Synthesis, structural characterization and catalytic activity of indenyl complexes of ruthenium bearing fluorinated phosphine ligands

Article abstract of DOI:10.1016/j.jorganchem.2017.03.043

The synthesis, characterization and catalytic activity of new ruthenium complexes of fluorinated triarylphosphines is described. The new ruthenium complexes [RuCl(ind)(PPh₃){P(p-C₆H₄CF₃)₃}] and [RuCl(ind)(PPh₃){P(3,5-C₆H₃(CF₃)₂)₃}] were synthesized in 57% and 24% isolated yield, respectively, by thermal ligand exchange of [RuCl(ind)(PPh₃)₂], where ind = indenyl ligand η⁵-C₉H₇^?. The electronic and steric properties of the new complexes were studied through analysis of the X-ray structures and through cyclic voltammetry. The new complexes [RuCl(ind)(PPh₃){P(p-C₆H₄CF₃)₃}] and [RuCl(ind)(PPh₃){P(3,5-C₆H₃(CF₃)₂)₃}] and the known complex [RuCl(ind)(PPh₃)₂}] differed only slightly in their steric properties, as seen from comparison of bond lengths and angles associated with the ruthenium center. As determined by cyclic voltammetry, the redox potentials of [RuCl(ind)(PPh₃){P(p-C₆H₄CF₃)₃}] and [RuCl(ind)(PPh₃){P(3,5-C₆H₃(CF₃)₂)₃}] are +0.173 and + 0.370 V vs. Cp₂Fe^0/+, respectively, which are substantially higher than that of [RuCl(ind)(PPh₃)₂] (?0.023 V). After activation through chloride abstraction, the new complexes are catalytically active in the etherification of propargylic alcohols (8–24 h at 90 °C in toluene, 1–2 mol% catalyst loading, 29–61% isolated yields). As demonstrated by a comparative study for a test reaction, the three precursor complexes [RuCl(ind)(PPh₃){P(p-C₆H₄CF₃)₃}], [RuCl(ind)(PPh₃){P(3,5-C₆H₃(CF₃)₂)₃}] and [RuCl(ind)(PPh₃)₂}] differed only slightly in catalytic activity.

Full text of DOI:10.1016/j.jorganchem.2017.03.043

Journal of Organometallic Chemistry xxx (2017) 1e13
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, structural characterization and catalytic activity of indenyl
complexes of ruthenium bearing fluorinated phosphine ligands
Matthew J. Stark , Michael J. Shaw , Arghavan Fadamin , Nigam P. Rath c,
Eike B. Bauer
a
a
b
b
a,
a, *
University of Missouri - St. Louis, Department of Chemistry and Biochemistry, One University Boulevard, St. Louis, MO 63121, USA
Southern Illinois University Edwardsville, Department of Chemistry, Edwardsville, IL 62025, USA
Center for Nanoscience, University of Missouri - St. Louis, One University Boulevard, St. Louis, MO 63121, USA
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 December 2016
Received in revised form
The synthesis, characterization and catalytic activity of new ruthenium complexes of fluorinated triar-
ylphosphines is described. The new ruthenium complexes [RuCl(ind)(PPh
RuCl(ind)(PPh ){P(3,5-C (CF }] were synthesized in 57% and 24% isolated yield, respectively, by
thermal ligand exchange of [RuCl(ind)(PPh
steric properties of the new complexes were studied through analysis of the X-ray structures and
through cyclic voltammetry. The new complexes [RuCl(ind)(PPh ){P(p-C CF }] and [RuCl(ind)(PPh
{P(3,5-C H (CF ) ) }] and the known complex [RuCl(ind)(PPh ) }] differed only slightly in their steric
3 6 4 3 3
){P(p-C H CF ) }] and
[
3
6
H
3
3 2 3
) )
24 March 2017
5
ꢀ
9 7
H . The electronic and
3
)
2
], where ind ¼ indenyl ligand
h
-C
Accepted 25 March 2017
Available online xxx
3
6
H
4
3
)
3
3
)
Dedicated to Professor John A. Gladysz on
the occasion of his 65th birthday.
6
3
3 2 3
3 2
properties, as seen from comparison of bond lengths and angles associated with the ruthenium center. As
determined by cyclic voltammetry, the redox potentials of [RuCl(ind)(PPh ){P(p-C CF }] and
3
6
H
4
3 3
)
0/þ
Keywords:
Electronic tuning
X-ray
Cyclic voltammetry
Propargylic alcohols
[RuCl(ind)(PPh ){P(3,5-C H (CF ) ) }] are þ0.173 and þ 0.370 V vs. Cp Fe , respectively, which are
3
6
3
3 2 3
2
substantially higher than that of [RuCl(ind)(PPh
3
)
2
] (ꢀ0.023 V). After activation through chloride
abstraction, the new complexes are catalytically active in the etherification of propargylic alcohols (8
ꢁ
e24 h at 90 C in toluene, 1e2 mol% catalyst loading, 29e61% isolated yields). As demonstrated by a
comparative study for a test reaction, the three precursor complexes [RuCl(ind)(PPh
RuCl(ind)(PPh ){P(3,5-C (CF }] and [RuCl(ind)(PPh }] differed only slightly in catalytic activity.
2017 Elsevier B.V. All rights reserved.
3 6 4 3 3
){P(p-C H CF ) }],
[
3
6
H
3
3
)
2
)
3
3 2
)
©
1
. Introduction
complexes are frequently applied in synthesis [9] and catalysis [10].
The increased reactivity of indenyl complexes has been ascribed to
the so called “indenyl effect” [11]. As part of our long standing
research program directed towards the catalytic activation of
propargylic alcohols [12], we identified ruthenium indenyl com-
plexes as valuable starting materials not only for the synthesis of
ruthenium complexes [12a,c,f], but also as potential catalysts in
nucleophilic substitution reactions [12a,c]. However, a serious
drawback of these catalyst systems are the high reaction temper-
Transition metal complexes of ruthenium are widely utilized in
catalysis and other areas of chemical research [1]. A large number of
ruthenium complexes have been described in the literature, and
they have found applications as catalysts in reactions such as oxi-
dations [2], olefin metathesis [3], and a number of carbon-carbon,
carbon-nitrogen and carbon-oxygen bond forming reactions [4].
The quest for sterically and electronically tuned ruthenium com-
plexes is ongoing to satisfy the growing need of such complexes in
the area of medicinal chemistry [5] and the development of optical
devices [6].
ꢁ
atures of 80e90 C required for transformations. The high reaction
temperatures are undesirable because of the energy required and
the difficulties of obtaining high enantiomeric excess values under
such conditions in addition to rearrangements that often occur as
side reactions, lowering the yield of the desired product. We hy-
pothesized that electron-withdrawing groups on the ruthenium
center might increase its reactivity, as these groups might facilitate
the nucleophilic attack on (potential) carbocation intermediates.
Our previous electronic tuning efforts utilizing electron-
3 2
The known [7] ruthenium indenyl complex [RuCl(ind)(PPh ) ]
5
ꢀ
7
(
ind ¼
9
h -C H ) has previously been utilized as a starting material
for organometallic syntheses [8] and other ruthenium indenyl
*
Corresponding author.
E-mail address: bauere@umsl.edu (E.B. Bauer).
http://dx.doi.org/10.1016/j.jorganchem.2017.03.043
022-328X/© 2017 Elsevier B.V. All rights reserved.
0
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2
M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
withdrawing ligands resulted in the synthesis of the tris(N-pyr-
rolyl)phosphine complex [RuCl(ind)(PPh ){P(pyr)
by NMR in the crude products.
The new complexes were characterized by multinuclear NMR,
MS, IR, elemental analysis and X-ray diffraction. In both complexes,
3
3
}] (pyr ¼ N-pyr-
rolyl, see Fig. 1), which catalytically activated propargylic alcohols,
ꢁ
albeit still at reaction temperatures around 85 C [12a].
the coordination of one fluorinated phosphine ligand and one PPh
3
31
1
Fluorinated phosphine ligands have previously been utilized to
electronically tune ruthenium complexes, representative examples
are shown in Fig. 1 [13]. Ruthenium complexes bearing fluorinated
phosphine ligands have been applied in catalysis [14] and also
exhibited anticancer activity [15]. Fluorinated phosphines have also
been employed in the synthesis of metal complexes to be employed
for fluorous biphasic catalysis [16]; for example, Gladysz published
fluorous analogs of Grubbs' second-generation catalyst to be
employed in ring-opening metathesis polymerization [17]. In
context of our own research, we hypothesized that ruthenium
indenyl complexes bearing electron-withdrawing, fluorinated
phosphine ligands show, due to their increased Lewis acidity,
enhanced catalytic activity in the transformation of propargylic
alcohols.
ligand is readily indicated by two distinct P{ H} NMR signals at
50.1 and 44.2 ppm and at 50.1 and 47.8 ppm, respectively. As ex-
pected for complexes with two magnetically different phosphorus
atoms in the metal coordination sphere, coupling between the two
signals was observed. Coupling constants
determined.
2
JPP of 42 Hz were
1
13
1
In general, the indenyl ligand gives very distinct H and C{ H}
NMR signals for the three protons and the five carbon atoms of its
coordinated five-membered ring [19]. All these carbon and proton
atoms of the indenyl ligand in the new complexes gave individual
1
13
1
signals in the corresponding H and C{ H} NMR spectra.
2.2. X-ray structures
Herein, we describe the synthesis and characterization of the
In order to unequivocally establish the structure of the new
ruthenium complexes [RuCl(ind)(PPh
RuCl(ind)(PPh ){P(3,5-C (CF }] where P(p-C
tris(4-(trifluoromethyl)phenyl)phosphine and P(3,5-C
tris(3,5-bis(trifluoromethyl)phenyl)phosphine. We investigated
the steric and electronic properties of the new complexes through
X-ray analysis and cyclic voltammetry. The new complexes were
demonstrated to be catalyst precursors for the etherification of
3
){P(p-C
6
H
4
CF
3
)
3
}] and
ruthenium complexes, the X-ray structures of [RuCl(ind)(PPh
3
)
[
3
6
H
3
3
)
2
)
3
6
H
4
CF
(CF
3
)
3
is
is
{P(p-C CF }] and [RuCl(ind)(PPh ){P(3,5-C (CF }] were
6
H
4
3
)
3
3
6
H
3
3 2 3
) )
6
H
3
3
)
2
)
3
determined (Fig. 2). Selected bond lengths and angles are listed in
Table 1, and for comparison purposes, the X-ray data for
[RuCl(ind)(PPh ) ] [20] and for [RuCl(Ind)(PPh ){P(pyr) }] (Fig. 1)
3 2 3 3
[12a] from the literature are also included. As previously observed
by us [12a], it appears that complexes of the general formula
propargylic alcohols. The catalytic activity of [RuCl(ind)(PPh
CF }], [RuCl(ind)(PPh ){P(3,5-C (CF }]
RuCl(ind)(PPh
active species in the reaction mixture were investigated.
3
){P(p-
and
[RuCl(ind)(PPh
the “parent” complex [RuCl(ind)(PPh
[RuCl(ind)(PPh ){P(3,5-C (CF }],
donor-acceptor interaction between one of the fluorinated aryl
rings and one of the phenyl rings of PPh was observed (Fig. 2,
3
)L] are structurally not significantly different from
]. For the complex
face-to-face aromatic
C
[
H
6 4
3
)
3
3
6
H
3
3
)
2
)
3
3 2
)
a
3
)
2
}] were compared and potential catalytically
3
H
6 3
3
)
2
)
3
3
bottom) [21]. The distance between the two aryl ring systems was
calculated to be 3.873 Å.
2
. Results and discussion
The P-Ru-P and P-Ru-Cl bond angles around the ruthenium
ꢁ
ꢁ
2
.1. Ruthenium complex syntheses
center range from 91.612(17) to 99.585(19) , and are also similar to
the bond angles of the other two complexes listed in Table 1. The
geometry of the new complexes is, thus, best described as slightly
distorted octahedral. The somewhat increased P-Ru-P bond angles
for the two new complexes indicates some steric repulsion of the
3 2
The known [7] ruthenium indenyl complex [RuCl(ind)(PPh ) ]
has previously been utilized as a starting material for organome-
tallic syntheses by us [12,18] and others [8], as one of the PPh
ligand can be thermally exchanged by other ligands. Accordingly,
when the complex [RuCl(ind)(PPh ] was refluxed with one
equivalent of either P(p-C CF or P(3,5-C (CF in THF for
h, the new complexes [RuCl(ind)(PPh ){P(p-C CF }] and
RuCl(ind)(PPh ){P(3,5-C (CF }] were isolated chromato-
3
PPh
phine P(3,5-C
compared to the less bulky phosphine P(p-C
3
and the fluorinated ligands. It appears that the bulkier phos-
(CF forms a smaller P-Ru-P angle with PPh
CF which might
3
)
2
H
6 3
3
)
2
)
3
3
H
6 4
3
)
3
H
6 3
3
)
H
2
)
3
6
H
4
3 3
)
4
[
3
6
4
3
)
3
be a consequence of the face-to-face interaction in the solid state
shown in Fig. 2. For the other two, structurally related complexes in
Table 1, increased P-Ru-P bond angles between the phosphine li-
gands were observed as well.
3
6
H
3
3 2 3
) )
graphically in 57 and 24% yields, respectively (Scheme 1). The low
yields may be due to decomposition reactions that occur during
reaction and workup, as little to no starting material was observed
The Ru-P bond lengths for the two new complexes range from
2.2696(5) to 2.3203(5) Å and are not appreciably different from
each other. It appears that the electron-withdrawing character of
the fluorinated ligands does not have a profound impact on the Ru-
P bond lengths compared to the structurally related complexes
3 2 3 3
[RuCl(ind)(PPh ) ] and [RuCl(Ind)(PPh ){P(pyr) }] (Fig. 1). Also, the
distances between the centroids of the C5 ring of the indenyl li-
gands and the ruthenium centers for both complexes are similar
(
(
1.904 and 1.903 Å) and comparable to that for [RuCl(ind)(PPh
1.918 Å).
3 2
) ]
As can be seen from the X-ray structures, the indenyl ligands for
5
both complexes are
h -coordinated, i.e. all five carbon atoms of the
cyclopentadienyl unit are coordinated to the ruthenium center. As
analyzed previously by us [12a] and others [11e], not all five carbon
atoms have the same RueC bond lengths. The bond lengths of the
two benzenoid carbons are longer compared to the other three
carbon atoms of the cyclopentadienyl ring. This can be quantified
by the
D Ru-C value (here 0.197 and 0.137 Å, respectively), which
Fig. 1. Representative electronically tuned ruthenium complexes.
describes the average difference in bond lengths of the two
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M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
3
Scheme 1. Synthesis of ruthenium complexes bearing fluorinated aryl phosphine ligands.
3 6 4 3 3 3 6 3 3 2 3
Fig. 2. The molecular structures of [RuCl(ind)(PPh ){P(p-C H CF ) }] (left) and [RuCl(ind)(PPh ){P(3,5-C H (CF ) ) }] (right and bottom). Hydrogen atoms are omitted for clarity.
Crystallographic parameters are given in the experimental, and key bond lengths and angles are listed in Table 1.
benzenoid carbon atoms and the other three carbon atoms of the
cyclopentadienyl unit [11e,12a,22]. Related complexes exhibit
takes the value 0 in an ideal h5-coordination, and for indenyl
complexes, the values typically range below 10 ; again,
ꢁ
similar
D
Ru-C values around 0.2 Å. The fold angle is the angle
[RuCl(ind)(PPh
3 6 4 3 3 3
){P(p-C H CF ) }] and [RuCl(ind)(PPh ){P(3,5-
ꢁ
ꢁ
between the plane formed by C1-C2-C3 of the C5 ring and by C1-
C3-C4-C5 or C1-C3-C4-C9 of two carbon atoms of the C5 ring and
the two carbon atoms shared by the C5 ring and the benzenoyl unit;
thus, it describes the angle that is formed by the plane of the C5 unit
and the benzene unit of the indenyl ligand [11e]. The fold angle
C
6
H
3
(CF }] fall in this range (9.57 and 7.45 , respectively) as
3 2 3
) )
3
do the other two complexes shown in Table 1. An
would be indicated by a fold angle around 60 [11e].
It has been observed before that the ligand with the strongest
trans influence will take the position trans to the benzo unit of the
h -coordination
ꢁ
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4
M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
Table 1
ꢁ
Selected bond lengths (Å) and angles ( ) for complexes of the general formula [RuCl(ind)(PPh
3
)PR
3
].
PR CF }] PR ¼ {P(3,5-C
3
¼ {P(p-C
6
H
4
3
)
3
3
6
H
3
(CF
)
3 2
)
3
}]
PR
3
¼ P(pyr)
3
PR
[20]
3
¼ PPh
3
(
Fig. 1) [12a]
Bond lengths (Å)
Ru-P(1)
2.2696(5)
PPh
2.3203(5)
P(p-C CF
2.2707(9)
(PPh
2.2929(9)
P(3,5-P
2.2323(15)
(P(Pyr)
2.2760(14)
(PPh
2.331
(PPh
2.268
(PPh
(
3
)
3
)
3
)
3
)
Ru-P(2)
Ru-Cl
6
H
4
3
)
3
H
6 3
(CF
3
2
) )
3
3
)
3
)
2.4422(5)
2.4372(8)
2.4362(15)
2.437
ꢁ
Bond angles ( )
P(1)-Ru-P(2)
Cl-Ru-P(1)
Cl-Ru-P(2)
99.585(19)
92.389(18)
91.612(17)
95.59(3)
93.03(3)
95.50(3)
97.89(5)
93.51(5)
91.79(5)
99.21
92.42
92.19
Other geometrical parameters
Ru-C5-ring (Å)a
1.904
1.903
1.902
0.161
7.06
1.918
0.221
7.07
b
c
D
Ru-C
0.197
0.137
ꢁ
d
ꢁ
e
ꢁ
ꢁ
Fold angle
9.57
7.45
a
Distance between the C5 ring of the indenyl ligand and the ruthenium center.
b
c
Average difference between the Ru-C1, Ru-C2 and Ru-C3 bond lengths and the Ru-C4 and Ru-C5 bond lengths.
Average difference between the Ru-C1, Ru-C2 and Ru-C3 bond lengths and the Ru-C4 and Ru-C9 bond lengths.
Angle between the plane formed by C1-C2-C3 and by C1-C3-C4-C5.
d
e
Angle between the plane formed by C1-C2-C3 and by C1-C3-C4-C9.
indenyl ligand [11e]. The trans influence weakens the bond strength
3
current ratio ipc/ipa is 1.0 at a scan rate of 0.2 V/s for [RuCl(ind)(PPh )
(
and enlarges the bond length) of the two Ru-C bonds of the benzo
{P(p-C
6
H
4
)
CF
3
)
3
}]. For the complex [RuCl(ind)(PPh
3
){P(3,5-
ꢁ
unit coordinated to the ruthenium. Accordingly, the PPh ligand (as
3
C
6
H
3
(CF
3
2
)
3
}], the E ’ value is significantly higher (þ0.370 V). The
opposed to the fluorinated phosphine ligands) takes the position
trans to the benzoid portion of the indenylid ligand (schematic
structure A in in Fig. 3). This position provides some evidence that
oxidation of [RuCl(ind)(PPh
at different scan rates with an ipc/ipa ratio of 0.98 at 0.2 V/s. It ap-
pears that the introduction of CF -substituted tris(aryl)phosphine
ligands increases the redox potential of the respective complexes
3 6 3 3 2 3
){P(3,5-C H (CF ) ) }] is also reversible
3
3
PPh has a larger trans influence compared to the fluorinated li-
gands; however the solid state structures allow only limited con-
clusions for the situation in solution.
compared to the “parent” complex [RuCl(ind)(PPh
3
)
2
]
ꢁ
(E ’ ¼ ꢀ0.023 V) [12a], which is in line with the higher
p-acidic
In general, it appears that the placement of electron-
electron-demand of the fluorinated ligands. Interestingly, as
withdrawing CF
3
units on the aryl rings in triarylphosphine li-
determined before in our laboratory, the related complex
gands does not have a profound impact on the Ru-P bond length
and other geometric parameters of their respective ruthenium
complexes in the solid state when compared to structurally related
[RuCl(ind)(PPh
of þ0.34 V. Thus, it appears that the P(pyr)
comparable to that of P(3,5-C (CF [12a].
3
){P(pyr)
3
}] (Fig. 1) exhibited a redox potential
3
ligand has a -acidity
p
H
6 3
3 2 3
) )
ones, such as [RuCl(Ind)(PPh
RuCl(Ind)(PPh ] [7].
3 3
){P(pyr) }] (Fig. 1) and
[
3 2
)
2.4. Catalytic applications
2.3. Cyclic voltammetry
We then investigated the new complexes for their ability to
catalytically activate propargylic alcohols [25], and we chose as a
test reaction the etherification of propargylic alcohol 1b with
benzyl alcohol 2b to obtain the propargylic ether 3c (Table 2). We
performed preliminary screening reactions with the more easily
available precursor complex [RuCl(ind)(PPh ) ]; reactivity trends
3 2
established in Table 2 were similar to those observed for the new
Cyclic voltammetry has been used previously to characterize the
electronic properties of ruthenium phosphine complexes by us
[
12a,23] and others [24], and we recorded cyclic voltammograms of
RuCl(ind)(PPh ){P(p-C CF }] and [RuCl(ind)(PPh ){P(3,5-
(CF }]. The traces for a scan rate of 0.2 V/s are compiled
in Fig. 4.
The cyclic voltammograms of [RuCl(ind)(PPh
and [RuCl(ind)(PPh ){P(3,5-C (CF }] show a high degree of
[
3
H
6 4
3
)
3
3
C
H
6 3
3 2 3
) )
complexes with the fluorinated ligands. The complexes
3
6 4 3 3
){P(p-C H CF ) }]
[
[
RuCl(ind)(PPh
RuCl(ind)(PPh
3
)
2
],
[RuCl(ind)(PPh
3
){P(p-C
6
H
4
CF
3
)
3
}]
and
3
6
H
3
3 2 3
) )
){P(3,5-C
H
6 3
(CF }] themselves did not show
3 2 3
) )
reversibility at different scan rates in that their ipc/ipa values are
3
ꢁ
catalytic activity for the reaction. However, after activation by
close to a value of 1 at all scan rates. The E ’ value for the oxidation
0/þ
chloride abstraction using NaPF , catalytic activity was observed.
is þ0.173 V (vs. Cp
2
Fe , Cp ¼ cyclopentadienyl) and the peak
6
In general, a high-boiling, aliphatic solvent (such as toluene)
was required to observe catalytic activity. However, NaPF
minimally soluble in toluene and we determined that the addition
of a small amount of CH CN aided the dissolution of NaPF
Accordingly, the best results were obtained, when a 1: 9 ratio of
CH CN to toluene in the presence of 4e6 equivalents of NaPF
related to the ruthenium catalyst) was employed for the reaction
Table 2, entry 4; one equivalent of NaPF was insufficient, entry 1).
and NaClO obviously did
6
is
3
6
.
3
6
(
(
6
Other chloride abstractors such as KPF
6
4
not activate the ruthenium precursor complex as no reaction was
observed (entries 2 and 3), which might be due to the poor solu-
Fig. 3. Schematic representation of the position of the indenyl ring in the X-ray
structures of indenyl complexes determined in this study. B and C are discussed later in
the text.
6
bility in the solvent mixture. NaPF alone gave no etherification
product, but resulted in some elimination (entry 6).
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M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
5
Fig. 4. Cyclic voltammetry of ruthenium indenyl complexes in 0.1M n-Bu
4
PF
6
/CH
2
Cl
2
, 298K, recorded at a scan rate of 0.2 V/s, [RuCl(ind)(PPh
3 6
){P(p-C H
4
CF
3
)
3
}] (0.92 mM con-
centration, solid line) and [RuCl(ind)(PPh
3
){P(3,5-C
H
6 3
(CF
3
)
2
)
3
}] (0.73 mM concentration, dotted line …).
Table 2
Screening reactions.
Entry
1
Solvent
T e t
Catalysta
Activatorb
1 equiv.
Results/Products
no reaction
ꢁ
CH
CH
CH
CH
3
CN/toluene 1:9
3
CN/toluene 1:9
3
CN/toluene 1:9
3
CN/toluene 1:9
80
C
[RuCl(ind)(PPh
[RuCl(ind)(PPh
[RuCl(ind)(PPh
[RuCl(ind)(PPh
3
)
3
)
3
)
3
)
2
]
2
]
2
]
2
]
8
80
4
80
h
NaPF
KPF
6
ꢁ
ꢁ
2
3
4
C
C
6
no reaction
no reaction
h
NaClO
4
1
80
6 h
C
ꢁ
6 equiv.
4
h
NaPF
6
ꢁ
c
5
6
toluene
toluene
80
1
C
[Ru(ind)(MeCN)(PPh
3
)
2
]PF
6
none
NaPF
6 h
ꢁ
85
C
none
6
4
h
ꢁ
]BAr d
7
toluene
85
C
[Ru(ind)(MeCN)(PPh
3
)
2
F
none
Trace amounts of ether product
4
h
a
1
e2 mol%.
Number of equivalents for the activator given in relation to the ruthenium catalyst.
Preformed, chloride-abstracted complex obtained from reaction with NaPF , see text.
Preformed, chloride-abstracted complex obtained from reaction with NaBAr . BAr
¼ Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, see text.
b
c
6
d
F
F
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6
M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
Under optimized conditions, the complexes and NaPF
6
were first
abstraction, as indicated by corresponding peaks for the starting
ꢁ
31
1
preheated to 85 C for 20 min in CH
3
CN/toluene 1: 9, followed by
material in the P{ H} NMR spectrum (Fig. 5, top). Only some
minor singlets were observed in the spectrum between 47 and
55 ppm. It appears that the more electron-poor complex
[RuCl(ind)(PPh ){P(3,5-C H (CF ) ) }] is - compared to the other
3 6 3 3 2 3
two complexes - more difficult to ionize.
addition of the substrates to the preactivated complex. The acti-
vated complexes were employed in a number of etherification re-
actions to give the known [12d] propargylic ethers 3, and the
results are compiled in Scheme 2. All three precursor complexes
[
[
(
RuCl(ind)(PPh
3
)
2
],
[RuCl(ind)(PPh
3
){P(p-C
6
H
4
CF
3
)
3
}]
and
For all three complexes, peaks between 21 and 30 ppm indicated
RuCl(ind)(PPh
3
){P(3,5-C
6
H
3
(CF }] were employed in catalysis
3
)
2
)
3
the presence of the oxidized ligands O¼PPh (29 ppm), O¼ P(p-
3
experimental details are given in the Supplementary data), and the
C
6
H
4
CF (CF ) ) (21.8 ppm). The
3
)
3
(25.8 ppm) and O¼P(3,5-C
6
H
3
3 2 3
yields given in Scheme 2 are for all three precursor complexes. As
can be seen, the isolated yields do not significantly differ for the
complexes. The isolated yields are moderate; however, the prop-
argylic alcohol and the alcohol nucleophile were employed in
almost equimolar amounts. Excess of the alcohol nucleophile over
the propargylic alcohol is not required, as sometimes reported for
other catalytic systems [25e]. Also, the catalyst load used of
peak assignments for the latter two phosphine oxides were per-
formed based on NMR experiments, where the corresponding
phosphine ligands were oxidized with small amounts of H
CDCl and NMR spectra subsequently recorded.
2 2
O in
3
However, we were intrigued by the fact that the chloride
abstraction experiments resulted in a resonance around 63 ppm for
all three complexes, indicating the formation of a common species
1
1
e2 mol% is lower than that of many other catalyst systems re-
(Fig. 5). Furthermore, we observed a peak at ꢀ12 ppm in the H
ported in the literature [25e].
3 2
NMR spectrum of [RuCl(ind)(PPh ) ] after chloride abstraction,
Thus, the activated complexes exhibited catalytic activity, but
we could not reach our major goal, i.e. to lower the reaction tem-
perature and to increase the yield of the reactions. In order to
improve the catalyst system and to investigate the course of the
reaction in greater detail, we performed additional experiments.
pointing towards formation of a hydrido complex. Indeed, com-
1
31
1
parison with literature values showed that the H and P{ H} NMR
resonances for the known hydrido complex [RuH(ind)(PPh
matches those observed in the reaction mixture after chloride
abstraction [7]. Thus, it appeared that the complexes [Ru(ind)(PPh
3 2
) ]
3
)
þ
þ
{
P(p-C
dergo ligand metathesis to form [Ru(ind)(PPh
forms the hydrido complex [RuH(ind)(PPh
6
H
4
CF
3
)
3
}] and [Ru(ind)(PPh
3
){P(3,5-C
6
H
3
(CF
3
)
2
)
3
}]
un-
þ
3
)
2
] , which then
]. It is known that
2.5. Chloride abstraction products
3
)
2
ruthenium complexes can form hydrides in the presence of alco-
hols or water [26]. In order to determine whether the hydrido
complex [RuH(ind)(PPh ) ] is the actual catalytically active species
3 2
We first speculated that the chloride abstraction to activate the
complexes was inefficient. We, thus, investigated the chloride
abstraction by heating the complexes for several hours in presence
in solution, we synthesized the complex independently following a
literature procedure [7] and employed it as catalyst in test reactions
under the conditions in Scheme 2. Unfortunately, the complex
showed no catalytic activity under these conditions. Thus, the for-
mation of the complex [RuH(ind)(PPh ) ] constitutes a decompo-
3 2
sition pathway of the chloro complexes, resulting potentially in
catalyst deactivation.
6 3
of NaPF and CH CN but without any substrates, and investigated
the result by P{ H} NMR. The P{ H} NMR spectra are shown in
Fig. 5.
31
1
31
1
The parent complex [RuCl(ind)(PPh
3 2
) ] gave a relatively clean
(
albeit incomplete) reaction to the corresponding acetonitrile
þ
31
1
complex [Ru(ind)(CH
3
CN)(PPh
3
)
2
] , as indicated by a new P{ H}
NMR peak at 47.7 ppm (Fig. 5, bottom, see also vide infra for the
independent synthesis of that complex). For the two other com-
plexes [RuCl(ind)(PPh
P(3,5-C (CF }] with fluorinated ligands, the reaction was not
as clean (Fig. 5, middle and top) and a number of new peaks
3
){P(p-C
6
H
4
CF
3
)
3
}] and [RuCl(ind)(PPh
3
)
2.6. Syntheses of acetonitrile complexes and their reactivity
{
6
H
3
3 2 3
) )
3
It is known that ruthenium forms stable acetonitrile (CH CN)
31
1
appeared in the
P{ H} NMR spectra. For the complex
CF }], the starting material was
complexes [27]. We next decided to determine whether analytically
pure acetonitrile complexes could be employed as catalysts for the
title reaction. Accordingly, we synthesized the complex
[
RuCl(ind)(PPh ){P(p-C
3
H
6 4
3 3
)
consumed (Fig. 5, middle). Besides a couple of unidentified singlets
around 48 ppm, the reaction mixture after chloride abstraction
revealed a set of relatively small doublets at 49.3 and 47.4 ppm
[Ru(ind)(CH
the corresponding
[Ru(ind)(CH CN)(PPh
3
CN)(PPh
3
)
2
] PF
6
according to literature procedures for
tetrafluoroborate complex
, as there was no P{ H} NMR spec-
known
þ
31
1
(
J
PP ¼ 35 Hz), which was, based on the synthesis of an authentic
3
3
)
2
] BF
4
sample (vide infra), attributed to the acetonitrile complex
trum published together with its synthesis (Scheme 3) [28]. The
tetrafluoroborate complex has previously been characterized by H
þ
1
[Ru(ind)(CH
3
CN)(PPh
3
){P(p-C
H
6 4
CF
3
)
3
}] .
The
complex
[
RuCl(ind)(PPh
3
){P(3,5-C
6
H (CF
3 3
)
2
)
3
}] gave only partial chloride
NMR and X-ray; for comparison purposes in Fig. 5, in addition we
Scheme 2. Catalytic application of new ruthenium complexes.
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M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
7
Fig. 5. 31P{ H} NMR spectra of the complexes [RuCl(ind)(PPh
1
H
(CF
)
}] (middle) and [RuCl(ind)(PPh
3
){P(3,5-C
6
3
3
)
2
3
}] (top), [RuCl(ind)(PPh
3
){P(p-C
6
H
4
CF
3
)
3
3
)
2
] (bottom) after treat-
ment with NaPF
6
.
þ
Scheme 3. Synthesis of acetonitrile complexes [Ru(ind)(CH
3
CN)(PPh
3
){L}] PF
6
.
analyzed the complex by 31P{ H} NMR and IR. Following the same
1
þ
3 3 6 4 3 3
The molecular ion [Ru(ind)(CH CN)(PPh ){P(p-C H CF ) }] was
procedure, we also synthesized the new acetonitrile complex
not observed in the FAB-MS, but only the fragment [Ru(ind)(PPh
3
)
þ
[
Ru(ind)(CH
3
CN)(PPh
3
){P(p-C H
6 4
CF
3
)
3
}]PF
6
, which was character-
{P(p-C
6
H
4
CF
3
)
3
}] which resulted from CH
3
1
CN loss. The fragmen-
1
31
1
31
ized by H and P{ H} NMR and mass spectrometry (Scheme 3).
tation pattern for the complex and the P{ H} NMR shifts differed
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8
M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
from those of [RuCl(ind)(PPh
strong evidence that a new complex had formed. However, we
3
){P(p-C
6
H
4
CF
3
)
3
}], which provides
Table 3
Selected bond lengths (Å) and angles ( ).
ꢁ
observed a molecular ion for the fragment [Ru(ind)(CH
3
CN)(PPh
3
)
[Ru(ind)(CH CN)(PPh ) ]PF
2 3 2 6
[Ru(ind)(O )(PPh ) ]PF
3
3
2
6
þ
{
P(p-C
6
H
4
CF
3
)
3
}] in the ESI-MS spectrum. Unfortunately, attempts
Bond lengths (Å)
Ru-P(1)
Ru-P(2)
Ru-X
Ru-X
to convert [RuCl(ind)(PPh
3
){P(3,5-C
6
H
3
(CF
3
)
2
)
3
}] to the corre-
2.3913(4)
2.2958(4)
2.3415(16)
2.3782(17)
2.003(5) [X ¼ O(1)]
2.008(5) [X ¼ O(2)]
1.409(6)
sponding acetonitrile complex failed, which could be a conse-
quence of the fact that for this complex chloride abstraction with
2.0436(12) [X ¼ N(1)]
e
e
NaPF
6
is more difficult, as was demonstrated in Fig. 5.
CN)(PPh ]PF was also character-
O(1)-O(2)
Bond angles ( )
The complex [Ru(ind)(CH
3
3
)
2
6
ꢁ
ized structurally (Fig. 6). Selected bond lengths and angles are listed
in Table 3. Structural details will be discussed further below. During
P(1)-Ru-P(2)
X-Ru-P(1)
O(2)-Ru-P(1)
X-Ru-P(2)
O(1)-Ru-P(2)
O(1)-Ru-O(2)
Other geometrical parameters
103.540(12)
96.30(6)
93.56(4) [X ¼ N(1)]
81.78(13) [X ¼ O(1)]
e
105.38(14)
our characterization efforts for [Ru(ind)(CH
NMR, we observed the formation of red crystals precipitating out of
the CDCl solution in the NMR tube. X-ray analysis revealed that the
red crystals are a peroxo complex [Ru(ind)(
3 3 2 6
CN)(PPh ) ]PF by
84.87(3) [X ¼ N(1)]
83.86(14) [X ¼ O(2)]
119.85(14)
41.13(18)
e
e
3
2
h
-O
2
)(PPh
3
)
2
]PF
6
,
a
2
Ru-C5-ring(Å)
Ru-C
1.889
0.132
6.34
1.952
where O
2
is coordinated as
h side-on to the ruthenium center
b
c
2
D
0.204
(
Scheme 3). A number of ruthenium complexes with
h
-coordi-
ꢁ
d
ꢁ
e
5.70
Fold angle
nated O
2
have been structurally characterized [29], and they are
a
Distance between the centroid of the C5 ring of the indenyl ligand and the
ruthenium center.
typically obtained from a ruthenium precursor complex upon re-
action with O . However, attempts to synthesize the complex
)(PPh ]PF in bulk failed. Also, analysis of the
)(PPh ]PF by FAB and ESI-MS did not
give a molecular ion peak as proof of the coordination (or the
presence) of O in the sample. The coordination of O might be
2
b
Average difference between the Ru-C2, Ru-C3 and Ru-C4 bond lengths and the
2
[
Ru(ind)(
h
-O
2
3
)
h
2
6
Ru-C1 and Ru-C5 bond lengths.
2
c
crystals of [Ru(ind)(
-O
2
3
)
2
6
Average difference between the Ru-C1, Ru-C2 and Ru-C3 and the Ru-C4 and Ru-
C5 bond lengths, respectively.
d
Angle between the plane formed by C2-C3-C4 and C1-C2-C4-C5.
Angle between the plane formed by C1-C2-C3 and C1-C3-C4-C5.
2
2
e
reversible, as noted previously by others [28], making character-
ization efforts more difficult. However, the IR spectrum of the
complex in the solid state exhibited an intense absorption at
holds true for the h2-O complex. As discussed above for the other
complexes, one of the two PPh ligands takes the position trans to
the benzoid carbon atoms of the cyclopentadienyl unit of the
2
ꢀ
1
2
8
28 cm ; this absorption is in accordance with
h
-coordinated O
2
,
3
ꢀ
1
which typically shows bands between 800 and 900 cm [30]. The
X-ray data of [Ru(ind)(
precursor complex [Ru(ind)(CH
Fig. 6 and Table 3.
2
h
-O
2
)(PPh
3
)
2
]PF
6
together with those of its
]PF are presented in
indenylid ligand (B in Fig. 3), demonstrating the stronger trans in-
fluence of PPh compared to CH CN.
3
CN)(PPh
3
)
2
6
3
3
However, it seems that for the complex [Ru(ind)(h2-O )(PPh ) ]
2
3 2
In both complexes the ruthenium centers are slightly distorted
octahedra. The acetonitrile complex [Ru(ind)(CH CN)(PPh ]PF is
structurally related to the tetrafluoroborate analog previously
PF , the bond lengths around the ruthenium center are slightly
longer compared to the other complexes. The average Ru-P bond
6
3
3
)
2
6
length is slightly longer and the Ru-Cp distance between the
5
described in the literature [27]. The bond lengths [2.0436(12) to
ruthenium center and the centroid of the
h
-coordinated Cp unit of
(
2.3913(4) Å)] are comparable to those in the complexes bearing
the indenyl ligand is about 0.06 Å longer. The O(1)-O(2) bond
length is 1.409(6) Å and, thus, considerably longer compared to the
O-O bond length in O (1.21 Å) [29], as expected for side-on coor-
2
the fluorinated ligands described above despite the fact that the
complex is cationic. The bond angles around the ruthenium center
in [Ru(ind)(CH
3
CN)(PPh
3
)
2
]PF
6
are also similar except for the P(1)-
dinated O . Similar O-O bond length values have been observed
2
ꢁ
Ru-P(2) angle, which is larger [103.540(12) ] compared to those of
the complexes in Table 1 (all below 100 ). The linear CH
before in metal peroxo complexes [28], and they lie in between the
ꢁ
2ꢀ
3
CN ligand
bond lengths for superoxide (KO , 1.28 Å) [29] and peroxide (O
2
2
2
is obviously less spatially demanding compared to a Cl, allowing for
a larger P(1)-Ru-P(2) angle to better accommodate the bulky PPh
ligands coordinated to the ruthenium center. The parameters
1.49 Å) [29]. Most interestingly, the
h
-O
2
ligand is aligned parallel
3
to the indenyl ligand (C in Fig. 3). Typically, the indenyl ligand oc-
cupies an interstitial site between the two phosphine ligands (A
and B in Fig. 3).
5
corroborating the
h -coordination of the indenyl ligand (D Ru-C
and the fold angle) are similar to those in Table 1, which also
The X-ray structures demonstrate that in the presence of NaPF
6
(left) and [Ru(ind)(h2-O
)(PPh
)
(middle and right). Hydrogen atoms and PF
ꢀ
counterions are omitted for
Fig. 6. The molecular structures of [Ru(ind)(CH
3
CN)(PPh
3
)
2
]PF
6
2
3
2
]PF
6
clarity. Crystallographic parameters are compiled in the experimental, and key bond lengths and angles are listed in Table 3.
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M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
9
and CH
3
CN, for [RuCl(ind)(PPh
3
)
2
] the corresponding acetonitrile
3. Conclusion
complex is obtained. As shown by X-ray and IR, it appears that O
2
-
2
from air can replace the CH
3
CN ligand to give the corresponding
h
In conclusion, two new ruthenium complexes of the general
formula [RuCl(ind)(PPh )L] were synthesized, bearing phosphine
ligands L with CF -substituted aryl rings. Structural characteriza-
tion revealed that the geometry of the new complexes does not
differ significantly from related complexes. However, the place-
ment of the fluorinated ligands resulted in increased oxidation
O
2
complex. However, when applied as catalysts in the title reaction
under the conditions given in Table 3, only small reactivity or yield
differences between [Ru(ind)(CH CN)(PPh ]PF and
Ru(ind)(CH CN)(PPh ){ P(p-C CF }]PF and the in situ acti-
3
3
3
3
)
2
6
[
3
3
6
H
4
3
)
3
6
vated complexes were observed (Table 3, entry 5). We, thus, dis-
continued the investigation of preformed, isolated acetonitrile
complex catalysts.
3 2
potentials compared to the parent complex [RuCl(ind)(PPh ) ]. The
new complexes are, after activation through chloride abstraction,
catalytically active in the etherification of propargylic alcohols. As
31
1
investigated through P{ H} NMR, the chloride abstracted frag-
þ
ments [Ru(ind)(PPh
3
)L] are not very stable and undergo a
2.7. Comparison of catalytic activity
decomposition reaction in solution, and formation of the hydrido
complex [RuH(ind)(PPh ] was observed for the two precursor
complexes, indicating ligand metathesis after chloride abstraction.
When the catalytic activity of the new complexes [RuCl(ind)(PPh
L] was determined for a test reaction and compared to the activity
of the parent compound [RuCl(ind)(PPh ], it appeared that all
3 2
)
Finally, we speculated whether there were reactivity differences
between the three complexes [RuCl(ind)(PPh
3
)
2
], [RuCl(ind)(PPh
3
)
3
)
{
P(p-C CF }] and [RuCl(ind)(PPh ){P(3,5-C
6
H
4
3
)
3
3
H
6 3
3 2 3
(CF ) ) }].
Accordingly, the three precursor complexes were activated by
chloride abstraction for a test reaction; product formation was
followed over time by NMR. The results are compiled in Fig. 7.
Somewhat surprisingly, all three precursor complexes gave com-
parable activities over time, i.e. product formation was comparable
over time for the three complexes. This finding reflects the isolated
yields for the catalysis products presented in Scheme 2, which are
also fairly similar for the three complexes.
3 2
)
three complexes exhibited similar reactivities. Investigation of the
catalytically active species is ongoing.
4. Experimental
While somewhat speculative, the similarities in reactivity point
4.1. General
towards a common catalytically active species for all three catalysts
ꢀ
appear to be involved. It is known from the literature that the PF
6
All reactions were carried out under an inert N
using standard Schlenk techniques. The ligands tris(4-(tri-
fluoromethyl)phenyl)phosphine, P(p-C CF and tris(3,5-
bis(trifluoromethyl)phenyl)phosphine, P(3,5-C (CF were
purchased from Strem Chemicals and used as is. All other chem-
icals, including NaPF , were used as supplied from Sigma-Aldrich
unless otherwise noted and used as received. The complex
[RuCl(ind)(PPh ] was synthesized following the literature [7]. THF
was distilled from Na/benzophenone under N . Ethyl acetate,
hexane, toluene, CH Cl , and ClCH CH Cl were distilled prior to
use; solvents used in catalysis were used as is.
2
atmosphere
anion can hydrolyze under aqueous conditions [31]. Thus, it cannot
ꢀ
be excluded that hydrolysis products of the PF
6
counter anion or
6
H
4
3 3
) ,
other, common decomposition products of the precursor com-
plexes contribute to the catalytic activity of the system. It appeared
that the chemistry of mixed phosphine complexes of ruthenium of
){P(p-C H CF ) }] and
3 6 4 3 3
RuCl(ind)(PPh ){P(3,5-C (CF }] is more complex than we
originally anticipated (as demonstrated in Fig. 5). Further in-
vestigations of the catalytic system and about the catalytically
active species are ongoing.
6
H
3
3 2 3
) ) ,
6
the general formula as in [RuCl(ind)(PPh
[
3
6
H
3
3
)
2
)
3
3 2
)
2
2
2
2
2
Fig. 7. Activity comparison for the ruthenium complexes [RuCl(ind)(PPh
chloride abstraction. The average of three runs for each complex are shown and error bars are given. For comparison, the activity of [RuCl(ind)(PPh )
3
){P(p-C
6
H
4
CF
3
)
3
}] (dotted line) and [RuCl(ind)(PPh
3
){P(3,5-C
6
H
3
(CF
3
)
2
)
3
}] (dashed) after activation by
] (solid line) is also included.
3 2
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10
M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
4.2. Instruments and measurements
2.70.
NMR spectra for characterization were collected at room tem-
perature on a Varian Unity 300 MHz or Bruker Avance 300 MHz
instrument; all chemical shifts ( ) are reported in ppm and are
referenced to a residual solvent signal. IR spectra were collected on
a Thermo Nicolet 360 FT-IR spectrometer. FAB and exact mass data
were collected on a JEOL MStation [JMS-700] Mass Spectrometer.
Melting points were determined on a Thomas Hoover uni-melt
capillary melting point apparatus and are uncorrected. Elemental
analyses were performed by Atlantic Microlab Inc., Norcross, GA,
USA.
4
3 3 2 6
.5. [Ru(ind)(CH CN)(PPh ) ]PF
d
A
Schlenk flask containing [RuCl(ind)(PPh
.401 mmol), NaPF (0.070 g, 0.417 mmol), CH
.829 mmol), and MeOH (15 mL) was refluxed gently for 4 h under
3
)
2
]
(0.311 g,
0
3
6
3
CN (0.200 mL,
nitrogen. An orange precipitate formed. The precipitate was iso-
lated by vacuum filtration and dried under high vacuum to give the
product as an orange solid (0.230 g, 0.248 mmol, 62%). H NMR
1
(300 MHz, CDCl
3
) d 7.29e7.21 (m, 20H, arom.), 7.18e7.12 (m, 14H,
arom.), 6.88e6.80 (m, 14H, arom.), 4.66 (br s, 1H, indenyl), 4.42 (s,
2
d
3
1
1
H, indenyl), 2.12 (s, 3H, CH
3
CN); P{ H} NMR (121 MHz, CDCl
3
)
3 6 4 3 3
4.3. [RuCl(ind)(PPh ){P(p-C H CF ) }]
ꢀ
47.7 (s), ꢀ146.0 (septet, JFP ¼ 712 Hz, PF
6
). IR (neat, solid):
ṽ ¼ 3637 (w), 3322 (w), 3049 (w), 2278 (w), 1626 (w), 1582 (w),
A
3 2
Schlenk flask containing [RuCl(ind)(PPh ) ] (0.260 g,
1531 (w),1478 (m),1431 (m),1329 (w), 1187 (w),1156 (w), 1088 (w),
0
.335 mmol), P(p-C CF (0.158 g, 0.339 mmol), and THF (5 mL)
6
H
4
3 3
)
ꢀ
1
1026 (w), 996 (w), 829 (s), 755 (s), 746 (s) cm . FAB-MS m/z (%) 741
was refluxed gently for 4 h under nitrogen. The solvent was
removed via vacuum. The complex was isolated as a red solid
þ
þ
(80) [Ru(ind)(PPh
3
)
2
] , 479 (100) [Ru(ind)(PPh
3
)] . ESI-MS m/z (%)
] , 741 (100) [Ru(ind)(PPh
þ
þ
7
82 (20) [Ru(ind)(CH
3
CN)(PPh
3
)
2
3
)
2
] .
(
(
0.148 g, 0.125 mmol, 57%) by column chromatography, silica gel
2 ꢂ 10 cm) using CH Cl and petroleum ether (1:3) as eluent. The
Cl layered with hexanes. m. p.
22e124 C (dec., capillary). H NMR (300 MHz, CDCl 7.40e7.29
m, 24H, arom.), 7.20e7.11 (m, 6H, arom.), 6.92e6.81 (m, 2H, arom.),
2
2
product was recrystallized from CH
1
(
2
2
3 3 6 4 3 3 6
4.6. [Ru(ind)(CH CN)(PPh ){P(p-C H CF ) }]PF
ꢁ
1
3
) d
A Schlenk flask containing [RuCl(ind)(PPh
3
){P(p-C
6
4
H CF
3
)
3
}]
4
.73e4.70 (m, 1H, indenyl), 4.43 (br s, 1H, indenyl), 3.74 (s, 1H,
(0.042 g, 0.043 mmol), NaPF (0.008 g, 0.050 mmol), CH
6
3
CN
13
1
indenyl); C{ H} NMR (75 MHz, CDCl
s),136.0 (s),134.2 (s),134.1 (s),133.8 (s),133.6 (s),131.6 (s),131.2 (s),
30.8 (s), 130.3 (s), 129.7 (s), 129.4 (s), 129.0 (s), 128.6 (s), 127.8 (s),
27.7 (s), 125.8 (s), 125.5 (s), 124.7 (m), 123.4 (s), 122.2 (s), 118.6 (s),
3
)
d
140.7 (s), 140.2 (s), 136.6
(0.200 mL, 3.829 mmol), and MeOH (10 mL) was stirred at room
temperature for 1.5 h under nitrogen. The solvent was removed and
solids were washed with diethyl ether and dried. The residue was
passed through a cotton-filled pipette using chloroform. The res-
(
1
1
1
12.8 (s), 112.7 (s), 110.6 (br s), 89.6 (s), 70.9 (s), 70.8 (s), 64.8 (s),
idue was dried and the product was isolated as a yellow-orange
1
5
3.7 (s, CH
2
Cl
2
), 31.8 (s, hexanes), 22.9 (s, hexanes), 14.4 (s, hex-
50.1 (d, JPP ¼ 42 Hz), 44.2 (d,
PP ¼ 42 Hz); F{ H} NMR (282 MHz, CDCl ꢀ62.9. IR (neat,
solid (0.034 g, 0.030 mmol, 69.9%). H NMR (300 MHz, CDCl
3
)
3
1
1
anes); P{ H} NMR (121 MHz, CDCl
J
3
)
d
d
7.29e7.21 (m, 20H, arom.), 7.18e7.12 (m, 14H, arom.), 6.88e6.80
19
1
3
) d
(m, 14H, arom.), 4.66 (br s, 1H, indenyl), 4.42 (s, 2H, indenyl), 2.12 (s,
3
1
1
solid): ṽ ¼ 3041 (w), 2956 (w), 2923 (w), 1604 (w), 1479 (w), 1395
3H, CH
3
CN); P{ H} NMR (121 MHz, CDCl
3
)
d
49.5 (d, JPP ¼ 35 Hz),
ꢀ
(
w),1317 (w),1162 (w),1113 (w),1085 (s),1055 (s),1012 (s), 842 (m),
47.4 (d, JPP ¼ 35 Hz), ꢀ141.0 (septet, JFP ¼ 712 Hz, PF
6
). IR (neat,
ꢀ
1
8
23 (m), 778 (m), 746 (m) cm . FAB-MS m/z (%) 718 (20) [RuCl(ind)
solid): ṽ ¼ 3069 (w), 2930 (w), 2864 (w), 2320 (w), 1604 (w), 1478
(w), 1433 (w), 1394 (w), 1318 (s), 1165 (m), 1120 (s), 1088 (m), 1056
(s), 1012 (m), 824 (s), 745 (m). FAB-MS m/z (%) 945 (70) [Ru(ind)
þ
þ
{
P(p-C
6
H
4
CF
3
)
CF
3
}] , 683 (22) [Ru(ind){P(p-C
6
H
4
CF
3 3
) }] , 483 (32)
þ
þ
[
C
5
O¼P(p-C
6
H
4
3
)
3
] , 466 (100) [P(p-C
6
H
4
CF
3
)
3
] , 321 (15) [P(p-
Ru (980.24): calcd. C
þ
þ
þ
þ
H
6 4
CF
3
)
2
] , 262 (43) [PPh
3
] . C48
H34ClF
9
P
2
{P(p-C
6
H
4
CF
[Ru(ind)(PPh
CN)(PPh
)(P(p-C
3
)
3
}(PPh
3
)] , 683 (40) [Ru(ind){P(p-C
6
H
4
CF
3
)
3
}] , 479
þ
8.81, H 3.50; found C 59.19, H 3.89.
(100)
3
)] .
){P(p-C
CF
ESI-MS
þ
3 3
CF ) }] , 945 (100) [Ru(In-
m/z
(%)
986
(25)
[Ru(ind)(CH
3
3
6
H
4
þ
4.4. [RuCl(ind)(PPh ){P(3,5-C (CF
3
6
H
3
3
)
2
)
3
}]
denyl)(PPh
3
6
H
4
3
)
3
)] .
]PF
A NMR tube containing [Ru(ind)(CH
A
Schlenk flask containing [RuCl(ind)(PPh
3 2
) ] (0.171 g,
4
.7. [Ru(ind)(
h
2-O
2
)(PPh
3
)
2
6
0
.219 mmol), P(3,5-C (CF (0.165 g, 0.242 mmol), and THF
6
H
3
3 2 3
) )
(
5 mL) was refluxed gently for 4 h under nitrogen. The solvent was
3
3 2 6 3
CN)(PPh ) ]PF in CDCl
removed via vacuum. The complex was isolated as a red solid
was allowed to rest on the bench top for 72 h, over which dark solid
(
0.077 g, 0.079 mmol, 24%) by column chromatography, silica gel
2 ꢂ 10 cm) using CH Cl and petroluem ether (1:3/v:v) as eluent.
Cl layered with hexanes,
mp 141e143 C (dec., capillary). H NMR (300 MHz, CDCl
crystals deposited. IR (neat, solid): ṽ ¼ 3056 (w), 2920 (m), 2850
(
2
2
(
(
w), 2283 (w), 1479 (m), 1432 (m), 1186 (w), 1087 (m), 996 (w), 909
The complex was recrystallized from CH
2
2
2
ꢀ1
m), 828 (s,
h -O ), 723 (s) cm . From X-ray sample (in Nujol): FAB-
2
ꢁ
1
3
)
þ
þ
MS m/z (%) 741 (52) [Ru(ind)(PPh
3
)
2
] , 625 (10) [Ru(PPh
3
)
2
] , 479
].
d
7.89e7.85 (m, 9H, arom.), 7.39e7.27 (m, 10H, arom.), 7.19e7.14 (m,
H, arom.), 6.95e6.92 (m,1H, arom.), 6.59e6.55 (m, 2H, arom.), 5.15
þ
(100) [Ru(ind)(PPh
3
)] , 363 (16) [Ru(PPh
3
)], 279 (64) [O¼PPh
3
6
From separate crystal: ESI-MS m/z (%) 782 [Ru(in-
13
(
br s, 1H, indenyl), 4.84 (m, 1H, indenyl), 3.82 (s, 1H, indenyl);
C
þ þ
3 3 2 3 2
d)(CH CN)(PPh ) ] , 741 [Ru(ind)(PPh ) )] .
1
{
H} NMR (75 MHz, CDCl
33.5 (d, JCP ¼ 9.7 Hz), 133.3 (m), 131.8 (d, JCP ¼ 9.1 Hz), 131.4 (d,
CP ¼ 9.1 Hz), 129.9 (s), 129.3 (s), 128.0 (d, JCP ¼ 9.7 Hz), 126.7 (s),
24.8 (s), 123.9 (s), 121.1 (s), 111.0 (s), 109.4 (s), 91.9 (s), 75.9 (s), 75.8
3
) d 138.3 (s), 137.8 (s), 136.5 (s), 135.9 (s),
1
J
1
4.8. Catalysis
31
1
(
(
d
s), 63.3 (s), 53.7 (s, CH
d, JPP ¼ 42 Hz), 47.8 (d, JPP ¼ 42 Hz); F{ H} NMR (282 MHz, CDCl
ꢀ62.8. IR (neat, solid): ṽ ¼ 3053 (w), 3022 (w), 2308 (w), 2117 (w),
888 (w), 1821 (w), 1614 (w), 1478 (w), 1432 (w), 1351 (s), 1275 (s),
2
Cl
2
); P{ H} NMR (121 MHz, CDCl
3
)
d
50.1
Unless otherwise indicated, the ruthenium complexes were
placed into a screw-capped vial containing 1 mL of acetonitrile in
toluene (1 MeCN: 9 Tol), and NaPF (4 molar equivalents with
6
respect to ruthenium), and heated for approximately 20 min. To
this solution, the propargyl alcohol and substituent nucleophile
were added and allowed to heat for the remainder of the reaction
time.
19
1
3
)
1
ꢀ
1
1176 (m),1117 (s), 1088 (s), 893 (m), 843 (m), 816 (m), 748 (m) cm
.
102
31 18 2
HRMS: calcd. for C51H F P Ru 1149.0657; found 1149.047.
C H31ClF18P Ru (1184.23): calcd. C 51.73, H 2.64; found C 50.72, H
51 2
Please cite this article in press as: M.J. Stark, et al., Journal of Organometallic Chemistry (2017), http://dx.doi.org/10.1016/
j.jorganchem.2017.03.043

M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
11
4.9. Activity determinations in Fig. 7
4.11. X-ray structure determination for [RuCl(ind)(PPh
3
){P(p-
C
6
H
4
CF
3
)
3
}], [RuCl(ind)(PPh
CN)(PPh )]PF
3
){P(3,5-C
6
H
3
(CF
h
3
)
-O
2
)
3
}],
)(PPh
2
The respective precursor complex (0.0061 mmol, 2 mol %) was
[Ru(ind)(CH
3
3
)
2
6
and [Ru(ind)(
2
3
)
2
]PF
6
placed into an NMR tube along with NaPF
and CH
6
(0.006 g, 0.036 mmol)
CN (0.02 mL). The mixture was heated for 5 min at 85 C. A
ꢁ
3
Crystals of [RuCl(ind)(PPh
{P(3,5-C (CF }] and [Ru(ind)(CH
priate dimension were obtained by diffusion of CH
3
){P(p-C
6
H
4
CF
3
)
3
}], [RuCl(ind)(PPh
)]PF of appro-
Cl into hexane
)(PPh ]PF
solution of
6
under aerobic conditions and directly
3
)
solution containing 1-phenyl-2-propyn-1-ol (1a, 0.041 g,
.31 mmol), benzyl alcohol (2b, 42 mg, 0.39 mmol) and p-dime-
6
H
3
3
)
2
)
3
3
CN)(PPh
3
)
2
6
0
2
2
2
thoxybenzene (internal standard, 0.002 g) in toluene-d
8
(0.6 mL)
solutions of the complexes. Crystals of [Ru(ind)(
were obtained by storage of CDCl
[Ru(ind)(CH CN)(PPh )]PF
h
-O
2
3
)
2
6
ꢁ
was added to each NMR tube. The mixture was heated at 85 C for
a
3
2
4 h, where 1H NMR spectra were recorded for each reaction
3
3
)
2
mixture over a consistent time period. Integration of the diaster-
eotopic doublets at , 2H) for the product
4.78 (d, JHH ¼ 11.7 Hz, CH
in the spectrum were referenced to the aromatic protons of p-
dimethoxybenzene at 6.71 (4H).
taken from the reaction mixture. Crystals of approximate di-
mensions were mounted on MiTeGen cryoloops in random orien-
tations. Preliminary examination and data collection were
performed using a Bruker X8 Kappa Apex II Charge Coupled Device
d
2
d
(
CCD) Detector system single crystal X-ray diffractometer equipped
with an Oxford Cryostream LT device. All data were collected using
graphite monochromated Mo K radiation (
a
l
¼ 0.71073 Å) from a
fine focus sealed tube X-ray source. Preliminary unit cell constants
were determined with a set of 36 narrow frame scans. Typical data
4
.10. Cyclic voltammetry
sets consist of combinations of
u and F scan frames with typical
ꢁ
scan width of 0.5 and counting time of 15 s/frame at a crystal to
detector distance of 4.0 cm. The collected frames were integrated
using an orientation matrix determined from the narrow frame
scans. Apex II and SAINT software packages [33] were used for data
collection and data integration. Analysis of the integrated data did
not show any decay. Final cell constants were determined by global
refinement of reflections harvested from the complete data set.
Collected data were corrected for systematic errors using SADABS
Voltammograms were recorded in a three-electrode BAS elec-
trochemical cell in a Vacuum Atmospheres HE-493 drybox under
an atmosphere of argon in 0.1M NBu PF /CH Cl at 298 K. A
.6 mm Pt disk electrode was used as the working electrode, a
4
6
2
2
1
platinum wire was used as the auxiliary electrode, and a silver wire
was used a pseudo-reference electrode. Potentials were calibrated
0/þ
against the Cp*
2
Fe
couple, which is known to occur at ꢀ0.548 V
couple for this solvent medium [32]. The potentials
in this paper can be changed to SCE reference values by addition of
.56 V. Voltammograms were collected at 0.05e1.6 V/s with an
0/þ
2
vs the Cp Fe
[32] based on the Laue symmetry using equivalent reflections.
Crystal data and intensity data collection parameters are listed
in Table 4.Structure solution and refinement were carried out using
the SHELXTL- PLUS software package [34]. The structures were
0
EG&G PAR 263A potentiostat interfaced to a computer operated
with EG&G PAR Model 270 software.
Table 4
Crystallographic parameters.
[
C
RuCl(ind)(PPh
CF }]
3
){P(p-
[RuCl(ind)(PPh
(CF }]
3
){P(3,5-
[Ru(ind)(CH
3
CN)(PPh
3
)
2
]PF
6
[Ru(ind)( 2
h -O )(PPh ) ]PF
2 3 2 6
6
H
4
3
)
3
C
6
H
3
3 2 3
) )
Empirical formula
Formula weight
(C48
H
34ClF
9
P
2
Ru)
2
(CHCl
)
3 3
(C51
Et
2456.54
H
O
31ClF18
P
2
Ru)
2
C
47
H
40
F
6
NP
3
Ru
45 37 6 2 3
C H F O P Ru
2
2318.52
926.78
917.72
Temperature K/Wavelength Å 100(2)/0.71073
100(2)/0.71073
Triclinic
100(2)/0.71073
Monoclinic
100(2) K/0.71073
Triclinic
Crystal system
Space group
Unit cell dimensions
Triclinic
Pꢀ1
Pꢀ1
P2
1
Pꢀ1
a ¼ 9.5521(3) Å
a ¼ 11.3198(4) Å
a ¼ 10.5101(13) Å
b ¼ 17.3270(19) Å
a ¼ 9.8032(5) Å
b ¼ 14.8889(8) Å
b ¼ 11.5438(4) Å
b ¼ 20.1160(10) Å
c ¼ 21.3297(8) Å
c ¼ 22.2959(10) Å
c ¼ 11.2487(13) Å
c ¼ 19.5349(10) Å
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
a
b
g
¼ 90.0613(19)
a
b
g
¼ 101.841(2)
¼ 93.1865(18)
a
b
g
¼ 90
a
b
g
¼ 72.190(3)
ꢁ
ꢁ
ꢁ
ꢁ
¼ 90.123(2)
¼ 96.677(7)
¼ 79.428(3)
ꢁ
ꢁ
ꢁ
¼ 90.9485(18)
¼ 94.4486(19)
¼ 90
¼ 71.868(3)
3
3
3
3
Volume/Z
2351.64(14) Å /1
4940.7(4) Å /2
1.651 Mg/m
0.545 mm
2034.6(4) Å /2
2567.5(2) Å /2
3
3
3
3
Density (calculated)
Absorption coefficient
F(000)
1.637 Mg/m
0.786 mm
1162
0.499 ꢂ 0.348 x 0.337
1.531 Mg/m
0.567 mm
1.187 Mg/m
0.451 mm
ꢀ
1
ꢀ1
ꢀ1
ꢀ1
2456
944
932
Crystal size/mm3
0.406 ꢂ 0.337 x 0.189
0.598 ꢂ 0.365 x 0.219
0.384 ꢂ 0.199 x 0.107
ꢁ
ꢁ
ꢁ
ꢁ
Theta range for data collection 1.764e37.238
0.936e27.799
1.823e40.516
1.100e26.492
Index ranges
ꢀ16 ꢃ h ꢃ 16,
ꢀ14 ꢃ h ꢃ 14,
ꢀ18 ꢃ h ꢃ 19,
ꢀ28 ꢃ k ꢃ 30,
ꢀ20 ꢃ l ꢃ 19
92778
24235 [R(int) ¼ 0.028]
Semi-empirical from
equivalents
ꢀ9ꢃh ꢃ 12,
ꢀ
ꢀ
17 ꢃ k ꢃ 19,
36 ꢃ l ꢃ 36
ꢀ26 ꢃ k ꢃ 25,
ꢀ18 ꢃ k ꢃ 18,
ꢀ24 ꢃ l ꢃ 24
39837
0 ꢃ l ꢃ 29
Reflections collected
Independent reflections
Absorption correction
59057
22976
59057 [R(int) ¼ 0.018]
Semi-empirical from
equivalents
22976 [R(int) ¼ 0.042]
10242 [R(int) ¼ 0.070]
Semi-empirical from
equivalents
Semi-empirical from equivalents
Max. and min. transmission
Data/restraints/parameters
Goodness-of-fit on F2
0.791035 and 0.737117
59057/37/624
1.058
0.862066 and 0.748420
22976/343/1392
1.011
0.7693 and 0.7103
24235/1/523
1.053
0.7672 and 0.6547
10242/73/545
1.044
Final R indices [I > 2sigma(I)] R1 ¼ 0.0497,
R1 ¼ 0.0499,
R1 ¼ 0.0236,
R1 ¼ 0.0788,
wR2 ¼ 0.1803
1.356 and ꢀ1.905
R indices (all data)
wR2 ¼ 0.1341
wR2 ¼ 0.1289
1.617 and ꢀ0.837
wR2 ¼ 0.0530
0.763 and ꢀ0.551
Largest diff. peak and hole/
2.245 and ꢀ1.603
ꢀ
3
e.Å
Please cite this article in press as: M.J. Stark, et al., Journal of Organometallic Chemistry (2017), http://dx.doi.org/10.1016/
j.jorganchem.2017.03.043

12
M.J. Stark et al. / Journal of Organometallic Chemistry xxx (2017) 1e13
solved and refined successfully in the space groups P2
Ru(ind)(CH CN)(PPh )]PF
and Pꢀ1 for all other complexes. Full
matrix least-squares refinements were carried out by minimizing
1
for
D.T.T. Yapp, C.J. Walsby, Chem. Eur. J. 19 (2013) 17031e17042;
c) O. Mazuryk, K. Kurpiewska, K. Lewi nꢁ ski, G. Stochel, M. Brindell, J. Inorg.
Biochem. 116 (2012) 11e18;
d) N.P.E. Barry, P.J. Sadler, Chem. Soc. Rev. 41 (2012) 3264e3279;
(e) Y.K. Yan, M. Melchart, A. Habtemariam, P.J. Sadler, Chem. Commun. (2005)
764e4776.
(
[
3
3
)
2
6
(
2
2 2
o c
Sw(F -F ) . The non-hydrogen atoms were refined anisotropically
4
to convergence. All hydrogen atoms were treated using appropriate
riding model (AFIX m3). The final residual values and structure
refinement parameters are listed in Table 4.
[
[
6] (a) J.M. Cole, K.Y.M. Yeung, G. Pace, S.O. Sylvester, D. Mersch, R.H. Friend,
CrystEngComm 17 (2015) 5026e5031;
(b) A. Breivogel, C. Kreitner, K. Heinze, Eur. J. Inorg. Chem. (2014) 5468e5490;
(c) S. Fantacci, F. De Angelis, Coord. Chem. Rev. 255 (2011) 2704e2726.
Absolute structure determination was carried out using Parson's
7] L.A. Oro, M.A. Ciriano, M. Campo, C. Foces-Foces, F.H.J. Cano, J. Organomet.
method [35] for [Ru(ind)(CH
3
CN)(PPh
3
)
2
)]PF
6
with Flack
Chem. 289 (1985) 117e131.
x ¼ ꢀ0.021(4) from 10263 selected quotients.
[8] (a) K.M.E. Burton, D.A. Pantazis, R.G. Belli, R. McDonald, L. Rosenberg, Or-
2
ganometallics 35 (2016) 3970e3980;
For the compound [Ru(ind)(
36] was used to remove badly disordered solvent molecules
) The counter ion PF is also disordered and the disorder
h
-O
2
)(PPh
3
)
2
]PF
6
Platon-Squeeze
(b) V. Cadierno, J. Díez, M. Pilar Gamasa, J. Gimeno, E. Lastra, Coord. Chem. Rev.
[
(
193e195 (1999) 147e205;
3 ꢂ CHCl
3
6
(c) M. Pilar Gamasa, J. Gimeno, C. Gonzalez-Bernardo, B.M. Martín-Vaca,
D. Monti, M. Bassetti, Organometallics 15 (1996) 302e308.
9] Examples: (a) I. García de la Arada, J. Díez, M. Pilar Gamasa, E. Lastra, Or-
ganometallics 34 (2015) 1345e1353;
was resolved with partial occupancy F atoms with geometrical
restraints.
[
For the complex [RuCl(ind)(PPh
molecule of ethylacetate was found in the lattice. Two CF
and the CH
modeled with partial occupancy atoms and geometrical restraints.
The data for [RuCl(ind)(PPh ){P(3,5-C (CF }] was twinned.
A two component twin model was used for refinement with
BASF ¼ 0.49.1.5 molecules of CHCl /Ru were found in the lattice.
Disordered CF group was refined with partial occupancy F atoms
3
){P(p-C
6
H
4
CF
3
)
3
}], half
a
(b) I. García de la Arada, J. Díez, M.P. Gamasa, E. Lastra, J. Organomet. Chem.
797 (2015) 101e109.
10] (a) S. Nolan, Acc. Chem. Res. 47 (2014) 3089e3101;
3
groups
[
3
of the solvent were disordered. The disorder was
(
b) C.A. Mebi, R.P. Nair, B.J. Frost, Organometallics 26 (2007) 429e438;
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(
ꢀ
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3
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H
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) )
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3
with geometrical restraints.
Tables of calculated and observed structure factors are available
in electronic format.
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Acknowledgments
(
(
(
c) L.F. Veiros, Organometallics 19 (2000) 3127e3136;
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We would like to thank the National Science Foundation (NSF
CHE-1300818, EBB; CHE-156509, MJS) for financial support. Further
funding from the National Science Foundation for the purchase of
the NMR spectrometer (CHE-9974801), the ApexII diffractometer
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2
(
(
MRI, CHE-0420497), and the mass spectrometer (CHE-9708640) is
acknowledged.
(
4
Appendix A. Supplementary data
(
1
(
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2017.03.043.
(
[
13] Representative examples: (a) O. bin Shawkataly, M.A.A. Pankhi, M.G. Alam,
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