Ruthenium carbonyl complexes bearing secondary phosphine oxides and phosphinous acids: Synthesis, characterization, and application in catalysis

Article abstract of DOI:10.1021/om501300p

Two series of ruthenium carbonyl complexes bearing either one secondary phosphine oxide ligand or two phosphinous acids have been synthesized and characterized. The catalytic behavior of these complexes has been then investigated for the cycloisomerizatio

Full text of DOI:10.1021/om501300p

Article
pubs.acs.org/Organometallics
Ruthenium Carbonyl Complexes Bearing Secondary Phosphine
Oxides and Phosphinous Acids: Synthesis, Characterization, and
Application in Catalysis
†
‡
,†
Clavier*,†
Lionel V. Graux, Michel Giorgi, Ger
́
ard Buono,* and Herve
́
†
Aix Marseille Universite,
Aix Marseille Universite,
S Supporting Information
́
́
Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France
‡
Spectropole, Federation des Sciences Chimiques de Marseille, 13397 Marseille, France
́
́
*
ABSTRACT: Two series of ruthenium carbonyl complexes
bearing either one secondary phosphine oxide ligand or two
phosphinous acids have been synthesized and characterized.
The catalytic behavior of these complexes has been then
investigated for the cycloisomerization of arenynes. This study
highlighted a strong relationship between ligands’ and
substrates’ substructures.
INTRODUCTION
Secondary phosphine oxides (SPO) and phosphinous acids
PA) are interesting phosphorus compounds, especially as
knowledge, for late transition metals, only a few examples have
■
(
been reported. With nickel, these complexes are difficult to
7
isolate (32% yield in the best case), and with rhodium,
3
,8
1
complexes D have been only observed in solution. The
intricacy of SPOs’ and PAs’ coordination modes might explain
why these ligands have been little investigated so far.
ligands in coordination chemistry. As depicted in Scheme 1, a
Scheme 1. Tautomeric Equilibrium between SPO and PA
and Their Resulting Coordination Modes
Yet, they have attracted an ever-growing attention since Li
reported that PA-containing palladium complexes are com-
Figure 1. Ruthenium complexes bearing PA or SPO ligands.
petent to perform C−C and C−X bond formations by cross-
tautomeric equilibrium between the tricoordinated trivalent
9
,10
3
3
coupling reactions.
As a testimony of SPO potential in
(
σ λ ) phosphinous acid and the tetracoordinated pentavalent
2
4
5
catalysis, Cramer described recently a nickel-based catalytic
system including a chiral diaminophosphine oxide for the
(σ λ ) phosphine oxide form does exist in solution and is
generally completely shifted in favor of the phosphine oxide
form. Nevertheless, the P(III) compound can coordinate a
transition metal to afford complexes A or B bearing respectively
one or two PA units. In this case, SPOs are considered as
preligands. In the presence of base, B is converted into complex
C bearing the phosphinito-phosphinous acid pincer ligand. The
study of the electronic properties of these ligands showed
comparable electron-donating abilities between phosphinous
acids and the corresponding phosphines, but phosphinito
11
enantioselective hydrocarbamoylation of alkenes. As well,
these ligands were also successfully applied to gold-catalyzed
12
cycloisomerization of enynes. On the other hand, it has been
demonstrated that PAs were more than phosphine mimics, as
they promote an unusual palladium-mediated [2+1] cyclo-
addition between activated C−C double bonds (norbornene
13
derivatives) and terminal alkynes. Platinum-based complexes
have shown a similar catalytic behavior, and even an
unprecedented intermolecular tandem [2+1]/[3+2] cyclo-
3
ligands are significantly more donating. Alternatively, SPO can
14
addition sequence was achieved.
coordinate the metal through the oxygen atom to give rise to
complex D. However, this mode of coordination has been
4
scarcely observed, mainly with rare earth metals, early
Received: December 18, 2014
5
6
transition metals, or group 13 elements. To the best of our
©
XXXX American Chemical Society
A
DOI: 10.1021/om501300p
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
a
room temperature was monitored by 31P NMR spectroscopy
and showed the rapid appearance of a new resonance at 57.4
Scheme 2. Preparation of [RuCl (CO) (SPO)] Complexes
2
3
1
ppm with a J(P,H) = 504.6 Hz, whereas the free SPO presents
1
a higher field signal at 47.4 ppm with a J(P,H) = 452.8 Hz.
The complex was isolated as an air-stable pale yellow solid in an
1
almost quantitative yield (Scheme 2). The J(P,H) coupling
constant indicates that the phosphorus atom is tetracoordi-
nated; thus in 5a, the ruthenium binds the SPO through the
oxygen. To unambiguously establish the structure of 5a,
suitable crystals for single-crystal diffraction studies were
obtained. The thermal ellipsoid representation with selected
bond distances and angles is presented in Figure 2. 5a shows
a
Ad = adamantyl; NR = no reaction.
Table 1. 31P Chemical Shifts and J-Coupling of Complexes 5
and Free SPOs in CDCl at 25 °C
3
1
δ (ppm) ( J(P,H) (Hz))
entry
R1, R2
complex 5
free SPO 4
1
2
3
4
Ph, tBu (a)
Ph, nBu (b)
Ph, Me (c)
Cy, Cy (e)
57.36 (504.6)
43.70 (515.5)
61.20 (483.4)
37.42 (534.0)
47.41 (452.8)
27.98 (463.1)
49.97 (433.8)
20.21 (472.2)
Table 2. Carbonyl and PO Stretching Frequencies of
Complexes 5 (IR Spectra Recorded Using an ATR Device)
Figure 2. Molecular structure of complex 5a represented at the 50%
ellipsoid probability level. Most of the H atoms have been omitted for
clarity. Selected bond lengths (Å) and angles (deg): Ru(1)−O(1)
entry
complex
νCO (cm−1)
νPO (cm−1
)
1
2
3
4
5a
5b
5c
5e
2130, 2069, 2025
2130, 2043
1139
1134
1136
1097
2
.103(5); Ru(1)−C(11) 1.890(9); Ru(1)−C(12) 1.891(9); Ru(1)−
C(13) 1.899(10); Ru(1)−Cl(1) 2.398(2); Ru(1)−Cl(2) 2.3853(17);
2134, 2067, 2049
2129, 2044, 1993
O(1)−P(1) 1.513(5); P(1)−H(1) 1.4895; C(11)−Ru(1)−O(1)
8
9
9
9.1(3); C(11)−Ru(1)−C(12) 92.1(4); C(11)−Ru(1)−C(13)
4.3(4); C(11)−Ru(1)−Cl(1) 85.7(3); Cl(1)−Ru(1)−Cl(2)
1.17(8); Ru(1)−O(1)−P(1) 129.8(3); O(1)−P(1)−H(1) 122.7.
Scheme 3. Synthesis of Complex
RuCl (CO) (PhtBuPOH) ] 6a
[
2
2
2
It is noteworthy that, when the two substituents of the
phosphorus atom are different, this center becomes stereogenic
and does not racemize during the tautomeric equilibrium. Thus,
chiral SPOs were successfully applied in asymmetric
13c,15
catalysis.
In spite of interesting applications of ruthenium-SPO
17
16
catalytic systems, such as C−H activation, hydrogenation,
1
8
and nitrile hydration, the preparation of well-defined
Scheme 4. Preparation of 6a Starting from Complex
RuCl (CO) (PhtBuPHO)], 5a
ruthenium complexes bearing SPO or PA ligands has been
[
2
3
6
1 2
barely investigated. Few [Ru(η -arene)(R R POH)] complexes
18−20
1
or 2 have been reported (Figure 1).
Stephenson
reported a complex 3 containing a polydentate ligand
21
composed from two PAs and one phosphinito species.
Another study on cyclopentadiene ruthenium species high-
lighted the difficulty to prepare and isolate well-defined
22
complexes bearing SPO and PA ligands.
Herein, we disclose a general study on the coordination
mode of SPO and PA ligands to ruthenium. Two series of
ruthenium carbonyl complexes bearing either one SPO ligand
or two PAs have been synthesized and fully characterized. The
catalytic behavior of these complexes has been investigated for
the cycloisomerizations of arenynes.
the expected distorted octahedral geometry around the metal
center with bond angles between 85.7° and 94.3°. The Ru(1)−
O(1) distance (2.103 Å) suggests a dative covalent bond,
whereas the short O(1)−P(1) bond length (1.513 Å) is in
agreement with a double-bond character. Other bond distances
were found comparable to those reported for similar complexes.
We prepared other complexes 5 using different SPOs
(Scheme 2). Whereas SPOs 4b, 4c, and 4e gave quantitatively
the corresponding complexes, no reaction was observed with
sterically demanding SPO 4h and 4i despite a prolonged
RESULTS AND DISCUSSION
■
23
After the examination of several ruthenium sources, we
focused our efforts on the commercially available
tricarbonyldichlororuthenium(II) dimer. The treatment of
[
RuCl (CO) ] with 1 equiv of PhtBuPHO 4a in THF at
2 3 2
B
DOI: 10.1021/om501300p
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Table 3. Preparation of Complexes [RuCl (CO) (PA) ] 6
By examining the PO stretching frequencies, we confirmed
2
2
2
the coordination of the ligand to the ruthenium through the
25
−1
oxygen atom (Table 2). For complex 5a, a band at 2374 cm
relative to the P−H bond stretching frequency was even
detected.
We then treated the [RuCl (CO) ] dimer with 4 equiv of
2
3 2
SPO 4a under harsher reaction conditions (toluene at 110 °C)
31
(
Scheme 3). The P NMR monitoring showed the appearance
time
yield
(%)
e.d.
of new resonances at 113.0 and 113.8 ppm. After 10 days, 6a
was isolated in 85% yield as an air- and moisture-stable light
yellow solid. We attributed the two resonances to the formation
of a 1:1 mixture of diastereomers like (S *S *) and unlike
26
a
entry
1
SPO ligand
complex
(days)
(%)
(±)-PhtBuPHO,
6a
10
10
3
85
92
82
30
0
(
±)-4a
p
p
2
3
4
(S )-PhtBuPHO, (S )-
6a
6b
6c
90
20
20
20
p
p
4a
(R *S *), resulting from the use of the racemic SPO (±)-4a.
p p
(±)-PhnBuPHO,
±)-4b
To confirm this hypothesis, the reaction was carried out with
(
the enantiopure SPO (S )-4a, and almost exclusively the
p
(±)-PhMePHO,
±)-4c
3
diastereomer like (S S ) was formed in 92% yield (Scheme 3).
p
p
(
It also evidenced that the P-stereogenic center is configura-
tionally stable since only a slight racemization was observed
despite the harsh reaction conditions. The NMR monitoring of
5
6
7
8
(±)-PhCyPHO, (±)-4d
6d
6e
6f
3
3
81
92
53
83
Cy PHO, 4e
2
Ph PHO, 4f
2
3
6a synthesis showed an early formation of 5a, which was
(p-F-C H ) PHO, 4g
6g
6h
3
6
4 2
c
suspected to be an intermediate. Indeed, the heating of complex
9
tBu PHO, 4h
10
10
NR
2
b
5a in toluene for 10 days gave rise to 6a quantitatively; the yield
10
Ad PHO, 4i
2
6i
NR
27
is based on phosphorus species (Scheme 4). However, we
a
b
c
e.d. refers to like/unlike ratio. Ad = adamantyl. NR = no reaction.
were unable to determine if the coordination of the second
phosphinous acid by CO displacement occurred before or after
the already bound SPO ligand switches its coordination mode.
The preparation of a series of complexes 6 was then achieved
using various dissymmetric and symmetric SPO preligands
(Table 3). Complexes 6 were isolated in moderate to good
yields, except for 6c, which presented a low stability (30%,
Table 4. Stretching Frequencies of Complexes 6 (IR Spectra
Recorded Using an ATR Device)
ν
ν
O−H
P−O
−1
−1
entry
1
complex
νCO (cm−1)
2050, 1993
(cm
)
(cm )
6a,
873
3221
[
RuCl (CO) (PhtBuPOH) ]
2
2
2
entry 4). Bulky phosphinous acids, such as tBu POH 4h and
2
2
3
6b,
2056, 1992
2050,1990
876
873
3163
Ad POH 4i, were unable to coordinate the ruthenium center
2
[
RuCl (CO) (PhnBuPOH) ]
2
2
2
despite a prolonged heating at 110 °C (entries 9 and 10). With
racemic dissymmetric SPOs 4b−d, low diastereoselectivities
were observed, and the relative configurations of the major
diastereomers could not attributed (entries 3−5). The
6d,
3250
(br)
[
RuCl (CO) (PhCyPOH) ]
2 2 2
4
5
6e, [RuCl (CO) (Cy POH) ] 2048,1991
856
879
3266
2
2
2
2
6f, [RuCl (CO) (Ph POH) ] 2058,1991
3100
br)
2
2
2
2
(
quantification of the steric parameter of phosphinous acids
6
6g, [RuCl (CO) (p−F-
2065,2002
879
3171
28,29
2
2
through the percent buried volume (%V )
has been
bur
12
C H ) POH) ]
6
4
2
2
previously determined on gold complexes. It revealed that
tBu POH is significantly more sterically demanding than
2
tBuPhPOH (32.6% vs 29.2%) and might explain the absence
of coordination we noticed.
3
1
heating at 80 °C in dioxane. P NMR spectra of the complexes
b, 5c, and 5e showed a characteristic low-field resonance with
a shift from 10 to 17 ppm compared to the free SPO ligands
Table 1). These low values expressed a weak interaction
5
The IR stretching frequencies of complexes 6 allowed us to
collect structural information (Table 4). The νP−O and νO−H
−
1
−1
(
bands in the ranges 856−879 cm and 3100−3266 cm ,
between the ligand and the metal. In the same manner, J-
couplings increased slightly, from about 50 Hz, and revealed a
more pronounced s character of the P−H bond.
respectively, confirmed the formation of Ru−P bonds.
−
1
Moreover, the two ν
bands at 2050−2065 cm and
CO
24
−1
1990−2002 cm indicated a cis arrangement of the carbonyl
Table 5. Selected Bond Lengths (Å) and Angles (deg) for Complexes [RuCl (CO) (PA) ] 6a, 6c, and 6e
2
2
2
entry
1
complex
Ru−P (Å)
Ru−C (Å)
Ru−Cl (Å)
P−O (Å)
1.6016(17)
15995(17)
1.607(4)
O···Cl (Å)
6a
2.4050(6)
1.860(2)
1.863(2)
2.4399(6)
2.4404(6)
2.4306(16)
2.4274(17)
2.400(4)
3.048
3.051
2.983
3.077
3.036
3.226
2
.4060(7)
2.3919(18)
.3940(19)
2.3988(9)
.4045(8)
2
2
6d
6e
1.863(7)
2
1.856(7)
1.603(5)
1.612(2)
1.616(2)
1.892(15)
1.893(13)
P−Ru−P (deg)
2
2.424(4)
entry
complex
C−Ru−C (deg)
Cl−Ru−Cl (deg)
4
5
6
6a
6d
6e
164.50(2)
170.34(6)
180.00(4)
91.37(11)
92.7(3)
88.55(2)
88.04(6)
83.03(17)
90.6(9)
C
DOI: 10.1021/om501300p
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Organometallics
Article
Figure 3. Molecular structures of complexes 6a (left), 6d (middle), and 6e (right) represented at 50% ellipsoid probability. Most of the H atoms
have been omitted for clarity.
a
groups. Indeed, for [RuCl (CO) (PPh ) ], the trans arrange-
Table 6. Cycloisomerization of Arenyne 7
2
2
3 2
ment of the CO ligands is characterized by a single asymmetric
−1
stretching band at 2011 cm , whereas the cis configuration
shows symmetric and asymmetric stretching bands at 2059 and
−1
30
1
997 cm . The CO symmetric stretching frequencies of
complexes 6 allowed the ranking of PA ligands according to
their σ-donating properties, Cy POH being the most electron-
2
donating ligand and (p-F-C H ) POH the least. This is in good
loading
time
(h)
conversion
6
4 2
31
b
entry
1
[Ru]
[RuCl (CO)
(mol %)
(%)
agreement with Tolman’s seminal work. In this series, the
difference of electronic properties between phosphinous acids
]
8 (16 mol %
Ru)
3
traces
2
3
2
−1
and phosphines was found to be small (2058 cm for Ph POH
2
c
vs 2059 cm−1 for PPh3).
2
[RuCl (CO) ]
8 (16 mol %
Ru)
3
traces
2
3
2
A single-crystal X-ray diffraction study was performed to
unambiguously determine the atom connectivity in complexes
d
3
none
16
16
3
3
15
11
4
5
6
5a
6a, 6d, and 6e. ORTEP representations are shown in Figure 3,
[RuCl (CO) (PhtBuPHO)]
2
3
and selected bond lengths and angles are reported in Table 5.
The ruthenium atom adopted an octahedral geometry around
the metal center in all the complexes with cis arrangements of
chlorines and carbonyls. PAs were positioned in trans position
with a hydrogen bonding with chlorines, attested by O···Cl
distances less to 3.2 Å. The P−Ru−P angle for 6a (164.50°)
indicated a tilt probably to accommodate both the steric bulk of
PhtBuPOH and the hydrogen bondings. Other bond distances
and angles were similar to those reported for analogous
complexes.
6a,
16
16
1
1
50
90
[
RuCl (CO) (PhtBuPOH) ]
2
2
2
6d,
[
RuCl (CO) (PhCyPOH) ]
2 2 2
e
7
8
9
6e, [RuCl (CO) (Cy POH) ] 16
0.5
1
100 (77)
2
2
2
2
6f, [RuCl (CO) (Ph POH) ] 16
83
64
2
2
2
2
6g, [RuCl (CO) (p-F-
16
3
2
2
C H ) POH) ]
6
4
2
2
10
11
12
6e, [RuCl (CO) (Cy POH) ]
8
5
2
2
1
1
1
8
100
95
2
2
2
2
6e, [RuCl (CO) (Cy POH) ]
2
2
2
2
6e, [RuCl (CO) (Cy POH) ]
38
2
2
2
2
As Murai reported that [RuCl (CO)3]2 was a versatile
2
13
6e, [RuCl (CO) (Cy POH) ]
100
2
2
2
2
32
catalyst for the cycloisomerization of arenynes, we decided to
evaluate the performances of the new complexes 5 and 6 in this
transformation. Arenyne 7, with an electron-rich aryl, was first
selected as a benchmark substrate (Table 6). Under the
optimized reaction conditions (16 mol % of Ru, 16% of AgOTf,
in toluene at 25 °C), control experiments showed that
a
Reaction conditions: [Ru]/AgOTf, 1:1, 7 (0.5 mmol), toluene (2.5
mL, 0.2 M), 25 °C. Conversions determined by H NMR. Without
silver salt. Only AgOTf was used. Isolated yield.
b
1
c
d
e
We also scrutinized a less activated arenyne 9 bearing only
one methoxy group on the aryl moiety; the reaction mixture
required a thermal activation at 80 °C to form products 10 and
11 (Table 7). Due to the steric congestion caused by the
methoxy, isomer 10 is mainly detected, and the catalyst used
does not seem to influence this selectivity. Surprisingly,
catalysts 6a and 6f exhibited a significantly better activity
than 6d and 6e (entries 1−4). Whereas 6a and 6d presented
similar stretching frequencies (Table 4), the higher catalytic of
6a over 6d is certainly due to the difference in steric congestion.
In general, the trend observed with this substrate is the
[
RuCl (CO) ] was ineffective (entries 1 and 2). Low
2 3 2
conversions were observed with the silver salt alone and with
catalyst 5a (entries 3 and 4). We were pleased to see that better
33
conversions were achieved with complexes 6. Whereas 6a and
g gave moderate transformation rates (entries 5 and 9), much
6
better activities were reached with catalysts 6d, 6f, and
especially 6e, bearing the more electron-rich PA ligands
(
entries 6−8). Thus, the catalyst loading could be reduced
down to 2 mol % with a slight increase of the reaction duration
to complete the cycloisomerization (entries 10−13).
D
DOI: 10.1021/om501300p
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Organometallics
Article
a
Table 7. Cycloisomerization of Arenyne 9
steps. We hope this study will contribute to the better
understanding of the coordination chemistry of SPO and PA
ligands and will enhance their use to develop new catalytic
systems.
EXPERIMENTAL SECTION
General Information. All reactions were performed under an
argon atmosphere. All reagents were obtained from commercial
sources and used as received. SPO ligands 4 were obtained from a
■
conversion
10/11
b
b
entry
1
[Ru]
AgX
(%)
ratio
6a,
AgOTf
99
97:3
37
chemical supplier or by following literature procedures. Solvents
[
RuCl (CO) (PhtBuPOH) ]
2
2
2
(
THF and toluene) were purified and dried over a Braun solvent
2
6d,
AgOTf
45
95:5
purification system (MB-SPS-800). Analytical thin layer chromatog-
raphy (TLC) was carried out on Merck silica gel 60 F254. Products
were revealed by ultraviolet light (254 or 366 nm) and stained with
dyeing reagent solutions as a 5% phosphomolybdic acid solution,
potassium permanganate solution, or p-anisaldehyde solution in
ethanol followed by gentle heating. Flash chromatography purifications
were performed on Combiflash Companion or with Merck silica gel 60
[
RuCl (CO) (PhCyPOH) ]
2 2 2
3
4
5
6e, [RuCl (CO) (Cy POH) ] AgOTf
35
99
96:4
97:3
2
2
2
2
6f, [RuCl (CO) (Ph POH) ]
AgOTf
AgBF4
2
2
2
2
c
6a,
NR
[
[
[
[
RuCl (CO) (PhtBuPOH) ]
2
2
2
6
7
8
6a,
AgOAc
AgPF6
NR
NR
100
RuCl (CO) (PhtBuPOH) ]
2
2
2
1
13
31
19
(
230−400 mesh). H, C, P, and F NMR spectra were recorded in
6a,
RuCl (CO) (PhtBuPOH) ]
CDCl at ambient temperature on Bruker Avance III 300 or 400
3
2
2
2
1
13
spectrometers operating at 300 and 400 MHz, respectively for H. C,
6a,
AgSbF6
85:15
31
19
1
RuCl (CO) (PhtBuPOH) ]
P, and F nuclei were observed with H decoupling. Solvent residual
2
2
2
a
signals were used as internal standard. Chemical shifts (δ) and
coupling constants (J) are given in ppm and Hz, respectively. The peak
patterns are indicated in the following format: multiplicity (s: singlet;
d: doublet; t: triplet; q: quartet; sept: septuplet; m: multiplet; dd:
doublet of doublets; dt: doublet of triplets; dm: doublet of multiplets,
etc.). The prefix br indicates a broadened signal. Infrared spectra were
recorded on a Bruker VERTEX70 Fourier transform infrared
spectrometer equipped with a single reflection diamond attenuated
total reflectance (ATR) Bruker A222 accessory. IR data are reported as
characteristic bands (cm ). Elemental analyses were performed on a
Thermo Finnigan EA 1112 analyzer. HRMS were recorded on a
SYNAPT G2 HDMS (Waters) or on a QStar Elite (Applied
Biosystems SGIEX) equipped with an atmospheric pressure ionization
Reaction conditions: [Ru]/AgOTf, 1:1 (5 mol %), 9 (0.5 mmol),
b
1
c
toluene (2.5 mL, 0.2 M), 80 °C, 24 h. Determined by H NMR. NR
=
no reaction.
opposite of that with arenyne 7. This highlighted a strong
relationship between ligand and substrate structures and
34
suggested different rate-determining steps. In the case of
substrate 9, complexes containing electron-poor ligands (6a
and 6f) seemed to activate efficiently the alkyne by an
accentuation of the cationic character of the vinyl-ruthenium
intermediate and triggers the nucleophilic attack, which was less
favored. On the other hand, when the nucleophilic attack was
not the rate-determining step, for the activated arenyne 7,
electron-rich ligands might boost the demetalation process.
In this study, we also noticed a drastic effect of the silver salt
used. Whereas AgOTf and AgSbF performed well, no reaction
was observed with AgBF , AgOAc, or AgPF (entries 1 and 5−
7
Gandon for gallium complexes. According to their observa-
tions with anions BF and PF , the chlorine abstraction from
the metallic center was followed by a fluorine transfer to the
metal, while SbF is stable enough to prevent this transfer. The
lack of reactivity noticed with AgOAc is in agreement with the
higher coordination capacity of the counteranion OAc that
−1
(
API) source. Mass spectra were obtained a time of flight (TOF)
analyzer. Intensity data were collected on a Bruker-Nonius KappaCCD
diffractometer using graphite-monochromated Mo Kα radiation
(
0.71073 Å) at 293(2) K. The collected frames were processed with
6
the software HKL-2000, and structures were resolved by the direct
methods and refined using the SHELXL-97 software package.
General Procedure for the Synthesis of Complexes
4
6
). A similar observation was recently reported by Bour and
1
2
35
[RuCl (CO) (R R PHO)]. In a Schlenk flask, under argon, charged
2 3
with [RuCl (CO) ] (102 mg, 0.2 mmol), a solution of ligand SPO 4
2
3 2
4
6
(0.4 mmol, 2 equiv) in THF (4 mL, 0.1 M) was added. The reaction
mixture was stirred for 2 h at room temperature. The solvent was
removed under vacuum. The crude mixture was solubilized in
dichloromethane and precipitated in n-hexane. The solid was filtered,
washed with n-hexane, and dried under vacuum to give the desired
product.
6
36
decreases the Lewis acid character of Ag(I).
[
RuCl (CO) (tBuPhPHO)] (5a). According to the general procedure,
2 3
CONCLUSION
To summarize, we studied the coordination chemistry of
secondary phosphine oxides and phosphinous acids with
5a was prepared from SPO tBuPhPHO 4a and obtained as a white
■
1
solid (151 mg, 87%). H NMR (400 MHz, CDCl ): δ (ppm) = 7.70−
3
Ar
1
7
.50 (m, 5H, H ), 7.50 (d, J(H,P) = 504.6 Hz, 1H, P-H), 1.17 (d,
J(H,P) = 17.5 Hz, 9H, CH3). C{ H} NMR (101 MHz, CDCl3): δ
(ppm) = 187.3 (CO), 184.0 (CO), 133.5 (d, J(C,P) = 2.9 Hz, C -
H), 130.9 (d, J(C,P) =10.7 Hz, C -H), 129.1 (d, J(C,P) = 12.5 Hz,
C -H), 126.1 (d, J(C,P) = 94.8 Hz, C -P), 31.2 (d, J(C,P) = 70.7
Hz, C), 24.0 (d, J(C,P) = 2.2 Hz, CH ). P NMR (162 MHz,
): δ (ppm) = 57.4 (dm, J(H,P) = 504.6 Hz). HRMS (ESI+):
m/z calcd for C H Cl NO PRu 455.9464 [M + NH ] ; found
13
1
[
RuCl (CO) ] and achieved the preparation of two series of
4
Ar
2
3 2
ruthenium complexes. It was found that SPOs could bind
ruthenium through the oxygen atom to give rare and stable
SPO-metal complexes, which were fully characterized. On the
other hand, the modification of the reaction conditions led to
the formation of another series of complexes bearing two PA
ligands. The complete characterization of these complexes
enabled the determination of PAs’ electronic parameter. Their
reactivity was evaluated in the cycloisomerization of arenynes
with two benchmark substrates. It was noticed a strong ligand
effect and a relationship between the ligand electronic
parameter and the structure of the substrates that can be
explained by an influence on two distinct rate-determining
Ar
Ar
1
Ar
1
2
31
3
1
CDCl
3
+
13 19
2
4
4
4
(
55.9471. IR (ATR, diamond crystal): 2979, 2374 (P−H), 2129
CO), 2069 (CO), 2025 (CO), 1590, 1475, 1437, 1369, 1139 (P
O), 1106, 905. Anal. Calcd for C H Cl O PRu: C, 35.63; H, 3.45.
13
15
2
4
Found: C, 35. 29; H, 3.27.
RuCl (CO) (nBuPhPHO)] (5b). According to the general procedure,
[
2
3
5
b was prepared from SPO nBuPhPHO 4b and obtained as a white
solid (162 mg, 93%). H NMR (400 MHz, CDCl ): δ (ppm) = 7.90
(dt, J(H,P) = 515.5 Hz, J(H,H) = 3.6 Hz, 1H, P-H), 7.75−7.50 (m,
1
3
1
E
DOI: 10.1021/om501300p
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Ar
5
0
H, H ), 2.31−2.23 (m, 2H, P-CH ), 1.55−1.37 (m, 4H, 2 CH ),
H), 1.27 (d, J(H,P) = 8.4 Hz, 9H, 3 CH ), 1.25 (d, J(H,P) = 7.8 Hz,
2
2
3
13
1
31
1
.89 (t, J(H,H) = 7.1 Hz, 3H, CH ). C{ H} NMR (75 MHz,
9H, 3 CH3). P{ H} NMR (162 MHz, CDCl ): δ (ppm) = 113.0 (s).
3
3
3
CDCl ): δ (ppm) = 187.2 (d, J(C,P) = 1.6 Hz, CO), 183.6 (d,
[RuCl (CO) (nBuPhPOH) ], 6b. According to the general procedure,
3
2
2
2
3
4
Ar
J(C,P) = 6.3 Hz, CO), 133.4 (d, J(C,P) = 2.8 Hz, C -H), 130.5 (d,
J(C,P) = 11.5 Hz, C -H), 129.3 (d, J(C,P) = 13.0 Hz, C -H), 126.9
(d, J(C,P) = 102.4 Hz, C ), 28.1 (d, J(C,P) = 68.1 Hz, P-CH ), 23.5
6b was prepared from SPO (±)-nBuPhPHO, (±)-4b, and was
obtained as a yellow solid (201 mg, 85%) as a mixture of like and unlike
Ar
Ar
Ar
1
1
(
(
compounds (de = 20%). H NMR (400 MHz, CDCl
3
): δ (ppm) =
),
), 0.86 (t, J(H,H) = 7.2
2
2
2
3
Ar
d, J(C,P) = 15.6 Hz, CH ), 23.1 (d, J(C,P) = 3.1 Hz, CH ), 13.4 (s,
7.70−7.30 (m, 10H, H ), 5.00 (br s, PO-H), 2.84 (m, 2.3H, CH
2.15 (m, 2H, CH ), 1.70−1.15 (m, 8.5H, CH
Hz, 2.3H, CH ), 0.83 (t, J(H,H) = 7.2 Hz, 3.7H, CH
(101 MHz, CDCl
136.3 (t, J(C,P) = 27.1 Hz, C , major), 135.7 (t, J(C,P) = 27.8 Hz,
2
2
2
31
1
CH3). P NMR (162 MHz, CDCl ): δ (ppm) = 43.7 (dm, J(H,P) =
2
3
1
3
1
5
4
2
6
15.5 Hz). HRMS (ESI+): m/z calcd for C H Cl NaO PRu
3
3
). C{ H} NMR
): δ (ppm) = 191.8 (t, J(C,P) = 11.4 Hz, CO),
3
1
3
15
2
4
+
2
60.9018 [M + Na] ; found 460.9022. IR (ATR, diamond crystal):
130 (CO), 2043 (CO), 1597, 1439, 1134 (PO), 1089, 935, 691,
18, 475. Anal. Calcd for C H Cl O PRu: C, 35.63; H, 3.45. Found:
Ar
Ar
Ar
Ar
C , minor), 131.0 (br s, C -H), 129.1 (t, J(C,P) = 5.1 Hz, C -H,
major), 128.9 (t, J(C,P) = 5.5 Hz, C -H, minor), 128.8 (t, J(C,P) = 6.2
13
15
2
4
Ar
C, 35.39; H, 3.31.
Ar
Ar
[
RuCl (CO) (MePhPHO)] (5c). According to the general procedure,
Hz, C -H, minor), 128.6 (t, J(C,P) = 6.6 Hz, C -H, major), 33.0 (t,
J(C,P) = 17.6 Hz, CH -P, minor), 32.5 (t, J(C,P) = 18.0 Hz, CH -P,
major), 23.9 (m, CH ). P{ H} NMR (162
MHz,CDCl ): δ (ppm) = 104.8 (s, minor), 103.7 (s, major). HRMS
(ESI+): m/z calcd for C22
2
3
5
c was prepared from SPO MePhPHO 4c and obtained as a yellow
solid (143 mg, 90%). H NMR (400 MHz, CDCl ): δ (ppm) = 8.05
2
2
1
31
1
), 13.7 (m, CH
2 3
3
1
(
dq, J(H,P) = 534.0 Hz, J(H,H) = 4.1 Hz, 1H, P-H), 7.80−7.50 (m,
3
Ar
2
+
5
H, H ), 2.03 (dd, J(H,P) = 13.8 Hz, J(H,H) = 4.1 Hz, 3H, CH ).
H34Cl NO P Ru 610.0378 [M + NH ] ;
2 4 2 4
3
1
3
1
3
C{ H} NMR (75 MHz, CDCl ): δ (ppm) = 187.2 (d, J(C,P) = 1.8
Hz, CO), 183.5 (d, J(C,P) = 3.0 Hz, CO), 133.6 (d, J(C,P) = 2.9 Hz,
found 610.0383. IR (ATR, diamond crystal): 3163 (OH), 2958, 2931,
3
3
4
2870, 2056 (CO), 1992 (CO), 1436, 1109, 876 (P−O), 743, 692, 577.
Ar
Ar
C -H), 130.4 (d, J(C,P) = 12.0 Hz, C -H), 129.3 (d, J(C,P) = 13.3
Anal. Calcd for C22
H, 5.22.
H30Cl O P Ru: C, 44.61; H, 5.10. Found: C, 44.77;
2 4 2
Ar
Ar
1
Hz, C -H), 127.9 (d, J(C,P) = 106.8 Hz, C ), 15.2 (d, J(C,P) = 70.0
Hz, CH3). 31P NMR (162 MHz, CDCl ): δ (ppm) = 37.4 (dq, J(H,P)
1
[RuCl (CO) (MePhPOH) ], 6c. According to the general procedure,
3
2 2 2
=
534.0 Hz, 2J(H,P) = 13.7 Hz). HRMS (ESI): m/z calcd for
6c was prepared from SPO (±)-MePhPHO, (±)-4c, and obtained as a
yellow oil (61 mg, 30%) as a mixture of like and unlike compounds (de
+
C H Cl NaO PRu 418.8548 [M + Na] ; found 418.8549. IR (ATR,
diamond crystal): 2134 (CO), 2067 (CO), 2049 (CO), 1587, 1437,
10
9
2
4
1
= 20%). H NMR (400 MHz, CDCl
): δ (ppm) = 7.70−7.45 (m,
3
Ar
2
1
406, 1301, 1136 (PO), 1071, 961. Anal. Calcd for
10H, H ), 5.39 (br s, P-OH), 2.21 (t, J(H,P) = 3.4 Hz, 2.5H, CH
3
),
2
13
1
C H Cl O PRu: C, 30.32; H, 2.29. Found: C, 29.98; H. 2.10.
2.18 (t, J(H,P) = 3.5 Hz, 3.5H, CH
3
). C{ H} NMR (101 MHz,
10
9
2
4
2
[
RuCl (CO) (Cy PHO)] (5e). According to the general procedure, 5e
CDCl
3
): δ (ppm) = 191.5 (t, J(C,P) = 11.6 Hz, CO), 138.5 (t, J(C,P)
2
3
2
Ar
Ar
was prepared from SPO Cy PHO 4e and obtained as a white solid
182 mg, 97%). H NMR (400 MHz, CDCl ): δ (ppm) = 6.76 (d,
J(H,P) = 483.7 Hz, 1H, P−H), 2.10−1.10 (complex multiplet, 22H,
CH and CH ). C{ H} NMR (75 MHz, CDCl ): δ (ppm) = 187.3
d, J(C,P) = 1.7 Hz, CO),184.0 (br s, CO), 34.5 (d, J(C,P) = 63.9
Hz, CH), 26.3 (s, CH ), 26.3 (br s, CH ), 26.1 (br s, CH ), 25.7 (d,
J(C,P) = 1.5 Hz, CH ), 25.6 (d, J(C,P) = 3.0 Hz, CH ). P NMR (121
MHz, CDCl ): δ (ppm) = 61.2 (dm, J(H,P) = 483.4 Hz). HRMS
= 28.7 Hz, C , major), 137.9 (t, J(C,P) = 27.1 Hz, C , minor), 131.3
2
1
Ar
Ar
(
(br s, C -H), 129.2 (t, J(C,P) = 5.2 Hz, C -H, major), 129.0 (t,
3
1
Ar
Ar
J(C,P) = 5.3 Hz, C -H, minor), 128.3 (t, J(C,P) = 6.5 Hz, C -H,
minor), 128.1 (t, J(C,P) = 6.5 Hz, C -H, major), 19.9 (t, J(C,P) =
9.0 Hz, CH , minor), 19.5 (t, J(C,P) = 19.4 Hz, CH , major). P{ H}
Ar
1
13
1
2
3
3
1
1
3
1
1
(
3
3
NMR (162 MHz, CDCl ): δ (ppm) = 101.6 (s, minor), 100.6 (s,
3
2
2
2
31
major). HRMS (ESI+): m/z calcd for C H Cl NaO P Ru 530.8992
16 18
2
4 2
2
2
+
1
[
M + Na] ; found 530.8974.
RuCl (CO) (CyPhPOH) ], 6d. According to the general procedure,
3
+
[
(
4
(
ESI): m/z calcd for C H Cl NaO PRu 492.9645 [M + Na] ; found
92.9663. IR (ATR, diamond crystal): 2928, 2854, 2129 (CO), 2044
2
2
2
15
23
2
4
6
d was prepared from SPO (±)-CyPhPHO, (±)-4d, and obtained as a
light yellow solid (209 mg, 81%) as a mixture of like and unlike
compounds (de = 20%). H NMR (300 MHz, CDCl ): δ (ppm) =
CO), 1993 (CO), 1449, 1097 (PO), 620. Anal. Calcd for
1
C H Cl O PRu: C, 38.31; H, 4.93. Found: C, 38.66; H, 4.89.
3
15
23
2
4
Ar
7
.70−7.40 (m, 10H, H ), 7.01 (s, 1H, PO-H, major), 6.72 (s, 1H, PO-
General Procedure for the Preparation of Complexes
RuCl (CO) (R R POH) ]. In a Schlenk flask, under argon, charged
with [RuCl (CO) ] (102 mg, 0.2 mmol), a solution of preligand SPO
(0.88 mmol, 4.4 equiv) in toluene (4 mL, 0.1 M) was added. The
reaction mixture was stirred from 3 to 10 days at 110 °C. The solvent
was removed under vacuum. The crude mixture was filtered over a pad
of silica gel, eluted by DCM, and dried under vacuum to give the
desired product.
1
2
13 1
[
H, minor), 2.70−0.80 (m, 22H, CH and CH2). C{ H} NMR (75
MHz, CDCl ): δ (ppm) = 192.7 (CO), 134.1 (t, J(C,P) = 24.9 Hz,
3
2
2
2
1
2
3 2
Ar
1
Ar
Ar
4
C -P), 133.8 (t, J(C,P) = 26.0, C -P), 131.1 (br s, C -H), 131.0 (br
s, C -H), 129.74 (t, J(C,P) = 6.2 Hz, C -H), 129.70 (t, J(C,P) = 6.3
Hz, C -H), 128.6 (t, J(C,P) = 5.1 Hz, C -H), 128.5 (t, J(C,P) = 5.2
Ar
Ar
Ar
Ar
Ar
1
1
Hz, C -H), 42.5 (t, J(C,P) = 17.1 HZ, CH, minor), 41.7 (t, J(C,P) =
17.2 HZ, CH, major), 26.8−26.2 (m, CH ), 26.1 (br s, CH ), 25.8 (br
, major). P{ H} NMR (121 MHz,
): δ (ppm) = 106.2 (s), 104.9 (s). HRMS (ESI+): m/z calcd for
2
2
31
1
[
RuCl (CO) (tBuPhPOH) ], 6a-like. According to the general
s, CH
CDCl
, minor), 25.6 (br s, CH
2 2
2
2
2
procedure, 6a was prepared from SPO (S )-(tBuPhPHO), (S )-4a,
and obtained as a light yellow solid (216 mg, 92%) as a mixture of like
and unlike compounds (de = 90%). H NMR (400 MHz, CDCl ): δ
ppm) = 7.74−7.64 (m, 4H, H ), 7.52−7.44 (m, 6H, H ), 6.94 (s,
H, PO-H), 1.23 (d, J(H,P) = 8.3 Hz, 9H, 3 CH ), 1.21 (d, J(H,P) =
.1 Hz, 9H, 3 CH ). C{ H} NMR (101 MHz, CDCl ): δ (ppm) =
94.1 (t, J(C,P) = 10.9 Hz, CO), 134.1 (t, J(C,P) = 25.2 Hz, C ),
30.9 (br s, C -H), 130.1 (t, J(C,P) = 5.9 Hz, C -H),128.3 (t, J(C,P)
5.1 Hz, C -H), 38.6 (t, J(C,P) = 16.4 Hz, C), 25.4 (t, J(C,P) = 2.6
Hz, CH3). P{ H} NMR (162 MHz, CDCl ): δ (ppm) = 113.9 (s).
HRMS (ESI+): m/z calcd for C H Cl NaO P2Ru 614.9932 [M +
Na] ; found 614.9930. IR (ATR, diamond crystal): 3221 (OH), 2981,
935, 2906, 2873, 2050 (CO), 1993 (CO), 1960, 1438, 1368, 1131,
73 (P−O), 697, 608, 513. Anal. Calcd for C H Cl O P Ru: C,
4.60; H, 5.10. Found: C, 44.78; H, 4.99.
3
p
p
+
C H34Cl NaO P Ru: 667.0247 [M + Na] ; found 667.0250. IR
26 2 4 2
1
(ATR, diamond crystal): 3500−3000, 3250 (OH), 2929, 2856, 2050
(CO), 1990 (CO), 1435, 1111, 873 (P−O), 746, 694, 622, 577. Anal.
3
Ar
Ar
(
2
8
1
1
=
Calcd for C26
5.19.
H34Cl O P Ru: C, 48.46; H, 5.32. Found: C, 48.60; H,
2 4 2
3
13
1
3
3
2
1
Ar
[RuCl (CO) (Cy POH) ], 6e. According to the general procedure, 6e
2 2 2 2
Ar
Ar
was prepared from SPO Cy PHO 4e and obtained as a yellow solid
2
Ar
1
2
1
(256 mg, 92%). H NMR (400 MHz, CDCl ): δ (ppm) = 6.12 (s, 2H,
PO-H), 2.48 (m, 4H, P-CH), 2,15−1.20 (m, 40H, 20 CH ). C{ H}
NMR (101 MHz, CDCl ): δ (ppm) = 194.5 (t, J(C,P) = 10.8 Hz,
3
31
1
13
1
3
2
2
22
30
2
4
3
+
1
CO), 40.6 ( J(C,P) = 14.8 Hz, 4 CH), 27.2 (s, CH ), 27.0 (t, J(C,P) =
2
3
1
1
2
8
4
6.1 Hz, CH ), 26.8 (m CH ), 26.3 (s, CH ). P{ H} NMR (162 MHz,
2 2 2
CDCl ): δ (ppm) = 119.5 (s). HRMS (ESI+): m/z calcd for
22
30
2
4
2
3
C H Cl NO P Ru 674.1632 [M + NH ]+; found 674.1629. IR
26
50
2
4
2
4
[
RuCl (CO) (tBuPhPOH) ], 6a-unlike. According to the general
(ATR, diamond crystal): 3266 (OH), 2929, 2852, 2048 (CO), 1991
(CO), 1953, 1446, 1147, 856 (P−O), 838, 743, 579. Anal. Calcd for
C H Cl O P Ru: C, 47.56; H, 7.06. Found: C, 47.68; H, 7.00.
2
2
2
procedure, 6a was prepared from SPO (±)-tBuPhPHO, (±)-4a, and
obtained as a light yellow solid (206 mg, 85%) as a mixture of like and
unlike compounds (de = 0%). H NMR (400 MHz, CDCl ): δ (ppm)
7.68−7.60 (m, 4H, H ), 7.47−7.40 (m, 6H, H ), 6.94 (s, 2H, PO-
26
46
2
4 2
1
[RuCl (CO) (Ph POH) ], 6f. According to the general procedure, 6f
2 2 2 2
3
Ar
Ar
=
was prepared from SPO Ph PHO 4f and obtained as a yellow solid
2
F
DOI: 10.1021/om501300p
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
1
(
(
131 mg, 53%). H NMR (300 MHz, CDCl ): δ (ppm) = 7.95−7.70
(4) Kapoor, P. N.; Saraswati, R.; McMahon, I. J. Inorg. Chim. Acta
1985, 110, 63−68.
3
Ar
Ar 13
1
m, 8 H ), 7.60−7.40 (m, 12 H ). C{ H} NMR (75 MHz, CDCl ):
δ (ppm) = 192.0 (t, J(C,P) = 11.6 Hz, CO), 135.3 (m, C ), 131.6 (br
s, C -H), 130.5 (t, J(C,P) = 6.8 Hz, C -H), 128.7 (t, J(C,P) = 5.5 Hz,
C -H). P{ H} NMR (121 MHz, CDCl ): δ (ppm) = 94.4 (s).
HRMS (ESI+): m/z calcd for C H Cl NO P Ru 649.9754 [M +
NH ] ; found 649.9752. IR (ATR, diamond crystal): 3600−2600,
100 (OH), 3057, 2922, 2900, 2851, 2136, 2058 (CO), 1991 (CO),
3
2
Ar
(5) Cotton, F. A.; Kibala, P. A.; Miertschin, C. S. Inorg. Chem. 1991,
30, 548−553. Teo, S.; Weng, Z.; Hor, T. S. A. Organometallics 2008,
27, 4188−4192.
Ar
Ar
Ar
31
1
3
26
26
2
4 2
́
(6) (a) Doux, M.; Ricard, L.; Mathey, F.; Le Floch, P.; Mezailles, N.
+
4
Eur. J. Inorg. Chem. 2003, 687−698. (b) Baker, R. J.; Bettentrup, H.;
Jones, C. Acta Crystallogr. C 2003, 59, m339−m341. (c) Dornhaus, F.;
3
1
436, 1101, 879 (P−O), 690, 523. Anal. Calcd for C H Cl O P Ru:
C, 49.38; H, 3.51. Found: C, 49.30; H, 3.32.
26
22
2
4
2
̈
Scholz, S.; Sanger, I.; Bolte, M.; Wagner, M.; Lerner, H. W. Z. Anorg.
Allg. Chem. 2009, 635, 2263−2272.
[
RuCl (CO) ({4-fluorophenyl} POH) ], 6g. According to the general
2 2 2 2
(7) (a) Pascu, S. I.; Coleman, K. S.; Cowley, A. R.; Green, M. L. H.;
Rees, N. H. New J. Chem. 2005, 29, 385−397. (b) Gushwa, A. F.;
Belabassi, Y.; Montchamp, J.-L.; Richards, A. F. J. Chem. Crystallogr.
2009, 39, 337−347. (c) Gentschow, S.-A.; Kohl, S. W.; Heinemann, F.
W.; Wiedemann, D.; Grohmann, A. Z. Naturforsch. 2010, 65b, 238−
procedure, 6g was prepared from SPO (p-FC H ) PHO 4g and
obtained as a white solid (234 mg, 83%). H NMR (400 MHz,
CDCl ): δ (ppm) = 7.80−7.65 (m, 8H, H ), 7.30−7.10 (m, 8H, H ).
C{ H} NMR (101 MHz, CDCl ): δ (ppm) = 191.8 (t, J(C,P) =
1.4 Hz, CO), 164.9 (d, J(C,F) = 254 Hz, C ), 133.1 (dd, J(C,P) =
.8 Hz, J(C,F) = 16.3 Hz, C ), 130.9 (td, J(C,P) = 31.7 Hz, J(C,F) =
.4 Hz, C ), 116.4 (td, J(C,P) = 6.2 Hz, J(C,F) = 21.8 Hz, C ).
P{ H} NMR (162 MHz, CDCl ): δ (ppm) = 94.3 (s). F{ H}
6
4 2
1
Ar
Ar
3
1
3
1
2
3
1
Ar
1
7
3
2
(
50.
8) Magiera, D.; Szmigielska, A.; Pietrusiewicz, K. M.; Duddeck, H.
Ar
1
4
Ar
Ar
Chirality 2004, 16, 57−64.
3
1
1
19
1
3
(9) Li, G. Y. Angew. Chem., Int. Ed. 2001, 40, 1513−1516.
(10) For reviews on the use of metal-SPO/PA in catalysis, see:
(a) Ackermann, L. Isr. J. Chem. 2010, 50, 652−663. (b) Shaikh, T. M.;
Weng, C.-M.; Hong, F.-E. Coord. Chem. Rev. 2012, 256, 771−803.
NMR (376 MHz, CDCl ): δ (ppm) = −106.6 (s). HRMS (ESI+): m/
3
+
z calcd for C H NO P Cl F Ru 721.9377 [M + NH ] ; found
2
6
22
4
2
2
4
4
7
(
5
4
21.9382. IR (ATR, diamond crystal): 3171 (OH), 3063, 3101, 2065
CO), 2002 (CO), 1588, 1498, 1235, 1160, 1105, 879 (P−O), 826,
30. Anal. Calcd for C H Cl F O P Ru: C, 44.34; H, 2.58. Found: C,
26 18 2 4 4 2
(
11) Donets, P. A.; Cramer, N. J. Am. Chem. Soc. 2013, 135, 11772−
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12) Schro
4.68; H, 2.86.
(
̈
der, F.; Tugny, C.; Salanouve, E.; Clavier, H.; Giordano,
L.; Moraleda, D.; Gimbert, Y.; Mouries-Mansuy, V.; Goddard, J.-P.;
ASSOCIATED CONTENT
Fensterbank, L. Organometallics 2014, 33, 4051−4056.
■
(13) (a) Bigeault, J.; Giordano, L.; Buono, G. Angew. Chem., Int. Ed.
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Supporting Information
Experimental procedures, H, 13C, 31P{H}, and 19F{H} NMR
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2005, 44, 4753−4757. (b) Bigeault, J.; De Riggi, I.; Gimbert, Y.;
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spectra. Crystallographic information files (CIF) for all XRD
structures (5a, 6a, 6d, and 6e, CCDC 1024151−1024155,
respectively), which can also be obtained from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif. The Supporting Information is available free of
charge on the ACS Publications website at DOI: 10.1021/
om501300p.
Moraleda, D.; Naubron, J.-V.; Bu
Tetrahedron: Asymmetry 2009, 20, 1912−1917.
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(15) (a) Jiang, X.-B.; Minnaard, A. J.; Hessen, B.; Feringa, B. L.;
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AUTHOR INFORMATION
Corresponding Authors
E-mail: gerard.buono@univ-amu.fr.
E-mail: herve.clavier@univ-amu.fr.
■
*
*
2
004, 15, 2223−2229. (c) Landert, H.; Spindler, F.; Wyss, A.; Blaser,
H.-U.; Pugin, B.; Ribourduoille, Y.; Gschwend, B.; Ramalingam, B.;
Pfaltz, A. Angew. Chem., Int. Ed. 2010, 49, 6873−6876.
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16) (a) Ackermann, L. Org. Lett. 2005, 7, 3123−3125.
Notes
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b) Ackermann, L.; Althammer, A.; Born, R. Angew. Chem., Int. Ed.
The authors declare no competing financial interest.
2
006, 45, 2619−2622. (c) Ackermann, L.; Mulzer, M. Org. Lett. 2008,
1
0, 5043−5045. (d) Ackermann, L. Acc. Chem. Res. 2014, 47, 281−
ACKNOWLEDGMENTS
This work was supported by the Minister
■
Super
295.
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(17) Rafter, E.; Gutmann, T.; Low, F.; Buntkowsky, G.; Philippot, K.;
Chaudret, B.; van Leeuwen, P. W. N. M. Catal. Sci. Technol. 2013, 3,
595−599.
̀
e de l’Enseignement
́
ieur et de la Recherche (L.G. Ph.D. grant), the CNRS,
AMU, and Centrale Marseille. We gratefully acknowledge Dr.
Jean-Valere Naubron, Gregory Excoffier, Dr. Valerie Monnier,
and Christophe Chendo (Spectropole, Federation des Sciences
Chimiques de Marseille) for respectively the IR, elemental
analyses, and MS analyses as well as Dr. Julie Broggi for useful
comments on the manuscript.
(
18) (a) Oshiki, T.; Muranaka, M. PCT Int. Appl.., WO 2012/
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Commun. 2014, 50, 9661−9664.
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DOI: 10.1021/om501300p
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
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DOI: 10.1021/om501300p
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