-[Au(P(p-Me-C6H4)tBu2)(ArF)(C6F5)(Cl)] (3e) is
somewhat slower than that from the complex cis-[Au(P(p-
MeO-C6H4)tBu2)(ArF)(C6F5)(Cl)] (3d), although the phos-
phine ligand P(p-OMe-C6H4)tBu2 in complex 3d is more
electron-rich than P(p-Me-C6H4)tBu2 in complex 3e. The order
D
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Figure 2. (A) Hammett plot of the rates of the reductive elimination from complexes 3d−h. (B) Hammett plot of the rates of reductive elimination
from complexes 3f,i,j. (C) Eyring plot for the thermolysis of complex 3f in CDCl3 over the temperature range 65−90 °C. (D) Effect of added n-
Bu4NCl on the rates of thermolysis of complex 3f at 85 °C in CDCl3. (E) Effect of added PPhtBu2 on the rates of thermolysis of complex 3f at 85 °C
in CDCl3.
of these rates for four of the para-substituted di-tert-butyl-
(aryl)phosphine-ligated diarylgold(III) complexes was p-CF3 >
p-Cl > p-H > p-MeO. For example, reductive elimination from
cis-[Au(P(p-CF3-C6H4)tBu2)(ArF)(C6F5)(Cl)] (3h; kobs = 6.72
× 10−4 s−1) was roughly 1.5 times faster than that from cis-
[Au(P(p-MeO-C6H4)tBu2)(ArF)(C6F5)(Cl)] (3d; kobs = 4.13 ×
10−4 s−1). A Hammett plot for the reductive elimination
reactions from complexes 3d−h is shown in Figure 2A. A linear
free energy correlation of the rates from complexes 3d,f−h with
the simple σ values derived from benzoic acid acidity was
observed. As shown in Figure 2A, a positive value for the
parameter ρ was obtained, which indicates that electron-
withdrawing substituents at the para position of the aryl group
of the phosphine ligands have an accelerating effect on the rate
of the C(sp2)−C(sp2) reductive elimination.
yields, respectively (Table 4, entries 7, 10, and 11). The rates of
the C(sp2)−C(sp2) reductive elimination from these complexes
were measured by 19F NMR spectroscopy, and they followed
first-order rate laws. As shown in Figure 2B, the C(sp2)−C(sp2)
reductive elimination from complex 3i was faster than those of
complexes 3f,j, which demonstrates that electron-donating
substituents at the para position of the aryl group that is trans
to the phosphine ligand have an accelerating effect on the rates
of the carbon−carbon reductive elimination from diarylgold-
(III) complexes.
Effect of Temperature on C(sp2)−C(sp2) Reductive
Elimination from cis-[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f). To
probe the effect of temperature on the reductive elimination
reactions of diarylgold(III) complexes, we studied the kinetics
of the C(sp2)−C(sp2) reductive elimination from cis-[Au-
(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) between 65 and 90 °C. It
showed a linear dependence of the rates of reductive
elimination from complex 3f with temperatures ranging from
65 to 90 °C, as shown in Figure 2C. The Eyring analysis
Electronic Effects of the Aryl Ligands on C(sp2)−C(sp2)
Reductive Elimination from cis-[Au(L)(ArF)(Ar′)(Cl)]
(3f,i,j). Thermolysis of complexes 3f,i,j at 85 °C for 2.0 h
generated cleanly the corresponding biaryls 4−6 in over 95%
E
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Figure 3. Possible pathways for reductive elimination from diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)].
revealed activation parameters of ΔH⧧ = 21.65 0.77 kcal/mol
and ΔS⧧ = −12.71 0.73 eu.
The rate constant of the reductive elimination of cis-
[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) in CDCl3 at 85 °C
increased with an increase in the concentration of n-Bu4NCl
(0−0.25 M), as shown in Figure 2D. The rate of the reductive
elimination from complex 3f in the presence of 0.25 M of n-
Bu4NCl (kobs = 1.01 × 10−3 s−1) was roughly 1.6 times faster
than that in the absence of n-Bu4NCl (kobs = 6.80 × 10−4 s−1).
These experiments suggest that the C(sp2)−C(sp2) reductive
elimination from complex 3f was not inhibited by the addition
of n-Bu4NCl and the increase in the rate constant indicates a
kinetic salt effect.
Effect of Solvent Polarity on C(sp2)−C(sp2) Reductive
Elimination from cis-[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f). It is
generally known that the rate of reductive elimination from a
transition-metal center is greatly affected by the polarity of the
reaction medium because of the different relative stabilization
effects on the ground and transition states of the transition-
metal complexes.18 To evaluate the effect of solvent polarity on
the C(sp2)−C(sp2) reductive elimination of the phosphine-
ligated diarylgold(III) complexes, we studied the reductive
elimination of the complex cis-[Au(PPhtBu2)(ArF)(C6F5)(Cl)]
(3f) in different solvents. It was found that heating of complex
3f in CCl4, CDCl3, and nitrobenzene led to full conversion after
8 h at 85 °C to give the corresponding biaryl product 4 in
almost quantitative yields. Thermolysis of complex 3f in
toluene, DMF, and CH3CN occurred with full conversion after
8 h to give the corresponding biaryl compound 4 in 97%, 99%,
and 99% yields, respectively. To determine the effect of the
solvent polarity more precisely, we conducted two sets of
parallel experiments to measure the rates of the C(sp2)−C(sp2)
reductive elimination from cis-[Au(PPhtBu2)(ArF)(C6F5)(Cl)]
(3f) at 85 °C in two kinds of solvents with different polarities
(CCl4 vs CDCl3 and toluene vs nitrobenzene). Reductive
elimination from the complex cis-[Au(PPhtBu2)(ArF)(C6F5)-
(Cl)] (3f) in the more polar solvent CDCl3 (kobs = 6.80 × 10−4
s−1) was roughly 1.7 times faster than that in CCl4 (kobs = 3.94
× 10−4 s−1). Likewise, reductive elimination in nitrobenzene
(kobs = 5.27 × 10−4 s−1) was 1.4 times faster than that in the less
polar solvent toluene (kobs = 3.61 × 10−4 s−1).
Effect of Added Phosphine Ligand on C(sp2)−C(sp2)
Reductive Elimination from cis-[Au(PPhtBu2)(ArF)(C6F5)-
(Cl)] (3f). To probe the impact of the addition of phosphine
ligand on the C(sp2)−C(sp2) reductive elimination reaction,
we studied the thermolysis of cis-[Au(PPhtBu2)(ArF)(C6F5)-
(Cl)] (3f) in the presence of various amounts of PPhtBu2 (0−
0.25 M). The yields of the reductive elimination reactions in
the presence of 1.0−5.0 equiv of PPhtBu2 were not affected.
Likewise, the rates were not significantly influenced in the
presence of different amounts of PPhtBu2, even though the
reductive elimination reactions in the presence of additional
ligand were slightly faster, as shown in Figure 2E.
DISCUSSION
■
Mechanism of C(sp2)−C(sp2) Reductive Elimination
from cis-[Au(L)(ArF)(Ar′)(Cl)]. Mechanistically, three possible
reaction pathways are proposed for the C(sp2)−C(sp2)
reductive elimination from diarylgold(III) complexes cis-
[Au(L)(ArF)(Ar′)(Cl)]. In pathway A, a reversible phosphine
dissociation generates a three-coordinated Y-shaped Au(III)
intermediate, which undergoes C(sp2)−C(sp2) reductive
elimination by direct means or through an autocatalytic
elimination pathway13h to give the biaryl product. Alternatively,
in pathway B, chloride anion dissociation generates a cationic
three-coordinated Y-shaped Au(III) intermediate, followed by a
fast reductive elimination to form biaryl product and a cationic
Au(I) species, which is trapped by chloride anion to form L−
Au−Cl. A third pathway (C) for the C(sp2)−C(sp2) reductive
elimination from cis-[Au(L)(Ar)(Ar′)(Cl)] involves a classic
concerted bond-forming process via a three-centered transition
state, as shown in Figure 3.
To further evaluate the effect of solvent polarity, we studied
the kinetics of the reductive elimination from cis-[Au(PPhtBu2)-
(ArF)(C6F5)(Cl)] (3f) in polar solvents DMF and CH3CN.
Interestingly, reductive eliminations from the complex cis-
[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) in the more polar solvents
DMF (kobs = 5.91 × 10−4 s−1) and CH3CN (kobs = 6.11 × 10−4
s−1) were slightly slower than that in CDCl3.
Effect of Added Chloride Anion on C(sp2)−C(sp2)
Reductive Elimination from cis-[Au(PPhtBu2)(ArF)(C6F5)-
(Cl)] (3f). To examine the effect of added chloride anion on the
C(sp2)−C(sp2) reductive elimination reaction of cis-[Au(L)-
(ArF)(Ar′)(Cl)], we studied the reductive elimination of cis-
[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) in the presence of
different amounts of n-Bu4NCl in CDCl3. The yields of the
corresponding biaryl product 4 were not significantly
influenced even by the addition of 5.0 equiv of n-Bu4NCl.
Both the experimental and computational results suggest
that, of the three possible mechanistic pathways shown in
Figure 3, pathway C is consistent with our experimental data
for biaryl reductive elimination from cis-[Au(L)(ArF)(Ar′)-
F
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Article
(Cl)]. Our rationale for proposing such a classic concerted
biaryl-forming reductive elimination pathway is described
below.
indicating that the pathway involving the dissociation of
chloride anion is disfavored.
Third, if the reductive elimination proceeds via paths A and
B, first-order kinetic behaviors would not be observed, which
provides additional evidence for the concerted reductive
elimination pathway.
Fourth, in pathway C, the calculated actvation free energy
and enthalpy of biaryl reductive elimination via transition state
7-ts are determined to be 22.6 and 20.2 kcal/mol, respectively.
The calculated actvation enthalpy is very close to the
corresponding experimentally observed activation enthalpy
First, pathway A was disfavored because experimental results
showed that the C(sp2)−C(sp2) reductive elimination from cis-
[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) was not inhibited by the
addition of free phosphine ligand PPhtBu2. If a pathway that
undergoes an initial reversible dissociation of the phosphine
ligand followed by direct or autocatalytic reductive elimination
from the resulting three-coordinated Y-shaped diarylgold(III)
intermediate is proceeding, an inhibition of the reductive
elimination upon the addition of free phosphine ligand should
be observed. For example, Kochi’s studies showed that the
C(sp3)−C(sp3) bond-forming reductive elimination from
[(Ph3P)ArMe3] was significantly retarded in the presence of
20 mol % of free PPh3.10 In addition, theoretical calculations
showed that dissociation of the phosphine ligand from cis-
[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) is a slower process which
needs to overcome a much higher energy barrier (43.9 kcal/
mol) in comparison to pathway C (22.6 kcal/mol) (Figure 4).
value (21.65
0.77 kcal/mol), which further indicates that
the direct biaryl reductive elimination from four-coordinated
complex 3f is favorable in this system.
Effects of the Steric Hindrance of the Phosphine
Ligands on C(sp2)−C(sp2) Reductive Elimination from
cis-[Au(L)(ArF)(Ar′)(Cl)]. Steric hindrance of the phosphine
ligands plays an important role in promoting efficient C(sp2)−
C(sp2) bond-forming reductive elimination from cis-[Au(L)-
(ArF)(Ar′)(Cl)], as clearly demonstrated by the high-yielding
reductive elimination from PCytBu2-ligated diarylgold(III)
complex 3c at 85 °C, while the reductive elimination from
t
PCy3- or PCy2 Bu-ligated diarylgold(III) complexes 3a,b
required significantly higher reaction temperatures (120−150
°C). PCy3, PCy2 Bu, and PCytBu2 have similar electronic
t
properties, yet the steric hindrances of these ligands increase
from PCy3 to PCytBu2 since the bond angles Cl−Au−C(ArF)
in complexes cis-[Au(L)(ArF)(Ar′)(Cl)] 3a−c decrease from
173.89(14)/174.31(16)° to 171.27(11) and 170.5(8)/
169.4(8)°, respectively. As a result, the rates of the C(sp2)−
C(sp2) reductive elimination from complexes 3a−c increased.
The effect of the steric hindrance of the phosphine ligands
was also illustrated by the facile C(sp2)−C(sp2) reductive
elimination from PtBu3-ligated diarylgold(III) complex in
comparison to that from the analogous di-tert-butyl(aryl)-
phosphine-ligated diarylgold(III) complex cis-[Au(P(p-X-
C6H4)tBu2)(ArF)(Ar′)(Cl)]. The former occurred at room
temperature with 81% yield of biaryl 4, while the latter required
a higher temperature (85 °C) to afford the corresponding biaryl
and no reductive elimination was observed at room temper-
ature. Sterically, PtBu3 is bulkier than P(p-X-C6H4)tBu2
(Tolman cone angles: 182° vs 170°), and electronically,
PtBu3 is more strongly donating than P(p-X-C6H4)tBu2. Thus,
clearly, the acceleration of reductive elimination from PtBu3-
ligated diarylgold(III) complex is mainly due to the steric effect
of the ligand and obviously the steric effect exceeds the
decelerating effect resulting from the electron-donating ability
of PtBu3.
Figure 4. Calculated activation free energies for the C(sp2)−C(sp2)
reductive elimination of cis-[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f).
To further evaluate the steric effect of the phosphine ligands
on the C(sp2)−C(sp2) reductive elimination from complexes
cis-[Au(L)(ArF)(Ar′)(Cl)], we also studied the steric effect of
the ligands on the stability of the transition state by DFT
calculation. As shown in Table 6, with a decrease in steric
hindrance of the phosphine ligands, the activation free energies
of the reductive elimination transition states increased from
24.3 to 31.7 kcal/mol. We reasoned that the steric hindrance of
the ligands pushes the ArF group away from the phosphine
ligand but close to the Ar′ group, thus facilitating the formation
of the three-centered transition state. Since the formation of
this transition state from the more hindered phosphine-ligated
complexes requires a lower energy barrier in comparison to
those with less hindered phosphine ligated complexes,
Second, the observation that the rate of reductive elimination
upon the addition of n-Bu4NCl was slightly faster than that in
the absence of the n-Bu4NCl disfavors pathway B. If a reversible
dissociation of chloride anion followed by C(sp2)−C(sp2)
reductive elimination from the resulting cationic three-
coordicated Y-shaped Au(III) intermediate takes place, upon
addition of n-Bu4NCl, a retardation of the rate of the reduction
elimination would be expected. The small rate differences in
solvents with different polarities also do not support this
pathway. Furthermore, DFT calculations showed that the
energy barrier for dissociation of chloride anion from cis-
[Au(PPhtBu2)(ArF)(C6F5)(Cl)] (3f) is up to 48.1 kcal/mol,
which is 25.5 kcal/mol higher than that of pathway C,
G
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studies of the C(sp2)−C(sp2) reductive elimination combined
with DFT calculations indicate that the biaryl reductive
elimination from complexes cis-[Au(L)(ArF)(Ar′)(Cl)] pro-
ceeds through a concerted biaryl-forming pathway from the
four-coordinated Au(III) metal center. These studies also
disclose that the steric hindrance of the phosphine ligands plays
a major role in promoting the reductive elimination from
diarylgold(III) complexes, while the electronic properties of the
ligands have a much smaller effect. We have also shown that the
rates of the C(sp2)−C(sp2) reductive elimination were not
sensitive to the polarity of the solvents, while more weakly
electron withdrawing aryl ligands of the diarylgold(III) complex
can accelerate the reaction rate dramatically. In addition, DFT
calculations showed that the formation of the three-center
transition state is the critical step in the elimination process,
which is consistent with the observation that the reaction rates
were not sensitive to the polarity of the solvents.
Table 6. Calculated Activation Free Energies for the C(sp2)−
C(sp2) Reductive Elimination from cis-
[Au(L)(ArF)(Ar′)(Cl)]
entry
complex
ligand
ΔG⧧ (kcal/mol)
1
2
3
4
5
3c
3b
3a
3k
3l
PCytBu2
24.3
26.0
27.3
29.3
31.7
t
PCy2 Bu
PCy3
PPh3
PMe3
consequently, faster rates for the reductive elimination from the
more hindered ligand-ligated complexes were observed.
Electronic Effects of the Phosphine Ligands on the
C(sp2)−C(sp2) Reductive Elimination from cis-[Au(L)-
(ArF)(Ar′)(Cl)]. In contrast to the large differences in rates
resulting from changes in the steric hindrance of the ligands,
the electronic property of the phosphine ligands has a much
smaller effect on the reaction rates. For instance, our studies
showed that C(sp2)−C(sp2) reductive eliminations occurred
more quickly from the more electron-poor di-tert-butyl(aryl)-
phosphine-ligated diarylgold(III) complexes, although P(p-CF3-
C6H4)tBu2-ligated complex 3h underwent reductive elimination
only 1.5 times faster in comparison to the analogous P(p-MeO-
C6H4)tBu2-ligated complex 3d. These observations are
consistent with the conventional electronic effects of the
ancillary ligands on the rate of reductive elimination from
transition-metal complexes,1 but the magnitude of the rate
difference was small.
EXPERIMENTAL SECTION
■
General Information. All glassware was oven- or flame-dried
immediately prior to use. Solvents were freshly degassed according to
the procedures in Purification of Laboratory Chemicals prior to use.
Deuterated solvents were purchased from Cambridge Isotope
Laboratories, Inc., and were degassed and stored over activated 4 Å
molecular sieves. Unless otherwise noted, all other reagents and
starting materials were purchased from commercial sources and used
1
without further purification. The H, 19F, 31P, and 13C NMR spectra
were obtained at 293 K on a 400 or 500 MHz spectrometer, and
chemical shifts were recorded relative to the solvent resonance. 19F
shifts were determined relative to CFCl3 as an external standard, and
low field is positive. Coupling constants are reported in hertz. The
following abbreviations were used to explain the multiplicities: s =
singlet; d = doublet; t = triplet; q = quartet; m = multiplet; br = broad.
Suitable single crystals of complex 2i, 3a−f,h−j were selected by
optical examination and mounted on a glass fiber. The X-ray
diffraction (XRD) data were collected on a Bruker APEX-II CCD
diffractometer. The crystal was kept at 130 K during data collection.
Using Olex2,19 the structure was solved with the ShelXT20 structure
solution program using intrinsic phasing and refined with the ShelXL21
refinement package using least-squares minimization.
An unusual rate difference for reductive elimination reactions
t
from cis-[Au(PCy2 Bu)(ArF)(C6F5)(Cl)] (3b) and cis-[Au(P(p-
MeO-C6H4)tBu2)(ArF)(C6F5)(Cl)] (3d) was observed.
t
PCy2 Bu is slightly more sterically hindered than P(p-MeO-
C6H4)tBu2, which is indicated by the Cl−Au−C(ArF) bond
angle in the single crystals of complexes 3b,d (171.27(11) and
172.29(14)°, respectively) that resulted from the steric
hindrance of the ligands. Electronically, P(p-MeO-C6H4)tBu2
General Procedure for the Synthesis of (p-X-C6H4)tBu2P·
HBF4 and tBu2CyP·HBF4. In a glovebox, di-tert-butylchlorophosphine
(520 mg, 2.88 mmol), CuI (53 mg, 0.28 mmol), LiBr (48 mg, 0.55
mmol), and dry Et2O (8.0 mL) were placed in a 100 mL Schlenk tube
that was equipped with a stirring bar. (p-X-C6H4)MgBr or CyMgBr
(5.76 mmol, 1.00 mmol/mL in THF solution) was added dropwise at
0 °C in an ice−water bath, and the reaction mixture was stirred at
room temperature for 5 h. Then 5.0 mL of HBF4 (48% aqueous
solution) was added dropwise at 0 °C, and the reaction mixture was
stirred at room temperature for another 3 h. A 50 mL portion of
distilled water and 50 mL of dichloromethane were added, and the
organic phase was separated. The aqueous phase was extracted with
dichloromethane (2 × 50 mL). The organic phase was combined,
dried over anhydrous Na2SO4, filtered through Celite, and
concentrated in vacuo. The residue was purified by recrystallization
in dichloromethane and Et2O at room temperature.
t
is more electron withdrawing than PCy2 Bu. Yet, the reductive
elimination reaction of the complex cis-[Au(P(p-MeO-
C6H4)tBu2)(ArF)(C6F5)(Cl)] (3d) at 85 °C occurred in over
t
95% yield after 2 h, while decomposition of cis-[Au(PCy2 Bu)-
(ArF)(C6F5)(Cl)] (3b) was not detected under the same
conditions. A close examination of the single-crystal structure of
complex 3d discloses that the ring centroid distance between
the p-methoxyphenyl group of the P(p-MeO-C6H4)tBu2 ligand
and the 2,2′,3,3′,5,5′,6,6′-octafluoro-1,1′-biphenyl group (ArF)
of the complex is 3.733(4) Å, which indicates a π−π interaction
between the two aryl groups. Thus, we reasoned that the π−π
interaction between the p-methoxyphenyl group of the
phosphine ligand and the ArF group makes the phosphine
ligand much more electron withdrawing. As a result, the
reductive elimination from P(p-MeOC6H4)tBu2-ligated com-
plex 3d was accelerated.
(p-OMe-C6H4)tBu2P·HBF4. According to the general procedure, the
compound was obtained as a white solid in 22% yield on a 2.88 mmol
scale (230 mg). 1H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.82 (s,
2 H), 7.16 (d, J = 7.6 Hz, 2 H), 6.86 (d, J = 480.0 Hz, 1 H), 3.91 (s, 3
H), 1.41 (d, J = 17.2 Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ
−149.85 (m, 4 F). 31P NMR (162 MHz, CDCl3): δ 43.39 (s, 1 P). 13
C
NMR (101 MHz, CDCl3): δ 164.7 (d, J = 2.0 Hz), 116.2 (d, J = 13.0
Hz), 105.6, 104.9, 55.8, 34.3 (d, J = 35.0 Hz), 27.6. Anal. Calcd for
C15H26BF4OP: C, 52.97; H, 7.70. Found: C, 52.85; H, 7.63.
CONCLUSION
■
In summary, we have synthesized a series of well-defined
phosphine-ligated diarylgold(III) complexes cis-[Au(L)(ArF)-
(Ar′)(Cl)] and systematically studied the C(sp2)−C(sp2)
reductive elimination process from them. Detailed kinetic
(p-Me-C6H4)tBu2P·HBF4. According to the general procedure, the
compound was obtained as a white solid in 81% yield on a 2.88 mmol
scale (760 mg). 1H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.72 (s,
H
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Article
2 H), 7.44 (m, 2 H), 6.90 (d, J = 488.0 Hz, 1 H), 2.45 (s, 3 H), 1.49
(d, J = 16.0 Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ −149.80 (m,
4 F). 31P NMR (162 MHz, CDCl3): δ 44.25 (s, 1 P). 13C NMR (101
MHz, CDCl3): δ 146.17 (d, J = 2.7 Hz), 131.11 (d, J = 11.9 Hz),
121.11, 111.37, 34.16 (d, J = 34.6 Hz), 27.55, 21.80. Anal. Calcd for
C15H26BF4P: C, 55.58; H, 8.09. Found: C, 55.50; H, 8.07.
1.38 (d, J = 12.0 Hz, 27 H). 31P NMR (162 MHz, CDCl3): δ 90.51 (s,
1 P). 13C NMR (101 MHz, CDCl3): δ 39.4 (d, J = 21.1 Hz), 32.2 (d, J
= 4.0 Hz) ppm.
(PhtBu2P)AuCl. The general procedure A using PhtBu2P (267 mg,
1.20 mmol) and Me2SAuCl (294 mg, 1.00 mmol) in 5.0 mL of
dichloromethane gave (PhtBu2P)AuCl as a white solid (340 mg, 62%).
1H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.93 (t, J = 8.0 Hz, 2 H),
7.50 (m, 1 H), 7.42 (m, 2 H), 1.35 (d, J = 16.0 Hz, 18 H). 31P NMR
(162 MHz, CDCl3): δ 79.07 (s, 1 P). 13C NMR (101 MHz, CDCl3): δ
132.0 (d, J = 2.4 Hz), 128.6 (d, J = 10.7 Hz), 127.8, 127.3, 36.4 (d, J =
26.0 Hz), 30.2 (d, J = 6.0 Hz). Anal. Calcd for C14H23AuClP: C, 36.98;
H, 5.10. Found: C, 37.03; H, 5.12.
(p-Cl-C6H4)tBu2P·HBF4. According to the general procedure, the
compound was obtained as a white solid in 31% yield on a 2.88 mmol
scale (320 mg). 1H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.87 (t,
J = 8.0 Hz, 2 H), 7.64 (d, J = 8.0 Hz, 2 H), 6.90 (d, J = 488.0 Hz, 1 H),
1.49 (d, J = 16.0 Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ −149.27
(m, 4 F). 31P NMR (162 MHz, CDCl3): δ 44.32 (s, 1 P). 13C NMR
(101 MHz, CDCl3) δ 142.0 (d, J = 2.0 Hz), 130.9 (d, J = 12.0 Hz),
114.2, 113.5, 34.3 (d, J = 36.0 Hz), 27.4. Anal. Calcd for
C14H23BClF4P: C, 48.80; H, 6.73. Found: C, 48.99; H, 6.62.
((p-MeO-C6H4)tBu2P)AuCl. The general procedure B using (p-MeO-
C6H4)tBu2P·HBF4 (156 mg, 0.459 mmol), K3PO4 (187 mg, 0.882
mmol), and Me2SAuCl (118 mg, 0.401 mmol) in 3.0 mL of THF gave
((p-MeO-C6H4)tBu2P)AuCl as a white solid (140 mg, 72%). 1H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.89 (m, 2 H), 6.96 (d, J = 8.0 Hz,
2 H), 3.84 (s, 3 H), 1.37 (d, J = 16.0 Hz, 18 H). 31P NMR (162 MHz,
CDCl3): δ 77.04 (s, 1 P). 13C NMR (101 MHz, CDCl3): δ 162.4 (d, J
= 2.0 Hz), 118.4, 117.9, 114.1 (d, J = 12.0 Hz), 55.4, 36.4 (d, J = 27.0
Hz), 30.2 (d, J = 6.0 Hz). Anal. Calcd for C15H25AuClOP: C, 37.17; H,
5.20. Found: C, 37.20; H, 5.05.
tBu2CyP·HBF4. According to the general procedure, the compound
was obtained as a white solid in 52% yield on a 5.76 mmol scale (920
mg). 1H NMR (400 MHz, CDCl3, 293 K, TMS): δ 5.77 (d, J = 466.0
Hz, 1 H), 2.56 (m, 1 H), 2.16 (m, 2 H), 1.89 (m, 2 H), 1.78 (m, 3 H),
1.55 (d, J = 16.0 Hz), 1.41 (m, 3 H). 19F NMR (376 MHz, CDCl3): δ
−150.22 (m, 4 F). 31P NMR (162 MHz, CDCl3): δ 46.73 (s, 1 P). 13
C
NMR (101 MHz, CDCl3): δ 34.6 (d, J = 32.1 Hz), 32.3 (d, J = 34.4
Hz), 29.6 (d, J = 3.8 Hz), 28.3, 27.0 (d, J = 12.1 Hz), 25.2. Anal. Calcd
for C14H30BF4P: C, 53.18; H, 9.56. Found: C, 52.88; H, 9.52.
((p-Me-C6H4)tBu2P)AuCl. The general procedure B using (p-Me-
C6H4)tBu2P·HBF4 (211 mg, 0.651 mmol), K3PO4 (212 mg, 1.00
mmol), and Me2SAuCl (147 mg, 0.500 mmol) in 5.0 mL of THF gave
General Procedure for the Preparation of Complexes
(L)AuCl. General Procedure A.22 In a glovebox, Cy3P (672 mg,
2.40 mmol) and Me2SAuCl (588 mg, 2.00 mmol) were placed in a 25
mL round-bottom flask that was equipped with a stirring bar. A 10 mL
portion of dichloromethane was added, and the flask was sealed with a
rubber stopper. The mixture was stirred overnight and was then
filtered through a short plug of Celite. The solvent was removed under
vacuum to give a white solid. Recrystallization of the crude product
with dichloromethane and n-pentane gave (Cy3P)AuCl as a white solid
t
1
((p-Me-C6H4) Bu2P)AuCl as a white solid (150 mg, 64%). H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.87 (t, J = 8.0 Hz, 2 H), 7.28 (d, J
= 8.0 Hz, 2 H), 2.42 (s, 3 H), 1.41 (d, J = 16.0 Hz, 18 H). 31P NMR
(162 MHz, CDCl3): δ 78.06 (s, 1 P). 13C NMR (101 MHz, CDCl3): δ
142.6, 129.4 (d, J = 10.0 Hz), 124.3, 123.8, 36.4 (d, J = 27.0 Hz), 30.2
(d, J = 6.0 Hz), 21.4. Anal. Calcd for C15H25AuClP: C, 38.43; H, 5.38.
Found: C, 38.31; H, 5.39.
1
((p-Cl-C6H4)tBu2P)AuCl. The general procedure B using (p-Cl-
C6H4)tBu2PH·BF4 (68.8 mg, 0.198 mmol), K3PO4 (63.6 mg, 0.300
mmol), and Me2SAuCl (50.0 mg, 0.170 mmol) in 5.0 mL of THF gave
(497 mg, 48%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 1.95
(m, 9 H), 1.82 (m, 6 H), 1.70 (m, 3 H), 1.61 (s, 1 H), 1.42 (m, 6 H),
1.25 (m, 9 H). 31P NMR (162 MHz, CDCl3, 293 K, TMS): δ 54.01 (s,
1 P). 13C NMR (101 MHz, CDCl3, 293 K, TMS): δ 33.3 (d, J = 31.2
Hz), 30.8, 27.0 (d, J = 12.0 Hz), 25.8 ppm.
1
((p-Cl-C6H4)tBu2P)AuCl as a white solid (52 mg, 62%). H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.95 (t, J = 8.0 Hz, 2 H), 7.49 (d, J
= 8.0 Hz, 2 H), 1.42 (d, J = 16.0 Hz, 18 H). 31P NMR (162 MHz,
CDCl3): δ 78.26 (s, 1 P). 13C NMR (101 MHz, CDCl3): δ 138.8 (d, J
= 2.0 Hz), 128.9 (d, J = 11.0 Hz), 126.4, 125.9, 36.5 (d, J = 26.0 Hz),
30.2 (d, J = 6.0 Hz). Anal. Calcd for C14H22AuCl2P: C, 34.38; H, 4.53.
Found: C, 34.47; H, 4.62.
t
General Procedure B. In a glovebox, Bu2CyP·HBF4 (948 mg, 3.00
mmol) and K3PO4 (700 mg, 3.30 mmol) were placed into a 25 mL
round-bottom flask that was equipped with a stirring bar. A 5.0 mL
portion of THF was placed in the flask, and then the flask was sealed
with a rubber stopper. The reaction mixture was stirred at room
temperature for 3 h. The mixture was then filtered through a short
plug of Celite. Me2SAuCl (588 mg, 2.00 mmol) and 5.0 mL of
dichloromethane were placed in the flask. The reaction mixture was
stirred at room temperature overnight. The solvent was removed
under vacuum to give a white solid. The residue was purified by
recrystallization from dichloromethane and n-pentane to give
(CytBu2P)AuCl as a white solid (630 mg, 68%). 1H NMR (400
MHz, CDCl3, 293 K, TMS): δ 2.39 (m, 2 H), 2.03 (m, 1 H), 1.85 (m,
2 H), 1.70 (m, 3 H), 1.44 (d, J = 14.8 Hz, 18 H), 1.26 (m, 3 H). 31P
NMR (162 MHz, CDCl3): δ 81.53 (s, 1 P). 13C NMR (101 MHz,
CDCl3): δ 38.4 (d, J = 23.6 Hz), 37.3 (d, J = 24.2 Hz), 33.6, 31.0 (d, J
= 4.6 Hz), 28.1 (d, J = 11.4 Hz), 26.0 (d, J = 1.3 Hz). Anal. Calcd for
C14H29AuClP: C, 36.49; H, 6.34. Found: C, 36.39; H, 6.30.
((p-CF3-C6H4)tBu2P)AuCl. The general procedure A using (p-CF3-
C6H4)tBu2P·HBF4 (348 mg, 1.20 mmol) and Me2SAuCl (294 mg, 1.00
mmol) in 5.0 mL of dichloromethane gave ((p-CF3-C6H4)tBu2P)AuCl
1
as a white solid (365 mg, 58%). H NMR (400 MHz, CDCl3, 293 K,
TMS): δ 8.14 (t, J = 8.0 Hz, 2 H), 7.74 (d, J = 8.0 Hz, 2 H), 1.42 (d, J
= 16.0 Hz, 18 H). 31P NMR (162 MHz, CDCl3): δ 79.28 (s, 1 P). 19
F
NMR (376 MHz, CDCl3): δ −63.23 (s, 3 F). 13C NMR (101 MHz,
CDCl3): δ 133.8 (q, J = 33.0 Hz), 132.6, 132.1, 125.3 (m), 124.7 (q, J
= 271.0 Hz), 36.6 (d, J = 26.0 Hz), 30.2 (d, J = 6.0 Hz). Anal. Calcd
for C15H22AuClF3P: C, 34.47; H, 4.24. Found: C, 34.48; H, 4.11.
General Procedure for the Preparation of Complexes
(L)Au(octafluorobiphenyl) (1a−h).15 (Cy3P)AuCl (256 mg, 0.500
mmol), Ag2O (290 mg, 1.25 mmol), K2CO3 (121 mg, 1.75 mmol),
PivOH (128 mg, 1.25 mmol), and octafluorobiphenyl (596 mg, 1.00
mmol) were placed in an oven-dried 25.0 mL Schlenk tube that was
equipped with a stirring bar under Ar. Then 4.0 mL of freshly distilled
DMF was added and the reaction mixture was stirred at 55 °C
overnight. The mixture was then filtered through a short plug of
Celite. The solvent was removed under vacuum. The residue was
purified by flash chromatography on silica gel (n-pentane/dichloro-
methane 10/1) and further purified by recrystallization by dichloro-
methane and n-pentane to give (Cy3P)Au(octafluorobiphenyl) (1a) as
t
t
(Cy2 BuP)AuCl. The general procedure A using Cy2 BuP (763 mg,
3.00 mmol) and Me2SAuCl (588 mg, 2.00 mmol) in 5.0 mL of
t
dichloromethane gave (Cy2 BuP)AuCl as a white solid (672 mg, 69%).
1H NMR (400 MHz, CDCl3, 293 K, TMS): δ 2.03 (m, 6 H), 1.81 (m,
4 H), 1.67 (m, 2 H), 1.54 (m, 4 H), 1.29 (d, J = 14.4 Hz, 9 H), 1.20
(m, 6 H). 31P NMR (162 MHz, CDCl3): δ 67.66 (s, 1 P). 13C NMR
(101 MHz, CDCl3): δ 35.0 (d, J = 27.9 Hz), 34.3 (d, J = 28.7 Hz),
32.2, 30.9, 30.2 (d, J = 4.2 Hz), 27.2 (d, J = 7.9 Hz), 27.1 (d, J = 7.9
Hz), 25.7. Anal. Calcd for C16H31AuClP: C, 39.48; H, 6.42. Found: C,
39.28; H, 6.23.
1
a white solid (210 mg, 54%). H NMR (400 MHz, CD2Cl2, 293 K,
23
t
(tBu3P)AuCl. The general procedure A using Bu3P (5.3 mL, 10%
in n-pentane, 2.3 mmol) and Me2SAuCl (448 mg, 1.52 mmol) in 10.0
mL of freshly distilled dichloromethane gave (tBu3P)AuCl as a white
solid (539 mg, 82%).1H NMR (400 MHz, CDCl3, 293 K, TMS): δ
TMS): δ 7.21 (m, 1 H), 2.18−2.03 (m, 9 H), 1.86 (d, J = 12.0 Hz, 6
H), 1.73 (d, J = 8.0 Hz, 3 H), 1.54 (q, J = 12.0 Hz, 3 H), 1.39−1.21
(m, 9 H). 19F NMR (376 MHz, CD2Cl2): δ −118.16 (m, 2 F),
−140.25 (m, 4 F), −141.60 (m, 2 F). 31P NMR (162 MHz, CD2Cl2):
I
DOI: 10.1021/acs.organomet.7b00588
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
δ 56.54−56.36 (m, 1 P). Anal. Calcd for C30H34AuF8P: C, 46.52; H,
−140.12 (m, 2 F). 31P NMR (162 MHz, CDCl3): δ 79.30 (m, 1 P).
Anal. Calcd for C26H23AuClF8P: C, 41.59; H, 3.09. Found: C, 41.61;
H, 3.09.
4.42. Found: C, 46.54; H, 4.35.
t
(Cy2 BuP)Au(octafluorobiphenyl) (1b). The general procedure
t
using (Cy2 BuP)AuCl (488 mg, 1.44 mmol), Ag2O (249 mg, 1.07
((p-CF3-C6H4)tBu2P)Au(octafluorobiphenyl) (1h). The general
procedure using (p-CF3-C6H4)tBu2P)AuCl (783 mg, 1.50 mmol),
Ag2O (309 mg, 1.13 mmol), K2CO3 (362 mg, 2.63 mmol), PivOH
(382 mg, 3.75 mmol), and octafluorobiphenyl (894 mg, 3.00 mmol) in
5.0 mL of freshly distilled DMF gave ((p-CF3-C6H4)tBu2P)Au-
mmol), K2CO3 (345 mg, 2.50 mmol), PivOH (364 mg, 3.60 mmol),
and octafluorobiphenyl (852 mg, 2.86 mmol) in 3.0 mL of freshly
t
distilled DMF gave (Cy2 BuP)Au(octafluorobiphenyl) (1b) as a white
1
solid (460 mg, 43%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ
1
7.18 (m, 1 H), 2.26 (m, 4 H), 2.14 (m, 2 H), 1.92 (m, 4 H), 1.70 (m, 6
H), 1.43 (d, J = 14.0 Hz, 9 H), 1.33 (m, 6 H). 19F NMR (376 MHz,
CDCl3): δ −117.08 (m, 2 F), −138.62 (m, 2 F), −139.04 (m, 2 F),
−140.37 (m, 2 F). 31P NMR (162 MHz, CDCl3): δ 69.46 (m, 1 P).
Anal. Calcd for C28H32AuF8P: C, 44.93; H, 4.31. Found: C, 45.03; H,
4.31.
(octafluorobiphenyl) (1h) as a white solid (788 mg, 67%). H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 8.02 (s, 2 H), 7.51 (d, J = 8.0 Hz,
2 H), 7.19 (m, 1 H), 1.47 (d, J = 16.0 Hz, 18 H). 19F NMR (376 MHz,
CDCl3): δ −68.46 (s, 3 F), −122.25 (m, 2 F), −143.89 (m, 2 F),
−144.15 (m, 2 F), −145.33 (m, 2 F). 31P NMR (162 MHz, CDCl3): δ
80.36 (m, 1 P). Anal. Calcd for C27H23AuF11P: C, 41.34; H, 2.96.
Found: C, 41.15; H, 3.04.
(CytBu2P)Au(octafluorobiphenyl) (1c). The general procedure
using (CytBu2P)AuCl (660 mg, 1.43 mmol), Ag2O (249 mg, 1.07
mmol), K2CO3 (345 mg, 2.50 mmol), PivOH (364 mg, 3.60 mmol),
and octafluorobiphenyl (852 mg, 2.86 mmol) in 3.0 mL of freshly
distilled DMF gave (CytBu2P)Au(octafluorobiphenyl) (1c) as a white
(Ph3P)Au(octafluorobiphenyl) (1i). The general procedure using
Ph3PAuCl (306 mg, 0.619 mmol), Ag2O (100 mg, 0.433 mmol),
K2CO3 (138 mg, 1.00 mmol), PivOH (146 mg, 1.43 mmol), and
octafluorobiphenyl (895 mg, 2.48 mmol) in 3.0 mL of freshly distilled
DMF gave (Ph3P)Au(octafluorobiphenyl) (1i) as a white solid (446
1
solid (680 mg, 66%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ
1
mg, 67%). H NMR (400 MHz, CD2Cl2, 293 K, TMS): δ 7.68−7.43
7.18 (m, 1 H), 2.48 (s, 2 H), 2.12 (m, 1 H), 1.91 (m, 2 H), 1.77 (m, 3
H), 1.52 (d, J = 16.8 Hz, 18 H), 1.33 (m, 3 H). 19F NMR (376 MHz,
CDCl3): δ −117.00 (m, 2 F), −138.64 (m, 2 F), −139.03 (m, 2 F),
−140.39 (m, 2 F). 31P NMR (162 MHz, CDCl3): δ 82.36 (m, 1 P).
Anal. Calcd for C26H30AuF8P: C, 43.23; H, 4.19. Found: C, 43.33; H,
4.19.
(m, 15 H), 7.30−7.13 (m, 1 H). 19F NMR (376 MHz, CD2Cl2): δ
−115.11 (m, 2 F), −137.62 (m, 4 F), −138.75 (m, 2 F). 31P NMR
(162 MHz, CD2Cl2): δ 43.82 (m, 1 P). Anal. Calcd for C30H16AuF8P:
C, 47.67; H, 2.13. Found: C, 47.71; H, 2.12.
(tBu3P)Au(octafluorobiphenyl). The general procedure using
(tBu3P)AuCl (217 mg, 0.500 mmol), Ag2O (290 mg, 1.25 mmol),
K2CO3 (121 mg, 0.880 mmol), PivOH (128 mg, 1.25 mmol), and
octafluorobiphenyl (298 mg, 1.00 mmol) in 4.0 mL of freshly distilled
DMF gave (tBu3P)Au(octafluorobiphenyl) as a white solid (102 mg,
28%). 1H NMR (400 MHz, CD2Cl2, 293 K, TMS): δ 7.17−7.09 (m, 1
H), 1.46 (d, J = 12.0 Hz, 27 H) ppm; 19F NMR (376 MHz, CD2Cl2):
δ −115.52 (m, 2 F), −137.64 (m, 4 F), −139.04 (m, 2 F). 31P NMR
(162 MHz, CD2Cl2): δ 93.84 (m, 1 P). Anal. Calcd for C24H28AuF8P:
C, 41.39; H, 4.05. Found: C, 41.40; H, 3.90.
((p-MeO-C6H4)tBu2P)Au(octafluorobiphenyl) (1d). The general
procedure using ((p-OMe-C6H4)tBu2P)AuCl (131 mg, 0.270 mmol),
Ag2O (63 mg, 0.27 mmol), K2CO3 (65 mg, 0.47 mmol), PivOH (69
mg, 0.68 mmol), and octafluorobiphenyl (161 mg, 0.540 mmol) in 3.0
mL of freshly distilled DMF gave ((p-MeO-C6H4)tBu2P)Au-
1
(octafluorobiphenyl) (1d) as a white solid (85 mg, 42%). H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.96 (s, 2 H), 7.15 (m, 2 H), 7.00
(d, J = 8.0 Hz, 2 H), 3.85 (s, 3 H), 1.43 (d, J = 16.0, 18 H). 19F NMR
(376 MHz, CDCl3): δ −116.96 (m, 2 F), −138.65 (m, 2 F), −139.01
(m, 2 F), −140.31 (m, 2 F). 31P NMR (162 MHz, CDCl3): δ 78.85
(m, 1 P). Anal. Calcd for C27H26AuF8OP: C, 43.45; H, 3.51. Found: C,
43.56; H, 3.56.
General Procedure for the Preparation of Complexes cis-
(L)Au(octafluorobiphenyl)Cl2 (2a−h).13d,16 The complex (Cy3P)-
Au(octafluorobiphenyl) (1a; 600 mg, 0.775 mmol) and PhICl2 (742
mg, 2.70 mmol) were placed in an oven-dried Schlenk tube that was
equipped with a stirring bar. A 5.0 mL portion of CHCl3 was added,
and the reaction mixture was stirred at 45 °C for 3 h. The solvent was
removed under vacuum, and the residue was purified by flash
chromatography on silica gel (n-pentane/dichloromethane 10/1 to 1/
1) and further purified by recrystallization of dichloromethane and n-
pentane to give cis-(Cy3P)Au(octafluorobiphenyl)Cl2 (2a) as a white
((p-Me-C6H4)tBu2P)Au(octafluorobiphenyl) (1e). The general
procedure using ((p-Me-C6H4)tBu2P)AuCl (400 mg, 0.853 mmol),
Ag2O (199 mg, 0.858 mmol), K2CO3 (208 mg, 1.45 mmol), PivOH
(219 mg, 2.15 mmol), and octafluorobiphenyl (513 mg, 1.72 mmol) in
4.0 mL of freshly distilled DMF gave ((p-Me-C6H4)tBu2P)Au-
1
(octafluorobiphenyl) (1e) as a white solid (560 mg, 90%). H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.96 (s, 2 H), 7.33 (d, J = 8.0 Hz,
2 H), 7.19 (m, 1 H), 2.45 (s, 3 H), 1.48 (d, J = 16.0 Hz, 18 H). 19F
NMR (376 MHz, CDCl3): δ −116.94 (m, 2 F), −138.59 (m, 2 F),
−138.97 (m, 2 F), −140.27 (m, 2 F). 31P NMR (162 MHz, CDCl3): δ
78.74 (m, 1 P). Anal. Calcd for C27H26AuF8P: C, 44.40; H, 3.59.
Found: C, 44.63; H, 3.58.
1
solid (154 mg, 23%). H NMR (400 MHz, CD2Cl2, 293 K, TMS): δ
7.18 (m, 1 H), 2.76 (q, J = 4.1 Hz, 3 H), 1.94 (s, 6 H), 1.81 (s, 6 H),
1.72−1.60 (m, 9 H), 1.27 (s, 9 H). 19F NMR (376 MHz, CD2Cl2): δ
−127.25 (m, 2 F), −139.65 to −139.92 (m, 4 F), −140.05 (m, 2 F).
31P NMR (162 MHz, CD2Cl2): δ 66.21 (s, 1 P). Anal. Calcd for
C30H34AuCl2F8P: C, 42.62; H, 4.05. Found: C, 42.16; H, 4.03.
(PhtBu2P)Au(octafluorobiphenyl) (1f). The general procedure
using (PhtBu2P)AuCl (454 mg, 1.00 mmol), Ag2O (174 mg, 0.750
mmol), K2CO3 (241 mg, 1.75 mmol), PivOH (255 mg, 2.50 mmol),
and octafluorobiphenyl (596 mg, 2.00 mmol) in 3.0 mL of freshly
distilled DMF gave (PhtBu2P)Au(octafluorobiphenyl) (1f) as a white
t
cis-(Cy2 BuP)Au(octafluorobiphenyl)Cl2 (2b). The general proce-
t
dure using the complex (Cy2 BuP)Au(octafluorobiphenyl) (1b; 202
mg, 0.270 mmol) and PhICl2 (110 mg, 0.400 mmol) in 3.0 mL of
t
CHCl3 gave cis-(Cy2 BuP)Au(octafluorobiphenyl)Cl2 (2b) as a white
1
1
solid (176 mg, 80%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ
solid (366 mg, 51%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ
7.22 (m, 1 H), 2.96 (s, 2 H), 2.33 (s, 2 H), 2.00 (s, 2 H), 1.80 (s, 4 H),
1.71 (m, 2 H), 1.62 (d, J = 16.0 Hz, 9 H), 1.50 (m, 2 H), 1.50−1.16
(br, 8 H). 19F NMR (376 MHz, CDCl3): δ −119.92 (m, 2 F), −137.11
(m, 1 F), −137.39 (m, 3 F), −138.26 (m, 1 F), −139.52 (m, 1 F). 31P
NMR (162 MHz, CDCl3): δ 74.98 (s, 1 P). Anal. Calcd for
C28H32AuCl2F8P: C, 41.04; H, 3.94. Found: C, 41.29; H, 4.06.
cis-(CytBu2P)Au(octafluorobiphenyl)Cl2 (2c). The general proce-
dure using the complex (CytBu2P)Au(octafluorobiphenyl) (1c; 115
mg, 0.160 mmol) and PhICl2 (66 mg, 0.24 mmol) in 3.0 mL of CHCl3
gave cis-(CytBu2P)Au(octafluorobiphenyl)Cl2 (2c) as a white solid (78
8.04 (s, 2 H), 7.49 (m, 3 H), 7.15 (m, 1 H), 1.45 (d, J = 16.0 Hz, 18
H). 19F NMR (376 MHz, CDCl3): δ −117.00 (m, 2 F), −138.64 (m, 2
F), −139.02 (m, 2 F), −140.30 (m, 2 F). 31P NMR (162 MHz,
CDCl3): δ 79.79 (m, 1 P). Anal. Calcd for C26H24AuF8P: C, 43.59; H,
3.38. Found: C, 43.55; H, 3.40.
((p-Cl-C6H4)tBu2P)Au(octafluorobiphenyl) (1g). The general pro-
cedure using ((p-Cl-C6H4)tBu2P)AuCl (270 mg, 0.552 mmol), Ag2O
(96 mg, 0.41 mmol), K2CO3 (133 mg, 0.964 mmol), PivOH (140 mg,
1.372 mmol), and octafluorobiphenyl (328 mg, 1.10 mmol) in 3.0 mL
of freshly distilled DMF gave ((p-Cl-C6H4)tBu2P)Au-
1
1
mg, 63%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.22 (m, 2
(octafluorobiphenyl) (1g) as a white solid (270 mg, 65%). H NMR
H), 2.23 (s, 2 H), 1.82−1.61 (br, 23 H), 1.20 (m, 2 H), 0.73 (br, 2 H).
19F NMR (376 MHz, CDCl3): δ −118.30 (m, 1 F), −137.18 (m, 1 F),
−137.47 (m, 1 F), −137.61 (m, 2 F), −138.35 (m, 1 F), −139.55 (m,
(400 MHz, CDCl3, 293 K, TMS): δ 7.99 (s, 2 H), 7.48 (d, J = 8.0 Hz,
2 H), 7.16 (m, 1 H), 1.44 (d, J = 16.0 Hz, 18 H). 19F NMR (376 MHz,
CDCl3): δ −116.93 (m, 2 F), −138.67 (m, 2 F), −138.87 (m, 2 F),
J
DOI: 10.1021/acs.organomet.7b00588
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Organometallics
Article
1 F). 31P NMR (162 MHz, CDCl3): δ 89.25 (br, 1 P). Anal. Calcd for
C26H30AuCl2F8P: C, 39.36; H, 3.81. Found: C, 39.33; H, 3.81.
cis-((p-MeO-C6H4)tBu2P)Au(octafluorobiphenyl)Cl2 (2d). The gen-
eral procedure using the complex ((p-OMe-C6H4)tBu2P)Au-
(octafluorobiphenyl) (1d; 66 mg, 0.089 mmol) and PhICl2 (49 mg,
0.18 mmol) in 3.0 mL of CHCl3 gave cis-((p-MeO-C6H4)tBu2P)Au-
(octafluorobiphenyl)Cl2 (2d) as a white solid (45 mg, 62%). 1H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.66 (t, J = 8.0 Hz, 2 H), 7.18 (m,
1 H), 6.83 (dd, J = 8.0, 4.0 Hz, 2 H), 3.78 (s, 3 H), 1.71 (d, J = 16.0
Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ −119.79 (m, 2 F),
−137.16 (m, 1 F), −137.59 (m, 1 F), −137.77 (m, 2 F), −138.82 (m,
1 F), −139.72 (m, 1 F). 31P NMR (162 MHz, CDCl3): δ 74.44 (s, 1
P). Anal. Calcd for: C27H26AuCl2F8OP, 39.37; H, 3.28. Found: C,
39.68; H, 3.21.
cis-(Ph3P)Au(octafluorobiphenyl)Cl2·CH2Cl2 (2i). The general
procedure using the complex Ph3PAu(octafluorobiphenyl) (244 mg,
0.323 mmol) and PhICl2 (310 mg, 1.13 mmol) in 10.0 mL of CHCl3
gave cis-(Ph3P)Au(octafluorobiphenyl)Cl2·CH2Cl2 (2i) as a white
1
solid (220 mg, 82%). H NMR (400 MHz, CD2Cl2, 293 K, TMS): δ
7.74−7.39 (m, 15 H), 7.28−7.17 (m, 1 H), 5.38 (s, 2 H). 19F NMR
(376 MHz, CD2Cl2): δ −122.18 (m, 2 F), −135.73 (m, 4 F), −136.59
(m, 3 F), −137.15 (m, 1F). 31P NMR (162 MHz, CD2Cl2): δ 36.32
(m, 1 P). Anal. Calcd for C31H18AuCl4F8P: C, 40.82; H, 1.99. Found:
C, 40.78; H, 2.08.
General Procedure for the Preparation of Complexes cis-
[Au(L)(octafluorobiphenyl)(Ar′)(Cl)] (3a−h). In a glovebox, AgF
(56 mg, 0.44 mmol), TMSC6F5 (126 μL, 0.660 mmol), and MeCN
(2.0 mL) were placed in a 4.0 mL Schlenk tube that was equipped with
a stirring bar. The reaction mixture was stirred in the dark for 3 h.
Complex 2a (200 mg, 0.254 mmol) was placed in the Schlenk tube,
and the reaction mixture was stirred at room temperature in the dark
for 2 h. The mixture was then filtered through a short plug of Celite.
The solvent was removed under vacuum. The residue was purified by
flash chromatography on silica gel (n-pentane/dichloromethane 50/1
to 10/1) to give cis-[Au(PCy3) (octafluorobiphenyl)(C6F5)(Cl)] (3a)
cis-((p-Me-C6H4)tBu2P)Au(octafluorobiphenyl)Cl2 (2e). The gen-
eral procedure using the complex ((p-Me-C6H4)tBu2P)Au-
(octafluorobiphenyl) (1e; 197 mg, 0.270 mmol) and PhICl2 (148
mg, 0.538 mmol) in 3.0 mL of CHCl3 gave cis-((p-Me-C6H4)tBu2P)-
1
Au(octafluorobiphenyl)Cl2 (2e) as a white solid (210 mg, 97%). H
NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.61 (t, J = 9.0 Hz, 2 H),
7.18 (m, 1 H), 7.13 (d, J = 8.0 Hz, 2 H), 2.29 (s, 3 H), 1.71 (d, J =
16.8 Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ −119.77 (m, 2 F),
−137.04 (m, 1 F), −137.49 (m, 1 F), −137.91 (m, 2 F), −138.68 (m,
1 F), −139.69 (m, 1 F). 31P NMR (162 MHz, CDCl3): δ 74.75 (s, 1
P). Anal. Calcd for C30H32AuCl2F8P: C, 40.47; H, 3.27. Found: C,
40.13; H, 3.11.
1
as a white solid (130 mg, 56%). H NMR (400 MHz, CDCl3, 293 K,
TMS): δ 7.21 (m, 1 H), 2.44 (q, J = 11.6 Hz, 6 H), 1.96 (s, 6 H), 1.87
(d, J = 11.6 Hz, 6 H), 1.74−1.63 (br, 9 H), 1.27−1.10 (br, 9 H). 19F
NMR (376 MHz, CDCl3): δ −118.67 (m, 2 F), −123.58 (m, 2 F),
−137.30 (m, 2 F), −137.58 (m, 2 F), −138.10 (m, 1 F), −139.32 (m,
1 F), −157.00 (m, 1 F), −160.95 (m, 2 F). 31P NMR (162 MHz,
CDCl3): δ 37.60 (s, 1 P). Anal. Calcd for C36H34AuClF13P: C, 44.26;
H, 3.51. Found: C, 44.68; H, 3.75.
cis-(PhtBu2P)Au(octafluorobiphenyl)Cl2 (2f). The general proce-
dure using the complex (PhtBu2P)Au(octafluorobiphenyl) (1f; 143
mg, 0.200 mmol) and PhICl2 (110 mg, 0.400 mmol) in 3.0 mL of
CHCl3 gave cis-(PhtBu2P)Au(octafluorobiphenyl)Cl2 (2f) as a white
t
cis-[Au(PCy2 Bu)(octafluorobiphenyl)(C6F5)(Cl)] (3b). The general
1
procedure using AgF (56 mg, 0.44 mmol), TMSC6F5 (126 μL, 0.660
solid (110 mg, 70%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ
t
mmol), and cis-(Cy2 BuP)Au(octafluorobiphenyl)Cl2 (2b; 200 mg,
7.74 (t, J = 8.0 Hz, 2 H), 7.42 (m, 1 H), 7.33 (m 2 H), 7.18 (m, 1 H),
1.73 (d, J = 16.0 Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ −119.93
(m, 2 F), −137.16 (m, 1 F), −137.60 (m, 1 F), −137.83 (m, 2 F),
−138.56 (m, 1 F), −139.08 (m, 1 F). 31P NMR (162 MHz, CDCl3): δ
74.22 (m, 1 P). Anal. Calcd for C26H24AuCl2F8P: C, 39.67; H, 3.07.
Found: C, 39.68; H, 3.11.
t
0.244 mmol) in MeCN (2.0 mL) gave cis-[Au(PCy2 Bu)-
(octafluorobiphenyl)(C6F5)(Cl)] (3b) as a white solid (125 mg,
1
54%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.21 (m, 1 H),
2.81 (q, J = 11.5 Hz, 2 H), 2.28 (s, 2 H), 1.96 (d, J = 14.0 Hz, 2 H),
1.78 (s, 4 H), 1.71 (d, J = 14.4 Hz, 2 H), 1.57 (d, J = 14.8 Hz, 9 H),
1.52−1.50 (br, 2 H), 1.48−1.24 (br, 8 H). 19F NMR (376 MHz,
CDCl3): δ −118.63 (m, 2 F), −123.96 (m, 2 F), −137.34 to −137.68
(m, 4 F), −138.11(m, 1 F), −139.23 (m, 1 F), −157.03 (t, J = 19.9 Hz,
1 F), −160.77 (m, 2 F). 31P NMR (202 MHz, CDCl3): δ 49.51 (s, 1
P). Anal. Calcd for C34H32AuClF13P: C, 42.94; H, 3.39. Found: C,
43.28; H, 2.96.
cis-((p-Cl-C6H4)tBu2P)Au(octafluorobiphenyl)Cl2 (2g). The general
procedure using the complex ((p-Cl-C6 H4 )t Bu2 P)Au-
(octafluorobiphenyl) (1g; 203 mg, 0.270 mmol) and PhICl2 (148
mg, 0.540 mmol) in 3.0 mL of CHCl3 gave cis-((p-Cl-C6H4)tBu2P)-
1
Au(octafluorobiphenyl)Cl2 (2g) as a white solid (170 mg, 71%). H
NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.69 (t, J = 8.0 Hz, 2 H),
7.12 (dd, J = 8.0, 2.0 Hz, 2 H), 7.20 (m, 1 H), 1.78 (d, J = 16.0 Hz, 18
H). 19F NMR (376 MHz, CDCl3): δ −119.57 (m, 2 F), −137.74 (m, 3
F), −137.61 (m, 1 F), −138.40 (m, 1 F), −139.05 (m, 1 F). 31P NMR
(162 MHz, CDCl3): δ 76.05 (s, 1 P). Anal. Calcd for C26H23AuCl3F8P:
C, 38.00; H, 2.82. Found: C, 37.89; H, 2.95.
cis-[Au(PCytBu2)(octafluorobiphenyl)(C6F5)(Cl)] (3c). The general
procedure using AgF (56 mg, 0.44 mmol), TMSC6F5 (126 μL, 0.660
mmol), and cis-(CytBu2P)Au(octafluorobiphenyl)Cl2 (2c; 100 mg,
0.126 mmol) in MeCN (2.0 mL) gave cis-[Au(PCytBu2)-
(octafluorobiphenyl)(C6F5)(Cl)] (3c) as a white solid (72 mg,
1
cis-((p-CF3-C6H4)tBu2P)Au(octafluorobiphenyl)Cl2 (2h). The gen-
eral procedure using the complex ((p-CF3-C6H4)tBu2P)Au-
(octafluorobiphenyl) (1h; 235 mg, 0.300 mmol) and PhICl2 (165
mg, 0.600 mmol) in 3.0 mL of CHCl3 gave cis-((p-CF3-C6H4)tBu2P)-
62%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.20 (m, 1 H),
2.20 (s, 2 H), 1.79 (d, J = 13.2 Hz, 2 H), 1.74−1.54 (m, 23 H), 1.21
(q, J = 15.1 Hz, 2 H), 0.89 (s, 2H); 19F NMR (376 MHz, CDCl3): δ
−116.98 (m, 1.3 F), −123.95 (m, 2 F), −137.33 (m, 2 F), −137.57
(m, 2 F), −138.21 (m, 1 F), −139.38 (m, 1 F), −157.00 (t, J = 20.1
Hz, 1 F), −160.71 (m, 2 F). 31P NMR (202 MHz, CDCl3): δ 65.42 (s,
1 P). Anal. Calcd for C32H30AuClF13P: C, 41.55; H, 3.27. Found: C,
41.30; H, 3.44.
1
Au(octafluorobiphenyl)Cl2 (2h) as a white solid (130 mg, 51%). H
NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.97 (t, J = 8.0 Hz, 2 H),
7.69 (d, J = 8.0, 2 H), 7.24 (m, 1 H), 1.73 (d, J = 16.0 Hz, 18 H). 19F
NMR (376 MHz, CDCl3): δ −63.76 (d, J = 5.3 Hz, 3 F), −119.39 (m,
2 F), −137.07 (m, 2 F), −137.28 (m, 1 F), −137.54 (m, 1 F), −138.46
(m, 1 F), −139.24 (m, 1 F). 31P NMR (162 MHz, CDCl3): δ 76.40 (s,
1 P). Anal. Calcd for C27H23AuCl2F11P: C, 37.92; H, 2.71. Found: C,
37.74; H, 2.79.
cis-[Au(P(p-OMe-C6H4)tBu2)(octafluorobiphenyl)(C6F5)(Cl)] (3d).
The general procedure using AgF (56 mg, 0.44 mmol), TMSC6F5
(126 μL, 0.660 mmol), and cis-((p-MeOC6H4)tBu2P)Au-
(octafluorobiphenyl)Cl2 (2d; 200 mg, 0.245 mmol) in MeCN (2.0
mL) gave cis-[Au(P(p-OMe-C6H4)tBu2)(octafluorobiphenyl)(C6F5)-
(Cl)] (3d) as a white solid (94 mg, 45%). 1H NMR (400 MHz,
CDCl3, 293 K, TMS): δ 7.69 (t, J = 9.0 Hz, 2 H), 7.21 (m, 1 H), 6.95
(dd, J = 8.8, 2.0 Hz, 2 H), 3.84 (s, 3 H), 1.56 (d, J = 15.2 Hz, 18 H).
19F NMR (376 MHz, CDCl3): δ −117.60 (m, 2 F), −123.68 (m, 2 F),
−137.50 to −137.78 (m, 4 F), −138.46 (m, 1 F), −139.26 (m, 1 F),
−156.81 (m, 1 F), −160.68 (m, 2 F). 31P NMR (202 MHz, CDCl3): δ
62.43 (s, 1 P). Anal. Calcd for C33H26AuClF13OP: C, 41.77; H, 2.76.
Found: C, 41.99; H, 2.86.
cis-(tBu3P)Au(octafluorobiphenyl)Cl2. The general procedure using
complex (tBu3P)Au(octafluorobiphenyl) (63.1 mg, 0.0734 mmol) and
PhICl2 (99.8 mg, 0.363 mmol) in 3.0 mL of CHCl3 gave cis-
(tBu3P)Au(octafluorobiphenyl)Cl2 as a yellow solid (39 mg, 54%). 1H
NMR (400 MHz, CD2Cl2, 293 K, TMS): δ 7.22 (m, 1 H), 1.61 (d, J =
16.0 Hz, 27 H) ppm; 19F NMR (376 MHz, CD2Cl2): δ −119.75 (m, 2
F), −138.17 to −138.69 (m, 4 F), −139.14 (m, 1 F), −139.84 (m, 1
F). 31P NMR (162 MHz, CD2Cl2): δ 107.54 (s, 1 P). Anal. Calcd for
C24H28AuCl2F8PS: C, 37.57; H, 3.68. Found: C, 37.54; H, 3.67.
K
DOI: 10.1021/acs.organomet.7b00588
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
cis-[Au(P(p-Me-C6H4)tBu2)(octafluorobiphenyl)(C6F5)(Cl)] (3e).
The general procedure using AgF (56 mg, 0.44 mmol), TMSC6F5
(126 μL, 0.660 mmol), and cis-((p-Me-C6H4)tBu2P)Au-
(octafluorobiphenyl)Cl2 (2e; 200 mg, 0.250 mmol) in MeCN (2.0
mL) gave cis-[Au(P(p-Me-C6H4)tBu2)(octafluorobiphenyl)(C6F5)-
H). 19F NMR (376 MHz, CDCl3): δ −56.27 (t, J = 10.5 Hz, 3 F),
−117.80 (m, 2 F), −122.23 (m, 2 F), −137.24 (m, 2 F), −137.54 (m,
1 F), −137.67 (m, 1 F), −138.28 (m, 1 F), −138.89 (m, 1 F), −140.08
(m, 2 F). 31P NMR (202 MHz, CDCl3): δ 62.40 (s, 1 P). Anal. Calcd
for C33H24AuClF15P: C, 40.91; H, 2.50. Found: C, 41.02; H, 2.93.
General Procedure for Preparation of Reductive Elimination
Products from Biaryls: 2,2′,2″,3,3′,3″,4,5,5′,5″,6,6′,6″-Trideca-
fluoro-1,1′:4′,1″-terphenyl (4). In a glovebox, AgF (25 mg, 0.44
mmol), TMSC6F5 (62 mg, 0.26 mmol), and 2.0 mL of MeCN were
placed in a 4 mL Schlenk tube that was equipped with a stirring bar.
The reaction mixture was stirred in the dark for 3 h. (tBu3P)Au-
(octafluorobiphenyl)Cl2 (100 mg, 0.130 mmol) was placed in the
Schlenk tube, and the reaction mixture was stirred in the dark for 5 h.
The solvent was removed, and the residue was purified by flash
chromatography on silica gel (100%, n-pentane) to give
2,2′,2″,3,3′,3″,4,5,5′,5″,6,6′,6″-tridecafluoro-1,1′:4′,1″-terphenyl (4)
1
(Cl)] (3e) as a white solid (158 mg, 68%). H NMR (400 MHz,
CDCl3, 293 K, TMS): δ 7.63 (t, J = 8.0 Hz, 2 H), 7.23 (d, J = 8.0 Hz, 2
H), 7.21 (m, 1 H), 2.37 (s, 3 H), 1.58 (d, J = 16.0 Hz, 18 H). 19F
NMR (376 MHz, CDCl3): δ −117.70 (m, 2 F), −123.64 (m, 2 F),
−137.72 (m, 4 F), −138.42 (m, 1 F), −139.27 (m, 1 F), −156.81 (t, J
= 19.3 Hz, 1 F), −160.69 (m, 2 F). 31P NMR (202 MHz, CDCl3): δ
62.29 (s, 1 P). Anal. Calcd for C33H26AuClF13P: C, 42.49; H, 2.81.
Found: C, 42.35; H, 3.09.
cis-[Au(PPhtBu2)(octafluorobiphenyl)(C6F5)(Cl)] (3f). The general
procedure using AgF (56 mg, 0.44 mmol), TMSC6F5 (126 μL, 0.660
mmol), and cis-(PhtBu2P)Au(octafluorobiphenyl)Cl2 (2f; 180 mg,
0.229 mmol) in MeCN (2.0 mL) gave cis-[Au(PPhtBu2)-
(octafluorobiphenyl)(C6F5)(Cl)] (3f) as a white solid (94 mg,
1
as a white solid (43 mg, 71%). Mp: 144−145 °C. H NMR (400
MHz, CDCl3, 293 K, TMS): δ 7.31 (m, 1 H). 19F NMR (376 MHz,
CDCl3): δ −136.81 (m, 2 F), −137.00 (m, 4 F), −137.28 (m, 2 F),
−137.85 (m, 2 F), −149.38 (t, J = 20.9 Hz), −160.12 (m, 2 F) ppm.
GC-MS (EI; m/z): 464. HRMS (EI; m/z): calcd for C18HF13:
463.9871; found: 463.9870. IR: ν 3080, 1507, 1244, 1136, 980, 953,
742, 722, 706 cm−1.
2,2′,2″,3,3′,3″,5,5′,5″,6,6′,6″-Dodecafluoro-1,1′:4′,1″-terphenyl
(5).24 The general procedure using cis-(PhtBu2 P)Au-
(octafluorobiphenyl)(p-HC6F4)Cl (3i; 100 mg, 0.111 mmol) in 2.0
mL of CDCl3 gave 2,2′,2″,3,3′,3″,5,5′,5″,6,6′,6″-dodecafluoro-
1,1′:4′,1″-terphenyl (5) as a white solid (42 mg, 85%). 1H NMR
(400 MHz, CDCl3, 293 K, TMS): δ 7.30 (m, 2 H). 19F NMR (376
MHz, CDCl3): δ −137.08 (m, 4 F), −137.34 (m, 4 F), −137.82 (m, 4
F) ppm. GC-MS (EI; m/z): 464.
1
45%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.76 (t, J = 8.4
Hz, 2 H), 7.49−7.40 (m, 3 H), 7.20 (m, 1 H), 1.60 (d, J = 15.2 Hz, 18
H). 19F NMR (376 MHz, CDCl3): δ −117.76 (s, 2 F), −123.66 (m, 2
F), −137.62 to −137.79 (m, 4 F), −138.39 (m, 1 F), −138.89 (m, 1
F), −156.74 (m, 1 F), −160.50 (m, 2 F). 31P NMR (162 MHz,
CDCl3): δ 62.59 (m, 1 P). Anal. Calcd for C32H24AuClF13P: C, 41.83;
H, 2.63. Found: C, 41.96; H, 2.81.
cis-[Au(P(p-Cl-C6H4)tBu2)(ArF)(octafluorobiphenyl)(Cl)] (3g). The
general procedure using AgF (56 mg, 0.44 mmol), TMSC6F5 (126 μL,
0.660 mmol), and cis-((p-Cl-C6H4)tBu2P)Au(octafluorobiphenyl)Cl2
(2g; 160 mg, 0.195 mmol) in MeCN (2.0 mL) gave cis-[Au(P(p-Cl-
C6H4)tBu2)(ArF)(octafluorobiphenyl)(Cl)] (3g) as a white solid (98
1
mg, 53%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.71 (t, J =
2,2′,2″,3,3′,3″,5,5′,5″,6,6′,6″-Dodecafluoro-4-(trifluoromethyl)-
1,1′:4′,1″-terphenyl (6). The general procedure using cis-(PhtBu2P)-
Au(octafluorobiphenyl)(p-CF3C6F4)Cl (3j; 100 mg, 0.103 mmol) in
2.0 mL of CDCl3 gave 2,2′,2″,3,3′,3″,5,5′,5″,6,6′,6″-dodecafluoro-4-
(trifluoromethyl)-1,1′:4′,1″-terphenyl (6) as a white solid (45 mg,
87%). Mp: 150−151 °C. 1H NMR (400 MHz, CDCl3, 293 K, TMS):
δ 7.32 (m, 1 H). 19F NMR (376 MHz, CDCl3): δ −56.52 (t, J = 21.8
Hz, 3 F), −135.09 (m, 2 F), −136.26 (m, 2 F), −136.66 (m, 2 F),
−137.18 (m, 2 F), −138.74 (m, 2 F) ppm. GC-MS (EI; m/z): 514;
HRMS (EI; m/z): calcd for C19HF15, 513.9839; found, 513.9846. IR: ν
3087, 1657, 1480, 1342, 1256, 1150, 1002, 983, 726, 705 cm−1.
Typical Procedure for Kinetic Study of C(sp2)−C(sp2)
Reductive Elimination Reaction from Complex 3f. In an argon-
filled glovebox, 0.02 mmol of complex 3f was placed in a screw-cap
NMR tube. CDCl3 (0.4 mL) was used as the solvent, and
trifluorotoluene or fluorobenzene was used as the internal standard.
The NMR probe was heated at 85 °C. Thermolysis of complex 3f was
monitored by 19F NMR spectroscopy. Kinetic data were fit to the
expression y = m1 + m2 exp−t/K, in which 1/K is the first-order rate
constant kobs. All results were average of two runs.
Computational Methods. All of the DFT calculations were
carried out with the Gaussian 0925 series of programs. The B3LYP26
functional with the standard 6-31G(d) basis set (SDD27 for Au atoms)
was used for geometry optimizations. The vibrational frequencies were
computed at the same level of theory to determine whether the
optimized structure was at an energy minimum or a transition state
and to evaluate the corrections of enthalpy and Gibbs free energy. The
B3LYP-D328 functional with the 6-311+G(d) basis set (SDD for Au
atoms) was used to calculate the single-point energies. The solvent
effects were considered by single-point calculations of the gas-phase
stationary points with the SMD continuum model.29 The energies
reported in this paper are the B3LYP-D3 calculated Gibbs free
energies in CDCl3 on the basis of B3LYP calculated geometries with
thermodynamic corrections calculated at the same level. In this study,
the B3LYP functional, which has been verified to be a favorable
functional for geometry optimization in a transition-metal-catalyzed
system, was used for geometry optimization.30 On the other hand, the
addition of dispersion interaction into the B3LYP functional could
describe the long-range interactions better, and thus an atom−atom
9.0 Hz, 2 H), 7.44 (d, J = 6.8 Hz, 2 H), 7.22 (m, 1 H), 1.55 (d, J = 15.6
Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ −117.59 (m, 2 F),
−123.75 (m, 2 F), −137.18 (m, 2 F), −137.68 (m, 2 F), −138.23 (m,
1 F), −139.01 (m, 1 F), −156.44 (m, 1 F), −160.51 (m, 2 F). 31P
NMR (202 MHz, CDCl3): δ 62.86 (s, 1 P). Anal. Calcd for
C32H23AuCl2F13P: C, 40.32; H, 2.43. Found: C, 40.02; H, 2.76.
cis-[Au(P(p-CF3-C6H4)tBu2)(octafluorobiphenyl)(C6F5)(Cl)] (3h).
The general procedure using AgF (56 mg, 0.44 mmol), TMSC6F5
(126 μL, 0.660 mmol), and cis-((p-CF3-C6H4)tBu2P)Au-
(octafluorobiphenyl)Cl2 (2h; 60 mg, 0.070 mmol) in MeCN (2.0
mL) gave cis-[Au(P(p-CF3-C6H4)tBu2)(octafluorobiphenyl)(C6F5)-
(Cl)] (3h) as a white solid (37 mg, 53%). 1H NMR (400 MHz,
CDCl3, 293 K, TMS): δ 7.92 (t, J = 8.8 Hz, 2 H), 7.72 (d, J = 7.6 Hz, 2
H), 7.18 (m, 1 H), 1.55 (d, J = 16.0 Hz, 18 H). 19F NMR (376 MHz,
CDCl3): δ −63.49 (s, 3 F), −117.57 (m, 2 F), −123.75 (m, 2 F),
−136.99 (m, 2 F), −137.71 (m, 2 F), −138.25 (m, 1 F), −139.10 (m,
1 F), −156.25 (t, J = 19.9 Hz, 1 F), −160.41 (m, 2 F). 31P NMR (202
MHz, CDCl3): δ 64.09 (m, 1 P). Anal. Calcd for C33H23AuClF16P: C,
40.16; H, 2.35. Found: C, 40.51; H, 2.68.
cis-(PhtBu2P)Au(octafluorobiphenyl)(p-HC6F4)Cl (3i). The general
procedure using AgF (56 mg, 0.44 mmol), trimethyl(2,3,5,6-
tetrafluorophenyl)silane (126 μL, 0.660 mmol), and cis-(PhtBu2P)Au-
(octafluorobiphenyl)Cl2 (2f; 100 mg, 0.127 mmol) in MeCN (2.0
mL) gave cis-(PhtBu2P)Au(octafluorobiphenyl)(p-H-C6F4)Cl (3i) as a
white solid (63 mg, 55%). 1H NMR (400 MHz, CDCl3, 293 K, TMS):
δ 7.77 (t, J = 8.4 Hz, 2 H), 7.49−7.41 (m, 3 H), 7.22 (m, 1 H), 6.82
(m, 1 H), 1.59 (d, J = 15.2 Hz, 18 H). 19F NMR (376 MHz, CDCl3): δ
−117.60 (m, 2 F), −125.27 (m, 2 F), −137.63 (m, 1 F), −137.82 (m,
3 F), −138.45 (m, 1 F), −138.66 (m, 2 F), −138.96 (m, 1 F), −160.51
(m, 2 F). 31P NMR (202 MHz, CDCl3): δ 62.32 (m, 1 P). Anal. Calcd
for C32H25AuClF12P: C, 42.66; H, 2.80. Found: C, 42.61; H, 3.17.
cis-(PhtBu2P)Au(octafluorobiphenyl)(p-CF3C6F4)Cl (3j). The gen-
eral procedure using using trimethyl(2,3,5,6-tetrafluoro-4-
(trifluoromethyl)phenyl)silane (126 μL, 0.660 mmol), AgF (56 mg,
0.44 mmol), and cis-(PhtBu2P)Au(octafluorobiphenyl)Cl2 (2f; 80 mg,
0.10 mmol) in 2.0 mL of MeCN gave cis-(PhtBu2P)Au-
(octafluorobiphenyl)(p-CF3-C6F4)Cl (3j) as a white solid (66 mg,
1
67%). H NMR (400 MHz, CDCl3, 293 K, TMS): δ 7.76 (t, J = 9.2
Hz, 2 H), 7.50−7.41 (m, 3 H), 7.21 (m, 1 H), 1.61 (d, J = 15.2 Hz, 18
L
DOI: 10.1021/acs.organomet.7b00588
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Organometallics
Article
additive damped empirical potential of the form −f(R)C6/R6, which is
named B3LYP-D3, was employed in our work to give more accurate
energy information. This functional has also been widely used in Au
and other transition-metal-catalyzed systems.31 Consequently, the
conclusion can be drawn that the B3LYP-D3 functional could provide
accuracy in energetic information for this work. In general, the strain/
electronic effects on a reaction mechanism could be addressed by a
distortion/interaction model.32 However, this model only could be
applied on a bimolecular reaction system, which is for to this
intramolecular reaction.
(d) Murakami, Y.; Yamamoto, T. Inorg. Chem. 1997, 36, 5682.
(e) Yamamoto, T.; Abla, M.; Murakami, Y. Bull. Chem. Soc. Jpn. 2002,
75, 1997. (f) Yamamoto, T.; Yamaguchi, I.; Abla, M. J. Organomet.
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A.-W. J. Am. Chem. Soc. 2009, 131, 9892. (h) Xu, H.-W.; Diccianni, J.
B.; Katigbak, J.; Hu, C.-H.; Zhang, Y.-K.; Diao, T.-N. J. Am. Chem. Soc.
2016, 138, 4779.
(5) Selected examples of C(sp2)−C(sp2) reductive elimination from
Pd(II) complexes: (a) Moravskiy, A.; Stille, J. K. J. Am. Chem. Soc.
1981, 103, 4182. (b) Deacon, G. B.; Gray, I. L. Transition Met. Chem.
1983, 8, 131. (c) Ozawa, F.; Yamamoto, T.; Yamamoto, A. J.
Organomet. Chem. 1987, 330, 253. (d) Culkin, D. A.; Hartwig, J. F. J.
Am. Chem. Soc. 2001, 123, 5816. (e) Culkin, D. A.; Hartwig, J. F.
Organometallics 2004, 23, 3398. (f) Ananikov, V.; Musaev, D. G.;
Morokuma, K. Organometallics 2005, 24, 715. (g) Osakada, K.;
Onodera, H.; Nishihara, Y. Organometallics 2005, 24, 190. (h) Koizumi,
T.; Yamasaki, A.; Yamamoto, T. Dalton Trans. 2008, 3949. (i) Gensch,
T.; Ronnefahrt, M.; Czerwonka, R.; Jager, A.; Kataeva, O.; Bauer, I.;
Knolker, H. Chem. - Eur. J. 2012, 18, 770. (j) Klinkenberg, J. L.;
Hartwig, J. F. J. Am. Chem. Soc. 2012, 134, 5758. (k) Gioria, E.; del
Pozo, J.; Martinez-Ilarduya, J. M.; Espinet, P. Angew. Chem., Int. Ed.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.7b00588.
■
S
Synthesis details, analytical data, NMR data of
compounds 1a−i, 2a−i, 3a−j, and 4−6, X-ray diffraction
data of complexes 3a−f,h−j and cis-[Au(PPh3)(ArF)Cl2]
(2i),33 data for kinetic studies, and theoretical calculation
of reductive elimination from complexes 3 (PDF)
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Accession Codes
CCDC 1557972−1557981 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
*E-mail for Y.L.: lanyu@cqu.edu.cn.
*E-mail for Q.S.: shenql@sioc.ac.cn.
■
ORCID
Yu Lan: 0000-0002-2328-0020
Qilong Shen: 0000-0001-5622-153X
Notes
The authors declare no competing financial interest.
́
Chem. Soc. Rev. 2011, 40, 1910. (f) Miro, J.; del Pozo, C. Chem. Rev.
ACKNOWLEDGMENTS
■
2016, 116, 11924. (g) Hopkinson, M. N.; Tlahuext-Aca, A.; Glorius, F.
Acc. Chem. Res. 2016, 49, 2261.
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (21625206,
21632009, 21372247, 21572258, 21421002) and the Strategic
Priority Research Program of the Chinese Academy of Sciences
(XDB20000000).
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Jones, G. C.; Russell, C. A. Science 2012, 337, 1644. (e) Ball, L. T.;
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