Nucleophilic Additions to Allenylidene Ruthenium Complexes

Article abstract of DOI:10.1021/acs.organomet.5b00060

Allenylidene complexes [Ru(η⁵-C₉H₇)(=C=C=CPh₂){P(OR)₃}(PPh₃)][PF₆] (R = Et (1), Me (2)) have been synthesized by the reaction of the complexes [Ru(η⁵-C₉H

Full text of DOI:10.1021/acs.organomet.5b00060

Article
pubs.acs.org/Organometallics
Nucleophilic Additions to Allenylidene Ruthenium Complexes
Isaac García de la Arada, Josefina Díez, M. Pilar Gamasa, and Elena Lastra*
́ ́ ́
Departamento de Química Organica e Inorganica, Instituto de Química Organometalica “Enrique Moles” (Unidad Asociada al CSIC),
Universidad de Oviedo, 33006 Oviedo, Principado de Asturias, Spain
S
* Supporting Information
ABSTRACT: Allenylidene complexes [Ru(η5-C9H7)(C
CCPh2){P(OR)3}(PPh3)][PF6] (R = Et (1), Me (2)) have
been synthesized by the reaction of the complexes [Ru(η5-
C9H7)Cl{P(OR)3}(PPh3)] with 1,1-diphenyl-2-propyn-1-ol in
the presence of NaPF6. Addition of different nucleophiles to
complex 1 allows the synthesis of new allenyl or alkynyl
ruthenium complexes depending on the regiochemistry of the
reaction. Unexpected complexes [Ru(η5-C9H7){κ3(C,C,C)-C-
i
(R2PCH2CHCH2)CCPh2}{P(OEt)3}][PF6] (R = Pr
(9a), Ph (9b)), containing an unusual κ3(C,C,C)-ligand have
been obtained from the reaction of the allenylidene complex 1
i
with alkenylphosphane Ph2PCH2CHCH2 (ADPP) or Pr2PCH2CHCH2 (ADIP). The formation of these complexes is
proposed to proceed through an intermediate, [Ru(η5-C9H7)(CCCPh2){P(OR)3}{κ1(P)-R2PCH2CHCH2}][PF6].
occurs especially for electron-rich allenylidene ruthenium
complexes, leading to vinylidene complexes.6,12
INTRODUCTION
■
Transition metal allenylidene complexes display a versatile
chemistry,1 which makes them useful intermediates in
stoichiometric and catalytic processes.2 In particular, the
reactivity of ruthenium(II) allenylidene complexes has been
widely studied.3
It is well known that electrophilic attacks to allenylidene
complexes take place at the β-carbon atom of the allenylidene
chain, while Cα and Cγ atoms react with nucleophiles. This
reactivity agrees with theoretical calculations4 indicating the
contributions for the HOMO (mainly Cβ atom) and the
LUMO (mainly Cα and Cγ atoms) orbitals.
The regioselectivity of the nucleophilic addition reactions to
the allenylidene chain depends on both electronic and steric
factors of (i) the metallic fragment; (ii) the substituents on the
allenylidene chain; and (iii) the nucleophile. Thus, anionic
nucleophiles tend to react through the Cγ atoms, leading to
neutral alkynyl complexes.5,6 In fact, stereoselective nucleo-
philic attack on the Cγ atom has been used in the stoichiometric
formation of optically active alkynyl complexes,7 and recently
diastereoselective nucleophilic attacks on a chiral-at-metal
ruthenium allenylidene complex have been reported to give
alkynyl complexes in diasteromeric ratios up to 84:16.8
However, these nucleophilic attacks are not always regiose-
lective, and mixtures of complexes resulting from the attack to
both Cα and Cγ can be obtained.9
When neutral nucleophiles containing acidic hydrogens such
alcohols, amines, and thiols are used, vinylcarbene complexes,
resulting from the initial addition of the nucleophile to the α-
carbon and protonation of the β-carbon, are usually the
reaction products.10,11 However, depending on the metal
fragment and the substituents on the allenylidene chain, the
less frequent addition to Cγ can be obtained. This reaction
On the other hand, when phosphanes are used as
nucleophiles, both regioisomers can be obtained depending
on the reactants.11,13 Moreover, isomerization processes from
the kinetically controlled alkynyl complexes, resulting from the
attack to the γ-carbon, to the thermodynamically controlled
allenyl products, resulting from the attack to the α-carbon, are
observed for some complexes.14
In order to clarify the regioselectivity of nucleophilic attacks
on the allenylidene chain, in this paper we look into the
reaction of a number of neutral and anionic nucleophiles
toward the allenylidene [Ru(η5-C9H7)(CCCPh2){P-
(OEt)3}(PPh3)][PF6] (1), bearing the phosphite ligand
P(OEt)3, which presents a π-acceptor character intermediate
between the CO and phosphanes, which are commonly used as
ancillary ligands in the study of the reactivity of allenylidene
complexes.15
On the other hand, the reaction of the allenylidene 1 with
alkenylphosphanes Ph2PCH2CHCH2 (ADPP) or
iPr2PCH2CHCH2 (ADIP) allows the synthesis and charac-
terization of unexpected complexes [Ru(η5-C9H7){κ3(C,C,C)-
C(R2PCH2CHCH2)CCPh2}{P(OEt)3}][PF6], contain-
ing an unusual κ3(C,C,C)-ligand.
RESULTS AND DISCUSSION
■
Synthesis of [Ru(η5-C9H7)(CCCPh2){P(OR)3}-
(PPh3)][PF6] (R = Et (1), Me (2)). Complexes [Ru(η5-
C9H7)Cl{P(OR)3}(PPh3)] (R = Et, Me) were synthesized in
88% and 92% yield, respectively, by reaction of complex
Received: January 21, 2015
Published: March 20, 2015
© 2015 American Chemical Society
1345
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
[Ru(η5-C9H7)Cl(PPh3)2] with the stoichiometric amount of
phoshites, P(OEt)3 or P(OMe)3, in refluxing toluene. These
complexes have been recently synthesized in 75% yield when
the same reaction is carried out in refluxing THF. Analytical
and spectroscopic data agree with those reported in the
literature.16
The reaction of these complexes with 1,1-diphenyl-2-propyn-
1-ol and NaPF6, in refluxing methanol, gives rise to allenylidene
complexes [Ru(η5-C9H7)(CCCPh2){P(OR)3}(PPh3)]-
[PF6] (R = Et (1), Me (2)) in 85% (1) and 93% (2) yield
(Scheme 1). Both complexes are purple, air-stable solids.
Elemental analyses and electrospray (ES) mass spectra agree
with the proposed stoichiometry.
Scheme 1. Synthesis of Complexes 1 and 2
Figure 1. Molecular structure and atom-labeling scheme for the cation
of complex [Ru(η5-C9H7)(CCCPh2){P(OMe)3}(PPh3)]-
[PF6]·2CH2Cl2 (2·2CH2Cl2). Solvent molecules and hydrogen
atoms have been omitted for clarity. Non-hydrogen atoms are
represented by their 20% probability ellipsoids. Selected bond lengths
(Å): Ru(1)−P(1) = 2.301(2), Ru(1)−P(2) = 2.233(2), Ru(1)−C* =
1.936(1), Ru(1)−C(1) = 1.898(6), C(1)−C(2) = 1.247(9), C(2)−
C(3) = 1.366(9). Selected bond angles (deg): Ru(1)−C(1)−C(2) =
172.20(50), C(1)−C(2)−C(3) = 177.60(70), C*−Ru(1)−C(1) =
124.78(18), C*−Ru(1)−P(1) = 123.05(4), C*−Ru(1)−P(2) =
124.70(5), P(1)−Ru(1)−P(2) = 93.56(6), P(1)−Ru(1)−C(1) =
89.07(18), P(2)−Ru(1)−C(1) = 91.85(19), C* = centroid of C(34),
C(35), C(36), C(37), C(42). C** = centroid of C(37), C(38), C(39),
C(40), C(41), C(42).
Complexes 1 and 2 have been fully characterized by
spectroscopic methods. Characteristic features of the spectro-
scopic data for these complexes are the following: (i) The IR
spectra show the ν(CCC) absorption at 1936 (1) and
1939 (2) cm−1 along with the expected absorption for the PF6
group at 838 cm−1; (ii) the 31P{1H} NMR spectra in
dichloromethane show two doublets, one for the phosphane
Reaction of [Ru(η5-C9H7)(CCCPh2){P(OEt)3}-
(PPh3)][PF6] (1) with Anionic Nucleophiles: Synthesis of
Alkynyl Complexes [Ru(η5-C9H7){CC−C(OMe)Ph2}{P-
(OEt)3}(PPh3)] (3) and [Ru(η5-C9H7){CC−C(SR)Ph2}{P-
(OEt)3}(PPh3)] (R = Me (4a), iPr (4b), tBu (4c)). The reaction
of complex 1 with sodium methoxide at room temperature or
sodium alkylsulfides at low temperature leads respectively to
neutral alkynyl complexes [Ru(η5-C9H7){CCC(OMe)Ph2}-
{P(OEt)3}(PPh3)] (3) and [Ru(η5-C9H7){CCC(SR)Ph2}-
ligand at 51.0 ppm (2JPP = 50.2 Hz) (1) and 51.3 ppm (2JPP
=
51.8 Hz) (2) and another for the phosphite ligand at 135.9
ppm (1) and 141.3 ppm (2); (iii) the H and 13C{1H} NMR
1
spectra of both complexes show the expected signals for the
indenyl ligand; (iv) the 13C{1H} NMR spectra of these
complexes display the characteristic low-field resonances for the
Cα atom at 295.0 ppm (1) and 295.5 ppm (2) as a doublet of
doublets and two singlets for the Cβ and Cγ atoms of the
allenylidene group at 204.1 and 156.2 ppm (1) and 202.6 and
157.0 ppm (2), respectively (see Experimental Section).
The structure of complex 2 was determined by single-crystal
X-ray diffraction analysis. Slow diffusion of hexane into a
solution of 2 in dichloromethane allowed us to collect suitable
crystals for X-ray diffraction studies. An ORTEP-type
representation of the cation of complex 2·2CH2Cl2 is shown
in Figure 1, and selected bonding data are collected in the
caption.
i
t
{P(OEt)3}(PPh3)] (R = Me (4a), Pr (4b), Bu (4c)), which
were isolated as orange solids (Scheme 2). Even when
Scheme 2. Synthesis of Complexes 3 and 4a−c
The molecule exhibits a three-legged piano-stool geometry,
with the η5-indenyl ligand displaying the usual allylene
coordination mode. The benzo ring of the indenyl ligand is
oriented over the allenylidene chain, as shown by the dihedral
angle between the planes C*−C**−Ru and C*−Ru−C(1)17 of
20.61(2)°. The diphenylallenylidene ligand is bound to the
metal in a nearly linear fashion (C(1)−C(2)−C(3) bond angle
177.60(70)°) with bond lengths Ru−C(1) 1.898(6) Å, C(1)−
C(2) 1.247(9) Å, and C(2)−C(3) 1.366(9) Å. As expected, the
observed distances in the allenylidene chain indicate a
contribution of the canonical form [M]−CC−CPh2. These
bonding parameters can be compared with those shown by
complexes 4b,c were detected as pure complexes in the
reaction mixture by 31P{1H} NMR spectroscopy, they were
isolated as a mixture with small amounts (5−15%) of allenyl
complexes (see below) due to isomerization processes during
the reaction workup.
other ruthenium(II) allenylidene complexes, i.e., [Ru(η5-
18
C5H5)(CCCPh2)(PMe3)2]+
CCC-(C13H20)}(PPh3)2]+.19
and [Ru(η5-C9H7){
1346
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
Complexes 3 and 4a−c have been fully characterized by
spectroscopic methods. In particular, it must be noted that (i)
IR spectra show the ν(CC) absorption in the range 2073−
2078 cm−1. (ii) The 31P{1H} NMR spectra show two doublets
(2JPP = 65.6−66.8 Hz), one low field corresponding to the
phosphite ligand in the range 150.8−151.5 ppm and the other
corresponding to the phosphane ligand in the range 54.7−56.8
ligands, showing two doublets (2JPP = 64.4−64.8 Hz) in the
1
range 51.7−52.6 ppm and 144.0−145.4 ppm, respectively. H
and 13C{1H} NMR spectra indicate the presence of the alkyl
groups of the corresponding thiolate ligands (see Experimental
Section). 13C{1H} NMR spectra also show the signals
corresponding to the carbon atoms of the allenyl chain at
96.7 (5a), 94.8 (5b), and 90.8 ppm (5c) for Cα, 198.1 (5a),
197.6 (5b), and 197.2 ppm (5c) for Cβ, and 103.7 (5a), 102.4
(5b), and 100.7 ppm (5c) for Cγ.
1
ppm. (iii) The H NMR spectra show singlet signals at 3.58
ppm (OMe) and 2.22 ppm (SMe) for complexes 3 and 4a,
i
t
respectively. The hydrogen atoms for the Pr and Bu groups
appear at 1.25, 1.39, and 3.71 ppm (4b) and 1.68 ppm (4c),
respectively. (iv) The 13C{1H} NMR spectra exhibit signals
corresponding to the Cα and the Cβ at 104.2 and 110.8 ppm
(3), 101.2 and 109.4 ppm (4a), and 99.5 and 110.7 ppm (4b),
respectively. The 13C{1H} NMR spectra for complex 4c could
not be registered since this complex evolves readily, even at low
temperature, to the corresponding allenyl complex (see below).
Synthesis of the Allenyl Complexes [Ru(η5-C9H7){C-
(SR)CCPh2}{P(OEt)3}(PPh3)] (R = Me (5a), iPr (5b), tBu
(5c)). When the reaction of complex 1 with sodium
alkylsulfides is carried out at room temperature, the
thermodynamically stable allenyl complexes [Ru(η5-C9H7){C-
As shown, the kinetically stable alkynyl products isomerize to
the thermodynamically stable allenyl products depending on
the electronic and steric properties of the nucleophile, and the
migration from Cγ to Cα is easier for the bulkier substituents.
For example, the complete isomerization of complex 4a to 5a
requires stirring a THF solution of 4a for 2 days at room
i
t
temperature, while complexes 5b and 5c, bearing Pr and Bu
groups, were obtained by stirring THF solutions of the
corresponding complexes 4b,c overnight. A possible explan-
ation for this isomerization can be found in the small cone
angle of the phosphite auxiliary ligand. Analogous behavior has
been reported for complexes [Ru(η5-C9H7){C(PMe2Ph)
CCPh2}(dppm)], bearing dpppm as auxiliary ligand.14b
Reaction of [Ru(η5-C9H7)(CCCPh2){P(OEt)3}-
(PPh3)][PF6] (1a) with Neutral P-Donor Nucleophiles:
Synthesis of [Ru(η5-C9H7){CC−C(PMe3)Ph2}{P(OEt)3}-
(PPh3)] (6), [Ru(η5-C9H7){C(PMe3)CCPh2}{P(OEt)3}-
(PPh3)] (7), and [Ru(η5-C9H7){C{P(OEt)3}CCPh2}{P-
(OEt)3}(PPh3)] (8). In the same way, allenylidene complex 1
reacts with neutral P-donor nucleophiles, giving rise to γ-
phosphonio alkynyl or α-phosphonio allenyl complexes
depending on the nucleophile and the reaction conditions.
Thus, the reaction of complex 1 with PMe3 at room
temperature allows the synthesis of complex [Ru(η5-
C9H7){CC−C(PMe3)Ph2}{P(OEt)3}(PPh3)] (6) as a yel-
low solid. When complex 6 is heated in THF, irreversible
isomerization to thermodynamically stable α-phosphonio
allenyl 7 occurs. Complex 7 can also be obtained directly
from complex 1. Thus, when the reaction of 1 with PMe3 is
carried out in refluxing THF, the regioisomer α-phosphonio
allenyl complex [Ru(η5-C9H7){C(PMe3)CCPh2}{P-
(OEt)3}(PPh3)] (7) is directly obtained (Scheme 4).
i
(SR)CCPh2}{P(OEt)3}(PPh3)] (R = Me (5a), Pr (5b),
tBu (5c)) are isolated. These complexes can also be obtained by
stirring THF solutions of the alkynyl complexes 4a−c overnight
at room temperature, as the result of formal 1,3-migration of
alkylsulfide from the Cγ to the Cα of the allenylidene chain
(Scheme 3). Analogous migration of the methoxide group in
complex 3 does not occur even at refluxing temperature.
Scheme 3. Synthesis of Complexes 5a−c
Complexes 5a−c are isolated as orange, stable solids, and
they have been fully characterized by spectroscopic methods.20
The IR spectra show the ν(CCC) absorption at 1958
(5a), 1957 (5b), and 1956 (5c) cm−1. 31P{1H} NMR spectra
are indicative of the presence of both phosphane and phosphite
Complex 1 reacts with the stronger π-acceptor P(OEt)3 in
refluxing THF, to give complex [Ru(η5-C9H7){C{P(OEt)3}
CCPh2}{P(OEt)3}(PPh3)] (8) (Scheme 4). However, the
Scheme 4. Synthesis of Complexes 6−8
1347
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
Scheme 5. Synthesis of Complexes 9a,b
reaction did not take place at room temperature, and complex 1
was recovered unaltered.
the phosphonium group. (iii) 13C{1H} NMR spectra show the
signals corresponding to the allenyl chain at 78.6 (Cα), 208.7
(Cβ), and 100.5 ppm (Cγ) for complex 9a and at δ 81.2 (Cα),
214.8 (Cβ), and 103.5 ppm (Cγ) for complex 9b. (iv) Other
Complexes 6, 7, and 8 have been fully characterized
analytically and spectroscopically. The most significant
spectroscopic features for these complexes are as follows. (i)
The IR spectrum of the alkynyl complex 6 shows the
absorption for the ν(CC) bond at 2072 cm−1, and IR
spectra of complexes 7 and 8 show the ν(CCC)
absorption at 1859 (7) and 1864 (8) cm−1 along with the
expected absorption for the PF6 group at 840 cm−1. (ii)
31P{1H} NMR spectra are indicative of the presence of three
phosphorus in the molecule. Phosphorus−phosphorus coupling
constants in these complexes agree with the proposed structure.
Thus, for complex 6 the 31P{1H} NMR spectrum exhibits a
singlet at 30.6 ppm for the phosphorus atom of the PMe3
ligand and two doublets (2JPP = 64.8 Hz) at 54.4 and 148.3 ppm
for the PPh3 and P(OEt)3 ligands, respectively. For complex 7,
the phosphite bonded to the metal appears, in the 31P{1H}
NMR spectrum, as a doublet of doublets at 141.0 ppm coupled
1
signals in the H and 13C{1H} NMR spectra agree with the
proposed structures.
The structure of complex 9a was determined by single-crystal
X-ray diffraction analysis. Suitable crystals were obtained by
slow diffusion of hexane into a solution of complex 9a in
CHCl3. An ORTEP representation is shown in Figure 2, and
selected bonding data are collected in the caption.
The molecule exhibits a pseudooctahedral three-legged piano
stool geometry with the η5-indenyl ligand displaying the usual
allylene coordination mode. The angles between the five-
membered-ring centroid C* and the legs show values typical of
a pseudooctahedron (see the caption to Figure 2). The Ru−
C(17) and Ru−C(18) bond distances reflect the coordination
with both the PPh3 (2JPP = 71.3 Hz) ligand and PMe3 (3JPP
=
21.1 Hz). However, the signals for the phosphane ligand (59.2
ppm) and the phosphonium group (30.5 ppm) appear as
doublets, and no coupling between these phosphorus atoms is
observed. For complex 8, due to the larger coupling constants
observed for phosphite ligands,21 the signals for the three
phosphorus appear as doublet of doublets with coupling
2
3
constants JPP = 72.9 Hz and JPP = 9.7 and 7.3 Hz (see
Experimental Section). (iii) The 13C{1H} NMR spectrum for
complex 6 shows the signal corresponding to the Cα of the
alkynyl group as a multiplet at 98.7 ppm, while Cβ is masked by
the indenyl signals. 13C{1H} NMR spectra for complexes 7 and
8 show the allenyl chain at 75.7 and 74.2 ppm (Cα), 209.1 and
215.9 ppm (Cβ), and 96.6 and 98.9 ppm (Cγ) for complexes 7
1
and 8, respectively. (iv) Other signals in the H and 13C{1H}
NMR spectra agree with the proposed structure.
Synthesis of [Ru(η5-C9H7){κ3(C,C,C)-C(R2PCH2CH
i
CH2)CCPh2}{P(OEt)3}][PF6] (R = Pr (9a), R = Ph
Figure 2. Molecular structure and atom-labeling scheme for the cation
of complex [Ru(η5-C9H7){κ3-(C,C,C)-C(iPr2PCH2CHCH2)C
CPh2}{P(OEt)3}][PF6] (9a). Hydrogen atoms except those of the
coordinated olefin have been omitted for clarity. Non-hydrogen atoms
are represented by their 20% probability ellipsoids. Selected bond
lengths (Å): Ru(1)−C(1) = 2.137(4), Ru(1)−P(2) = 2.207(1),
Ru(1)−C(17) = 2.205(3), Ru(1)−C(18) = 2.214(4), Ru(1)−C* =
1.923(1), C(17)−C(18) = 1.402(5), C(1)−P(1) = 1.779(3), C(1)−
C(2) = 1.296(5), C(2)−C(3) = 1.327(5). Selected bond angles (deg):
C*−Ru(1)−C(1) = 121.74(9), C*−Ru(1)−P(2) = 124.34(3), C*−
Ru(1)−C(17) = 124.14(10), C*−Ru(1)−C(18) = 120.16(11),
Ru(1)−C(1)−C(2) = 125.50(30), C(1)−C(2)−C(3) = 174.50(40),
Ru(1)−C(1)−P(1) = 112.42(17), C(1)−P(1)−C(16) = 100.69(17),
C(16)−C(17)−C(18) = 121.80(40), P(2)−Ru(1)−C(1) = 84.31(9),
C(1)−Ru(1)−C(17) = 83.55(13), C(18)−Ru(1)−P(2) = 84.23(11).
C* = centroid of C(31), C(32), C(33), C(34), C(39). C** = centroid
of C(34), C(35), C(36), C(37), C(38), C(39).
(9b)). Complex 1 does not react with alkenylphosphanes
i
R2PCH2CHCH2 (R = Pr, Ph) at room temperature.
However, the reaction of 1 with these alkenylphosphanes in a
sealed tube at 110−120 °C leads to complexes [Ru(η5-
C9H7){κ3(C,C,C)-C(R2PCH2CHCH2)CCPh2}{P-
i
(OEt)3}][PF6] (R = Pr (9a), R = Ph (9b)), containing a
κ3(C,C,C)-ligand (Scheme 5).
Complexes 9a,b are air-stable solids, and both have been
analytically and spectroscopically characterized. The most
significant spectroscopy data are the following. (i) IR spectra
show the absorption at 1937 (9a) and 1931 (9b) for the allenyl
group and at 1437 (9a) and 1436 (9b) cm−1 for the
coordinated olefin. (ii) The 31P{1H} NMR spectra exhibit
two doublets (3JPP = 4.9 Hz) at 147.8 (9a) and 146.5 ppm (9b)
for the P(OEt)3 ligand and δ 82.2 (9a) and 60.0 ppm (9b) for
1348
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
of the olefin to the metal center, and the C(17)−C(18) bond
distance, 1.401(5) Å, is similar to that found in complex
[Ru(η5-C9H7){κ3(P,C,C)-Ph2PCH2CHCH2}(PPh3)][PF6]
(1.391(8) Å).22 It is also interesting to note that the benzo ring
of the indenyl ligand is oriented trans to the phosphite ligand,
as shown by the dihedral angle between the planes Ru−C*−
C** and C*−Ru−P(2)23 of 18.48(2)°. Figure 2 shows the
complex with relative configuration SRu and olefin coordination
through the re enantioface. However, both enantiomers are
present in equal proportion in the crystal, which belongs to the
or allenyl complexes depending on the reaction conditions. The
kinetically stable alkynyl complexes resulting from nucleophilic
addition to the Cγ evolve to the thermodynamically stable
allenyl complexes depending on the size and electronic
properties of the nucleophile.
Complex [Ru(η5-C9H7){κ3(C,C,C)-C(R2PCH2CH
CH2)CCPh2}{P(OEt)3}][PF6], containing an unusual
κ3(C,C,C)-ligand, was obtained by the addition of alkenylphos-
phanes to the allenylidene complex 1. The proposed
mechanism for this transformation starts with substitution of
PPh3 followed by an intramolecular attack of the phosphane to
the Cα of the allenylidene chain.
centrosymmetric space group P1.
̅
Nelson et al. reported the synthesis of the analogous complex
[RuCl(η6-C6Me6){κ3-(C,C,C)-C(Ph2PCHCH2)C
CPh2}][PF6] obtained, in 24% yield, through the reaction of
complex [RuCl(η6-C6Me6)(NCMe)(Ph2PCHCH2)][PF6]
with 1,1-diphenyl-2-propyn-1-ol (Figure 3). In this reaction,
migration of the coordinated vinyl phosphane to the previously
formed allenylidene takes place.24
EXPERIMENTAL SECTION
■
General Procedures. All manipulations were perfomed under an
atmosphere of dry nitrogen using vacuum-line and standard Schlenk
techniques. The reagents were obtained from commercial suppliers
and used without further purification. Solvents were dried by standard
methods and distilled under nitrogen before use. The phosphane
25
Ph2PCH2CHCH2 was prepared by a previously reported
i
procedure. Pr2PCH2CHCH2 was synthesized following the same
experimental procedure.
Infrared spectra were recorded on a PerkinElmer 1720-XFT
spectrometer. The C, H, and N analyses were carried out with a
PerkinElmer 240-B and a LECO CHNS-TruSpec microanalyzer. Mass
spectra (ESI) were determined with a Bruker Esquire 6000
spectrometer, operating in positive mode and using dichloromethane
and methanol solutions. NMR spectra were recorded on Bruker
spectrometers AV400 operating at 400.13 (1H), 100.61 (13C), and
161.95 (31P) MHz, AV300 operating at 300.13 (1H), 75.45 (13C), and
121.49 (31P) MHz, and AV600 operating at 600.15 (1H) MHz and
150.91 (13C) MHz. DEPT and 2D COSY HH, HSQC, and HMBC
experiments were carried out for all the compounds. Chemical shifts
are reported in parts per million and referenced to TMS or 85%
H3PO4 as standards. Coupling constants J are given in hertz.
Abbreviations used: s, singlet; d, doublet; dd, double doublet; t,
triplet; sept, septuplet; m, multiplet. For complexes 5a−c, analytically
Figure 3. Synthesis of complex [RuCl(η6-C6H6)(NCMe)(Ph2PCH
CH2)][PF6].
According to this reaction and taking into account the high
temperatures needed for the synthesis of complexes 9a,b, a
mechanism can be proposed for the formation of complexes
9a,b. Thus, the first step for the transformation from 1 into 9a,b
would be the PPh3 substitution for the alkenylphosphane,
followed by an intramolecular attack of the phosphane to the
Cα of the allenylidene chain (Scheme 6). The phosphane
substitution step would explain the high temperatures needed
for this reaction, in contrast with the low temperature observed
for the nucleophilic addition of PMe3 to the allenylidene chain
observed in the synthesis of complex 6.
1
pure samples could not be obtained. H, 31P{1H}, and 13C{1H} NMR
spectra of these complexes are provided as Supporting Information.
Synthesis of Complexes [Ru(η5-C9H7)(CCCPh2){P(OR)3}-
(PPh3)][PF6] (R = Et (1); R = Me (2)). To a solution of the complex
[Ru(η5-C9H7)Cl(PPh3){P(OR)3}] (0.3 mmol; R = Et, 204 mg; R =
Me, 191 mg) and NaPF6 (1.5 mmol, 252 mg) in MeOH (10 mL) was
added 1,1-diphenyl-2-propyn-1-ol (1.5 mmol, 312 mg). The initial
orange solution was stirred at reflux temperature for 30 min, after
which it turned to deep purple. Solvent was eliminated to dryness. The
residue was extracted with CH2Cl2 and filtered through kieselghur.
Solvents were evaporated, and the addition of hexane (30 mL)
afforded a deep purple solid, which was washed with hexane (2 × 15
SUMMARY
■
In summary, the nucleophilic attacks to the allenylidene
complex [Ru(η5-C9H7){CCC(Ph)2}{P(OEt)3}-
(PPh3)][PF6] (1) allow synthesizing the regioisomers’ alkynyl
Scheme 6. Proposed Mechanism for the Synthesis of Complexes 9a,b
1349
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
mL) and vacuum-dried. R = Et (1): yield 85%. 31P{1H} NMR (162.0
MHz, CD2Cl2, 20 °C): δ 135.9 (d, 2JPP = 50.2 Hz, P(OEt)3), 51.0 (d,
corresponding thiolate was formed. Then, it was cooled at −40 °C,
and the complex [Ru(η5-C9H7)(CCCPh2){P(OEt)3}(PPh3)]-
[PF6] (1) (0.06 mmol, 58 mg) was added. The mixture was stirred at
this temperature for 40 min, until it turned orange. Once the reaction
was completed, the solution was evaporated to dryness. The residue
was extracted with hexane and filtered. The resulting solution was
1
1
2JPP = 50.2 Hz, PPh3), −144.4 (sept, JPF = 711.2 Hz, PF6). H NMR
3
(400.1 MHz, CD2Cl2, 20 °C): δ 1.19 (t, JHH = 7.2 Hz, 9H,
P(OCH2CH3)3), 3.50 (m, 6H, P(OCH2CH3)3), 5.38, 5.47, 5.79 (3s, 3
× 1H, C9H7), 7.09−7.65 (m, 29H, PPh3, Ph2, C9H7). 13C{1H} NMR
i
3
evaporated to dryness, affording an orange solid. R = Pr (4b): yield
(100.6 MHz, CD2Cl2, 20 °C): δ 15.7 (d, JCP = 7.3 Hz,
2
71%. 31P{1H} NMR (121.5 MHz, C6D6, 20 °C): δ 151.0 (d, JPP
=
2
P(OCH2CH3)3), 63.2 (d, JCP = 8.9 Hz, P(OCH2CH3)3), 80.1, 84.2,
2
1
66.8 Hz, P(OEt)3), 55.6 (d, JPP = 66.8 Hz, PPh3). H NMR (400.1
95.9, 111.5, 112.7 (5s, C9H7), 123.7−144.7 (PPh3, Ph2, C9H7), 156.2
(s, Cγ), 204.1 (s, Cβ), 295.0 (dd, 2JCP = 15.8 Hz, 2JCP = 26.4 Hz, Ru
Cα). Conductivity (acetone, 20 °C): Λ = 130 S cm2 mol−1. IR (KBr,
cm−1): ν (CCC) 1936 (s), ν (PF6) 838 (s). MS (ESI) m/z: 835
([M]+, 100%). Anal. Calcd for C48H47F6O3P3Ru: C, 58.84; H, 4.83.
Found: C, 59.12; H, 4.76.
3
MHz, C63D6, 20 °C): δ 1.07 (t, JHH = 7.2 Hz, 9H, P(OCH2CH3)3),
3
1.25 (d, JHH = 6.9 Hz, 3H, SCHMe2), 1.39 (d, JHH = 6.9 Hz, 3H,
3
SCHMe2), 3.71 (sept, JHH = 6.9 Hz, 1H, SCHMe2), 3.88 (m, 6H,
P(OCH2CH3)3), 4.43, 5.34, 5.57 (3s, 3 × 1H, C9H7), 6.94−8.09 (m,
29H, PPh3, Ph2, C9H7). 13C{1H} NMR (100.6 MHz, CDCl3, −50 °C):
3
R = Me (2): yield 93%. 31P{1H} NMR (162.0 MHz, CD2Cl2, 20
δ 16.3 (d, JCP = 7.0 Hz, P(OCH2CH3)3), 24.4, 24.5 (2s, SCHMe2),
36.8 (s, SCH), 60.7 (d, 2JCP = 6.3 Hz, P(OCH2CH3)3), 68.3, 71.1, 93.1
(3s, C9H7), 76.0 (s, Cγ), 99.5 (m, Cα), 110.7 (s, Cβ), 107.8, 111.1 (2s,
C9H7), 122.2−147.2 (PPh3, Ph2, C9H7). IR (KBr, cm−1): ν (CC)
2075 (w). MS (ESI) m/z: 835 ([M − SiPr]+, 100%).
2
2
°C): δ 141.3 (d, JPP = 51.8 Hz, P(OMe)3), 51.3 (d, JPP = 51.8 Hz,
1
1
PPh3), −144.4 (sept, JPF = 711.2 Hz, PF6). H NMR (400.1 MHz,
CD2Cl2, 20 °C): δ 3.50 (d, 3JHP = 11.6 Hz, 9H, P(OMe)3), 5.32, 5.54,
5.86 (3s, 3 × 1H, C9H7), 7.08−7.64 (m, 29H, PPh3, Ph2, C9H7).
13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C): δ 53.5 (d, 2JCP = 8.7 Hz,
R = tBu (4c): yield 50%. 31P{1H} NMR (121.5 MHz, C6D6, 20 °C):
2
2
δ 150.8 (d, JPP = 66.8 Hz, P(OEt)3), 54.7 (d, JPP3 = 66.8 Hz, PPh3).
P(OMe)3), 79.4, 84.1, 95.2, 111.6, 111.7 (5s, C9H7), 123.5−144.7
(PPh3, Ph2, C9H7), 157.0 (s, Cγ), 202.6 (s, Cβ), 295.5 (dd, 2JCP = 13.8
Hz, 2JCP = 26.0 Hz, RuCα). Conductivity (acetone, 20 °C): Λ = 115
S cm2 mol−1. IR (KBr, cm−1): ν (CCC) 1939 (s), ν (PF6) 838
(s). MS (ESI) m/z: 793 ([M]+, 100%), 293 ([M − PPh3 − P(OEt)3]+,
28%). Anal. Calcd for C45H41F6O3P3Ru: C, 57.63; H, 4.41. Found: C,
57.48; H, 4.55.
1H NMR (400.1 MHz, C6D6, 20 °C): δ 1.09 (t, JHH = 7.2 Hz, 9H,
P(OCH2CH3)3), 1.68 (s, 9H, SCMe3), 3.92 (m, 6H, P(OCH2CH3)3),
4.43, 5.47, 5.68 (3s, 3 × 1H, C9H7), 6.93−8.24 (m, 29H, PPh3, Ph2,
C9H7). IR (KBr, cm−1): ν (CC) 2073 (w). MS (ESI) m/z: 835 ([M
− StBu]+, 100%).
Synthesis of Complex [Ru(η5-C9H7){C(SMe)CCPh2}{P(OEt)3}-
(PPh3)] (5a). To a solution of the complex [Ru(η5-C9H7)(CC
CPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol, 58 mg) in THF (10
mL) was added NaSMe (0.12 mmol, 8.4 mg). The initial purple
solution turned orange and was stirred at room temperature for 2 days
(monitored by 31P{1H} NMR). Solvent was then removed, and the
residue was extracted with hexane (2 × 15 mL). Solvent was
evaporated to dryness, affording an orange solid: yield 59%. 31P{1H}
Synthesis of Complex [Ru(η5-C9H7){CCC(OMe)Ph2}{P(OEt)3}-
(PPh3)] (3). NaH (0.12 mmol, 3 mg) was dissolved in MeOH, then
evaporated to dryness to isolate the NaOMe formed. It was solved
again in THF (10 mL), and the complex [Ru(η5-C9H7)(CC
CPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol, 58 mg) was added.
The initial purple solution was stirred at room temperature for 20 min,
until it turned yellow. Solvent was removed, and the residue was
extracted with diethyl ether (2 × 15 mL). Solvent was evaporated to
dryness, affording an orange solid: yield 62%. 31P{1H} NMR (121.5
MHz, C6D6, 20 °C): δ 151.5 (d, 2JPP = 65.6 Hz, P(OEt)3), 56.8 (d, 2JPP
= 65.6 Hz, PPh3). 1H NMR (400.1 MHz, C6D6, 20 °C): δ 1.05 (t, 3JHH
= 7.2 Hz, 9H, P(OCH2CH3)3), 3.58 (s, 3H, OMe), 3.84 (m, 6H,
P(OCH2CH3)3), 4.45, 5.23, 5.49 (3s, 3 × 1H, C9H7), 6.93−8.08 (m,
29H, PPh3, Ph2, C9H7). 13C{1H} NMR (100.6 MHz, C6D6, 20 °C): δ
2
NMR (162.0 MHz, C6D6, 20 °C): δ 145.4 (d, JPP = 64.8 Hz,
2
1
P(OEt)3), 52.6 (d, JPP = 64.8 Hz, PPh3). H NMR (400.1 MHz,
3
C6D6, 20 °C): δ 0.94 (t, JHH = 6.8 Hz, 9H, P(OCH2CH3)3), 2.08 (s,
3H, SMe), 3.58 (m, 3H, P(OCH2CH3)3), 3.73 (m, 3H, P-
3
(OCH2CH3)3), 5.44, 5.55, 5.99 (3s, 3 × 1H, C9H7), 6.38 (d, JHH
=
8.4 Hz, 1H, C9H7), 7.08−7.89 (m, 28H, PPh3, Ph2, C9H7). 13C{1H}
3
NMR (100.6 MHz, C6D6, 20 °C): δ 15.6 (d, JCP = 6.5 Hz,
2
16.0 (d, 3JCP = 6.0 Hz, P(OCH2CH3)3), 51.2 (s, OMe), 60.8 (d, 2JCP
=
P(OCH2CH3)3), 21.3 (s, SMe), 60.8 (d, JCP = 9.8 Hz, P-
(OCH2CH3)3), 68.0, 72.9 (2d, JCP = 8.1 Hz, JCP = 8.1 Hz, C9H7),
2
2
6.3 Hz, P(OCH2CH3)3), 68.8 (d, 2JCP = 7.7 Hz, C9H7), 72.4, 93.2 (2s,
C9H7), 82.1 (s, Cγ), 104.2 (m, Cα), 109.0 C9H7), 110.8 (Cβ), 123.0−
148.1 (PPh3, Ph2, C9H7). IR (KBr, cm−1): ν (CC) 2074 (w). Anal.
Calcd for C49H50O4P2Ru: C, 67.96; H, 5.82. Found: C, 67.62; H, 5.66.
Synthesis of Complex [Ru(η5-C9H7){CCC(SMe)Ph2}{P(OEt)3}-
(PPh3)] (4a). To a solution of the complex [Ru(η5-C9H7)(C
CCPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol, 58 mg) in THF
(10 mL) at −40 °C was added NaSMe (0.12 mmol, 8.4 mg). The
initial purple solution was stirred at this temperature for 15 min, until
it turned orange. Solvent was removed, and the residue was extracted
with hexane (2 × 15 mL). Solvent was evaporated to dryness, affording
an orange solid: yield 59%. 31P{1H} NMR (162.0 MHz, C6D6, 20 °C):
2
2
96.7 (dd, JCP = 12.3 Hz, JCP = 18.0 Hz, Cα), 98.8, 106.2, 111.9 (3s,
C9H7), 103.7 (s, Cγ), 122.8−147.1 (PPh3, Ph2, C9H7), 198.1 (d, 3JCP
4.9 Hz, Cβ). IR (KBr, cm−1): ν (CCC) 1958 (w).
=
Synthesis of Complexes [Ru(η5-C9H7){C(SR)CCPh2}{P(OEt)3}-
(PPh3)] (R = iPr (5b); R = tBu (5c)). By stirring NaOH (0.12 mmol, 4.8
mg) and the thiol (0.12 mmol) in THF (10 mL) for 30 min, the
corresponding thiolate was formed. Then, the complex [Ru(η5-
C9H7)(CCCPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol, 58
mg) was added. The mixture was stirred at room temperature
overnight. Once the reaction was completed (monitored by 31P{1H}
NMR), the solution was evaporated to dryness and the residue was
extracted with hexane and filtered. The resulting solution was
2
2
δ 151.3 (d, JPP = 66.5 Hz, P(OEt)3), 56.4 (d, JPP3 = 66.5 Hz, PPh3).
1H NMR (400.1 MHz, C6D6, 20 °C): δ 1.05 (t, JHH = 7.2 Hz, 9H,
P(OCH2CH3)3), 2.22 (s, 3H, SMe), 3.86 (m, 6H, P(OCH2CH3)3),
4.42, 5.29, 5.50 (3s, 3 × 1H, C9H7), 6.90−8.18 (m, 29H, PPh3, Ph2,
C9H7). 13C{1H} NMR (100.6 MHz, C6D6, 0 °C): δ 14.7 (s, SMe),
i
evaporated to dryness, affording an orange solid. R = Pr (5b): yield
71%. 31P{1H} NMR (121.5 MHz, C6D6, 20 °C): δ 144.8 (d, JPP
=
2
2
1
64.4 Hz, P(OEt)3), 52.5 (d, JPP = 64.4 Hz, PPh3). H NMR (400.1
MHz, C6D6, 20 °C): δ 0.84 (d, 3JHH = 6.8 Hz, 3H, SCHMe2), 0.93 (t,
3JHH = 6.8 Hz, 9H, P(OCH2CH3)3), 1.36 (d, JHH = 6.8 Hz, 3H,
3
3
2
16.0 (d, JCP = 6.7 Hz, P(OCH2CH3)3), 60.8 (d, JCP = 6.7 Hz,
3
P(OCH2CH3)3), 68.7 (d, 2JCP = 7.6 Hz, C9H7), 72.1, 93.1 (2s, C9H7),
75.2 (s, Cγ), 101.2 (dd, JCP = 29.4 Hz, JCP = 20.9 Hz, Cα), 109.4 (s,
SCHMe2), 3.18 (sept, JHH = 6.8 Hz, 1H, SCHMe2), 3.56 (m, 3H,
2
2
P(OCH2CH3)3), 3.72 (m, 3H, P(OCH2CH3)3), 5.44, 5.68, 6.07 (3s, 3
× 1H, C9H7), 6.27 (d, 3JHH = 8.4 Hz, 1H, C9H7), 7.10−7.95 (m, 28H,
PPh3, Ph2, C9H7). 13C{1H} NMR (100.6 MHz, C6D6, 20 °C): δ 15.6
2
2
Cβ), 111.0, 111.2 (2d, JCP = 5.7 Hz, JCP = 4.7 Hz, C9H7), 122.8−
147.1 (PPh3, Ph2, C9H7). IR (KBr, cm−1): ν (CC) 2078 (w). MS
(ESI) m/z: 835 ([M − SMe]+, 100%). Anal. Calcd for
C49H50O3P2RuS: C, 66.73; H, 5.71; S, 3.64. Found: C, 66.56; H,
5.72; S, 3.36.
3
(d, JCP = 8.7 Hz, P(OCH2CH3)3), 23.1, 23.7 (2s, SCHMe2), 41.3 (s,
SCHMe2), 60.8 (d, 2JCP = 8.9 Hz, P(OCH2CH3)3), 67.6, 73.5 (2d, 2JCP
= 8.8 Hz, 2JCP = 15.4 Hz, C9H7), 94.8 (dd, 2JCP = 16.6 Hz, 2JCP = 12.8
Hz, Cα), 102.4 (s, Cγ), 99.3, 105.9, 111.8 (3s, C9H7), 122.6−145.3
Synthesis of Complexes [Ru(η5-C9H7){CCC(SR)Ph2}{P(OEt)3}-
i
t
3
(PPh3)] (R = Pr (4b); R = Bu (4c)). By stirring NaOH (0.12 mmol,
(PPh3, Ph2, C9H7), 197.6 (d, JCP = 5.4 Hz, Cβ). IR (KBr, cm−1): ν
4.8 mg) and the thiol (0.12 mmol) in THF (10 mL) for 30 min, the
(CCC) 1957 (w).
1350
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
R = tBu (5c): yield 50%. 31P{1H} NMR (162.1 MHz, C6D6, 20 °C):
20 °C): δ 0.91 (t, 3JHH = 7.2 Hz, 9H, P(OCH2CH3)3), 1.30 (t, 3JHH
=
2
2
δ 144.0 (d, JPP = 64.8 Hz, P(OEt)3), 51.7 (d, JPP3 = 64.8 Hz, PPh3).
1H NMR (400.1 MHz, C6D6, 20 °C): δ 0.91 (t, JHH = 7.2 Hz, 9H,
P(OCH2CH3)3), 1.28 (s, 9H, SCMe3), 3.52 (m, 3H, P(OCH2CH3)3),
3.63 (m, 3H, P(OCH2CH3)3), 5.43, 5.80, 6.03 (3s, 3 × 1H, C9H7),
7.2 Hz, 9H, P(OCH2CH3)3), 3.57 (m, 6H, P(OCH2CH3)3), 3.92 (m,
3H, P(OCH2CH3)3), 4.16 (m, 3H, P(OCH2CH3)3), 4.84, 4.97, 5.04
(3s, 3 × 1H, C9H7), 6.63−7.52 (m, 29H, PPh3, Ph2, C9H7). 13C{1H}
3
NMR (100.6 MHz, CD2Cl2, 20 °C): δ 15.3 (d, JCP = 7.1 Hz,
P(OCH2CH3)3), 15.6 (d, 3JCP = 7.1 Hz, P(OCH2CH3)3), 61.8 (d, 2JCP
3
6.35 (d, JHH = 8.4 Hz, 1H, C9H7), 6.97−8.02 (m, 28H, PPh3, Ph2,
2
3
C9H7). 13C{1H} NMR (100.6 MHz, C6D6, 20 °C): δ 15.6 (d, JCP
=
= 10.0 Hz, P(OCH2CH3)3), 67.5 (d, JCP = 9.2 Hz, P(OCH2CH3)3),
2
67.3, 94.0 (2s, C9H7), 69.7 (d, JCP = 13.0 Hz, C9H7), 74.2 (m, Cα),
6.5 Hz, P(OCH2CH3)3), 30.1 (s, SCMe3), 49.0 (s, SCMe3), 60.7 (d,
3
2
2
2JCP = 9.3 Hz, P(OCH2CH3)3), 67.5, 74.0 (2d, JCP = 7.2 Hz, JCP
=
98.9 (d, JCP = 27.3 Hz, Cγ), 107.9, 111.9 (2s, C9H7), 123.8−136.3
2
2
(PPh3, Ph2, C9H7), 215.9 (br s, Cβ). Conductivity (acetone, 20 °C): Λ
= 116 S cm2 mol−1. IR (KBr, cm−1): ν (CCC) 1864 (m), ν (PF6)
840 (s). Anal. Calcd for C54H62F6O6P4Ru: C, 56.59; H, 5.45. Found:
C, 56.32; H, 5.41.
15.6 Hz, C9H7), 90.8 (dd, JCP = 15.6 Hz, JCP = 11.3 Hz, Cα), 100.7
(s, Cγ), 100.6, 106.1, 112.0 (3s, C9H7), 122.8−142.3 (PPh3, Ph2,
C9H7), 197.2 (d, JCP = 5.3 Hz, Cβ). IR (KBr, cm−1): ν (CCC)
3
1956 (w).
Synthesis of [Ru(η5-C9H7){κ3(C,C,C)-C(R2PCH2CHCH2)C
Synthesis of Complex [Ru(η5-C9H7){CCC(PMe3)Ph2}{P(OEt)3}-
(PPh3)][PF6] (6). To a solution of the complex [Ru(η5-C9H7)(C
CCPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol, 58 mg) in THF
(10 mL) was added PMe3 (0.12 mmol, 10.3 μL), and the initial purple
solution turned yellow. Solvent was partially evaporated and hexane
(20 mL) was added, affording a yellow precipitate. Solvents were
decanted, and the solid was washed with hexane (2 × 15 mL) and
vacuum-dried: yield 50%. 31P{1H} NMR (162.0 MHz, CD2Cl2, 20
i
CPh2}{P(OEt)3}][PF6] (R = Pr (9a), R = Ph (9b)). To a solution of
the complex [Ru(η5-C9H7)(CCCPh2){P(OEt)3}(PPh3)][PF6]
(1) (0.1 mmol, 98 mg) in THF (10 mL) was added
allyldiisopropylphosphane (0.3 mmol, 45 μL) or allyldiphenylphos-
phane (0.3 mmol, 65 μL). The solution was stirred in a sealed tube at
110 °C overnight (9a) or at 120 °C for 24 h (9b). The yellow solution
was then dropped into stirring hexane (80 mL), affording a brown
precipitate. Solvents were decanted, and the solid was washed with
2
2
°C): δ 148.3 (d, JPP = 64.8 Hz, P(OEt)3), 54.4 (d, JPP = 64.8 Hz,
i
PPh3), 30.6 (s, PMe3), −144.3 (sept, JPF = 711.2 Hz, PF6). 1H NMR
1
hexane (2 × 15 mL) and vacuum-dried. R = Pr (9a): yield 51%.
31P{1H} NMR (121.5 MHz, CD2Cl2, 20 °C): δ 147.8 (d, 3JPP = 4.9 Hz,
3
(400.1 MHz, CD2Cl2, 20 °C): δ 1.07 (t, JHH = 6.8 Hz, 9H,
3
1
2
P(OEt)3), 82.2 (d, JPP = 4.9 Hz, ADIP), −144.2 (sept, JPF = 712.0
P(OCH2CH3)3), 1.83 (d, JHP = 12.8 Hz, 9H, PMe3), 3.78 (m, 6H,
1
Hz, PF6). H NMR (400.1 MHz, CD2Cl2, 20 °C): δ 1.12−1.50 (m,
14H, Me2CHP, CHP, PCH2), 1.22 (t, JHH = 7.2 Hz, 9H,
P(OCH2CH3)3), 4.28, 5.31, 5.39 (3s, 3 × 1H, C9H7), 6.67−7.50 (m,
3
29H, PPh3, Ph2, C9H7). 13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C):
1
3
P(OCH2CH3)3), 2.40 (m, 2H, CH, CH2), 2.49 (m, 1H, CHP),
δ 8.2 (d, JCP = 56.3 Hz, PMe3), 16.0 (d, JCP = 4.5 Hz,
1
2
2.63 (m, 1H, PCH2), 3.47 (m, 1H, CH2), 4.04 (m, 6H,
P(OCH2CH3)3), 52.3 (d, JCP = 50.2 Hz, Cγ), 61.0 (d, JCP = 7.1
Hz, P(OCH2CH3)3), 66.4, 72.1, 93.3 (3s, C9H7), 98.7 (m, Cα), 110.7,
111.0, 114.5 (3s, Cβ, C9H7), 122.7−138.1 (PPh3, Ph2, C9H7).
Conductivity (acetone, 20 °C): Λ = 138 S cm2 mol−1. IR (KBr,
cm−1): ν (CC) 2072 (w), ν (PF6) 840 (s). Anal. Calcd for
C51H56F6O3P4Ru: C, 58.01; H, 5.35. Found: C, 57.90; H, 5.41.
Synthesis of Complex [Ru(η5-C9H7){C(PMe3)CCPh2}{P(OEt)3}-
(PPh3)][PF6] (7).26 To a solution of the complex [Ru(η5-C9H7)(C
CCPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol, 58 mg) in THF
(10 mL) was added PMe3 (0.12 mmol, 10.3 μL). After the initial
formation of complex 6, the solution was stirred at reflux temperature
for 5 h. Then, solvent was partially evaporated and hexane (20 mL)
was added, affording a yellow precipitate. The solid was washed with
hexane (2 × 15 mL) and vacuum-dried. Analytically pure samples were
obtained by recrystallization of CH2Cl2/hexane: yield 47%. 31P{1H}
3
P(OCH2CH3)3), 5.15, 5.53, 5.72 (3s, 3 × 1H, C9H7), 6.72 (d, JHH
= 8.4 Hz, 1H, C9H7), 7.04−7.65 (m, 13H, Ph2, C9H7). 13C{1H} NMR
(100.6 MHz, CD2Cl2, 20 °C): δ 15.3−17.9 (m, Me2CHP,
1
1
P(OCH2CH3)3), 21.2 (d, JCP = 42.0 Hz, CHP), 24.7 (d, JCP
=
1
3
60.0 Hz, PCH2), 25.6 (d, JCP = 27.1 Hz, CHP), 41.6 (dd, JCP = 5.2
2
2
Hz, JCP = 5.9 Hz, CH2), 56.9 (s, CH), 62.4 (d, JCP = 7.5 Hz,
1
2
P(OCH2CH3)3), 78.6 (dd, JCP = 31.6 Hz, JCP = 22.1 Hz, Cα), 73.8,
75.2, 90.2 (3s, C9H7), 100.5 (d, 2JCP = 18.9 Hz, Cβ), 108.0, 109.6 (2d,
2JCP = 7.0 Hz, JCP = 6.2 Hz, C9H7), 122.0−136.7 (Ph2, C9H7), 208.7
2
(s, Cγ). Conductivity (acetone, 20 °C): Λ = 130 S cm2 mol−1. IR (KBr,
cm−1): ν (CCC) 1937 (m), ν (CC) 1437 (w), ν (PF6) 839
(s). MS (ESI) m/z: 731 ([M]+, 100%). Anal. Calcd for
C39H51F6O3P3Ru: C, 53.48; H, 5.87. Found: C, 53.04; H, 5.63. R =
Ph (9b): yield 55%. 31P{1H} NMR (121.5 MHz, CD2Cl2, 20 °C): δ
3
3
2
NMR (162.0 MHz, CD2Cl2, 20 °C): δ 141.0 (dd, JPP = 71.3 Hz, 3JPP
146.5 (d, JPP = 4.9 Hz, P(OEt)3), 60.0 (d, JPP = 4.9 Hz, ADIP),
−144.5 (sept, JPF = 710.8 Hz, PF6). H NMR (400.1 MHz, CD2Cl2,
20 °C): δ 1.18 (t, JHH = 7.2 Hz, 9H, P(OCH2CH3)3), 2.02 (m, 1H,
1
1
2
3
= 21.1 Hz, P(OEt)3), 59.2 (d, JPP = 71.3 Hz, PPh3), 30.5 (d, JPP
=
3
21.1 Hz, PMe3), −144.3 (sept, 1JPF = 711.3 Hz, PF6). 1H NMR (400.1
MHz, CD2Cl2, 20 °C): δ 1.15 (t, 3JHH = 7.2 Hz, 9H, P(OCH2CH3)3),
1.65 (d, JHP = 12.8 Hz, 9H, PMe3), 3.57 (m, 3H, P(OCH2CH3)3),
CH), 2.30 (m, 1H, PCH2), 2.63 (m, 1H, CH2), 2.75 (m, 1H, 
CH2), 3.41 (m, 1H, PCH2), 3.98 (m, 6H, P(OCH2CH3)3), 5.38, 5.53,
5.69 (3s, 3 × 1H, C9H7), 6.48−7.72 (m, 24H, PPh2, Ph2, C9H7).
13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C): δ 15.9 (d, 3JCP = 5.7 Hz,
2
3.83 (m, 3H, P(OCH2CH3)3), 4.75, 4.97, 5.02 (3s, 3 × 1H, C9H7),
6.34−7.63 (m, 29H, PPh3, Ph2, C9H7). 13C{1H} NMR (100.6 MHz,
CD2Cl2, 20 °C): δ 13.2 (d, 1JCP2 = 54.9 Hz, PMe3), 15.4 (d, 3JCP = 5.7
Hz, P(OCH2CH3)3), 62.5 (d, JCP = 10.9 Hz, P(OCH2CH3)3), 71.0
(d, 2JCP = 16.5 Hz, C9H7), 75.7 (m, Cα), 96.6 (d, 3JCP = 23.5 Hz, Cγ),
65.1, 94.3, 107.3, 114.9 (4s, C9H7), 123.6−136.6 (PPh3, Ph2, C9H7),
209.1 (s, Cβ). Conductivity (acetone, 20 °C): Λ = 112 S cm2 mol−1. IR
(KBr, cm−1): ν (CCC) 1859 (m), ν (PF6) 840 (s). Anal. Calcd
for C51H56F6O3P4Ru: C, 58.01; H, 5.35. Found: C, 57.84; H, 5.29.
Synthesis of Complex [Ru(η5-C9H7){C(P(OEt)3)CCPh2}{P-
(OEt)3}(PPh3)][PF6] (8). To a solution of the complex [Ru(η5-
C9H7)(CCCPh2){P(OEt)3}(PPh3)][PF6] (1) (0.06 mmol,
58 mg) in THF (10 mL) was added P(OEt)3 (0.06 mmol, 10 μL).
The initial purple solution was stirred at reflux temperature for 45 min
and turned brown. Then, solvent was partially evaporated and hexane
(20 mL) was added, affording a brown precipitate. The solid was
washed with hexane (2 × 15 mL) and vacuum-dried. Analytically pure
samples were obtained by recrystallization of CH2Cl2/hexane: yield
3
P(OCH2CH3)3), 29.8 (d, 1JCP = 72.3 Hz, PCH2), 46.2 (dd, JCP = 5.0
2
2
Hz, JCP = 8.0 Hz, CH2), 58.6 (s, CH), 62.2 (d, JCP = 6.9 Hz,
1
2
P(OCH2CH3)3), 81.2 (dd, JCP = 27.6 Hz, JCP = 20.7 Hz, Cα), 73.8,
78.1, 89.7 (3s, C9H7), 103.5 (d, 2JCP = 22.3 Hz, Cβ), 105.9, 107.2 (2d,
2JCP = 8.6 Hz, JCP = 6.9 Hz, C9H7), 120.5−136.9 (PPh2, Ph2, C9H7),
2
214.8 (d, 3JCP = 3.8 Hz, Cγ). Conductivity (acetone, 20 °C): Λ = 116 S
cm2 mol−1. IR (KBr, cm−1): ν (CCC) 1931 (m), ν (CC) 1436
(w), ν (PF6) 839 (s). Anal. Calcd for C45H47F6O3P3Ru: C, 57.26; H,
5.02. Found: C, 57.03; H, 5.21.
X-ray Crystal Structure Determination of Complexes 2·
2CH2Cl2 and 9a·CHCl3. Crystals suitable for X-ray diffraction analysis
were obtained from dichloromethane/hexane and chloroform/hexane
solvent systems for 2 and 9a, respectively. The most relevant crystal
and refinement data are collected in the Supporting Information
(Table S1).
In both cases, diffraction data were recorded on an Oxford
Diffraction Xcalibur Nova (Agilent) single-crystal diffractometer, using
Cu Kα radiation (λ= 1.5418 Å). Images were collected at a 63 mm
fixed crystal−detector distance, using the oscillation method, with 1°
oscillation and variable exposure time per image (4−20 and 5−30 s,
68%. 31P{1H} NMR (121.5 MHz, CD2Cl2, 20 °C): δ 138.5 (dd, 2JPP
=
=
3
2
3
72.9 Hz, JPP = 9.7 Hz, Ru-P(OEt)3), 57.9 (dd, JPP = 72.9 Hz, JPP
3
3
7.3 Hz, PPh3), 36.4 (dd, JPP = 9.7 Hz, JPP = 7.3 Hz, C-P(OEt)3),
1
1
−144.4 (sept, JPF = 710.8 Hz, PF6). H NMR (400.1 MHz, CD2Cl2,
1351
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
respectively). Data collection strategy was calculated with the program
CrysAlis Pro CCD.27 Data reduction and cell refinement were
performed with the program CrysAlis Pro RED.27 An empirical
absorption correction was applied using the SCALE3 ABSPACK
algorithm as implemented in the program CrysAlis Pro RED.27
The software package WINGX28 was used for space group
determination, structure solution, and refinement. The structure of
complex 2 was solved by direct methods using SIR200429 and 9a by
Patterson interpretation and phase expansion using DIRDIF.30 In the
crystal of 2 two CH2Cl2 solvent molecules per unit formula of the
complex are present, and for 9a a CHCl3 solvent molecule per unit
formula of the complex was present. Isotropic least-squares refinement
on F2 using SHELXL9731 was performed. During the final stages of
the refinements, all the positional parameters and the anisotropic
temperature factors of all the non-H atoms were refined, the H atoms
were geometrically located, and their coordinates were refined riding
on their parent atoms. The maximum residual electron density is
located near heavy atoms.
A.; Sournia−Saquet, A.; Lugan, N.; Lavigne, G. J. Organomet. Chem.
2007, 692, 3207−3211. (i) Bruneau, C.; Dixneuf, P. H. Angew. Chem.,
Int. Ed. 2006, 45, 2176−2203.
́
(3) See for example: (a) Alos, J.; Bolano, T.; Esteruelas, M. A.;
̃
Olivan
́
, M.; Onate, E.; Valencia, M. Inorg. Chem. 2014, 53, 1195−1209.
̃
(b) Smith, E. J.; Johnson, D. G.; Thatcher, R. J.; Whitwood, A. C.;
Lynam, J. M. Organometallics 2013, 32, 7407−7417. (c) Strinitz, F.;
Waterloo, A.; Tucher, J.; Hubner, E.; Tykwinski, R. R.; Burzlaff, N.
̈
Eur. J. Inorg. Chem. 2013, 5181−5186. (d) Bruce, M. I.; Burgun, A.;
Fox, M. A.; Jevric, M.; Low, P. J.; Nicholson, B. K.; Parker, C. R.;
Skelton, B. W.; White, A. H.; Zaitseva, N. N. Organometallics 2013, 32,
3286−3299. (e) Chang, L.-H.; Yeh, C.-W.; Ma, H.-W.; Liu, S.-Y.; Lin,
Y.-C.; Wang, Y.; Liu, Y.-H. Organometallics 2010, 29, 1092−1099.
(f) Byrne, L. T.; Koutsantonis, G. A.; Sanford, V.; Selegue, J. P.;
Schauer, P. A.; Iyer, R. S. Organometallics 2010, 29, 1199−1209.
́
(g) García-Fernandez, A.; Gamasa, M. P.; Lastra, E. J. Organomet.
Chem. 2010, 695, 162−169. (h) Shaffer, E. A.; Chen, C. L.; Beatty, A.
M.; Valente, E. J.; Schanz, H.-J. J. Organomet. Chem. 2007, 692, 5221−
2
The function minimized was ([∑wFo2 − Fc2)/∑w(Fo )]1/2 where w
5233. (i) Kopf, H.; Pietraszuk, C.; Hubner, E.; Burzlaff, N.
̈
2
= 1/[σ2(Fo ) + (aP)2 + bP] (a and b values are collected in the
Organometallics 2006, 25, 2533−2546. (j) Díez, J.; Gamasa, M. P.;
Gimeno, J.; Lastra, E.; Villar, A. J. Organomet. Chem. 2006, 691, 4092−
4099. (k) Díez, J.; Gamasa, M. P.; Gimeno, J.; Lastra, E.; Villar, A.
Organometallics 2005, 24, 1410−1418. (l) Rigaut, S.; Touchard, D.;
Dixneuf, P. H. Coord. Chem. Rev. 2004, 248, 1585−1601.
Supporting Information Table S1) from counting statistics, and P =
2
(Max(Fo , 0) + 2Fc2)/3.
Atomic scattering factors were taken from the International Tables
for X-ray Crystallography International.32 The crystallographic plots
were made with PLATON.33
(4) (a) Coletti, C.; Marrone, A.; Re, N. Acc. Chem. Res. 2012, 45,
139−149. (b) Coletti, C.; Gonsalvi, L.; Guerriero, A.; Marvelli, L.;
Peruzzini, M.; Reginato, G.; Re, N. Organometallics 2010, 29, 5982−
5993. (c) Wong, C.-Y.; Lai, L.-M.; Lam, C.-Y.; Zhu, N. Organometallics
2008, 27, 5806−5814. (d) Auger, N.; Touchard, D.; Rigaut, S.; Halet,
J.-F.; Saillard, J.-Y. Organometallics 2003, 22, 1638−1644. (e) Cadierno,
ASSOCIATED CONTENT
* Supporting Information
■
S
1H, 31P{1H}, and 13C{1H} NMR spectra of complexes 5a−c
(Figures S1−S9). Crystal and refinement data for complexes 2·
2CH2Cl2 and 9a·CHCl3 (Table S1). X-ray crystallographic data
of 2·2CH2Cl2 and 9a·CHCl3 in CIF format. This material is
available free of charge via the Internet at http://pubs.acs.org.
V.; Gamasa, M. P.; Gimeno, J.; Gonzal
J.; García-Granda, S.; Perez-Carreno, E. Organometallics 1996, 15,
2137−2147.
́
ez-Cueva, M.; Lastra, E.; Borge,
́
̃
(5) (a) Chen, K.-H.; Feng, Y. J.; Ma, H.-W.; Lin, Y.-C.; Liu, Y.-H.;
Kuo, T.-S. Organometallics 2010, 29, 6829−6836. (b) Cadierno, V.;
Conejero, S.; Gamasa, M. P.; Gimeno, J.; Falvello, L. R.; Llusar, R. M.
Organometallics 2002, 21, 3716−3726. (c) Cadierno, V.; Gamasa, M.
P.; Gimeno, J. Organometallics 1998, 17, 5216−5218.
AUTHOR INFORMATION
Corresponding Author
*Fax: 34 985103446. E-mail: elb@uniovi.es (E. Lastra).
■
(6) Bustelo, E.; Jimenez-Tenorio, M.; Mereiter, K.; Puerta, M. C.;
Valerga, P. Organometallics 2002, 21, 1903−1911.
Notes
The authors declare no competing financial interest.
(7) (a) Cadierno, V.; Conejero, S.; Gamasa, M. P.; Gimeno, J. Dalton
Trans. 2003, 3060−3066. (b) Cadierno, V.; Conejero, S.; Gamasa, M.
P.; Gimeno, J. Organometallics 2001, 3175−3189.
ACKNOWLEDGMENTS
Financial support came from Spanish MICINN (CTQ2011-
26481) and Consolider Ingenio 2010 (CSD2007-00006)).
■
(8) Queensen, M. J.; Rath, N. P.; Bauer, E. B. Organometallics 2014,
33, 5052−5065.
́ ́
(9) Esteruelas, M. A.; Gomez, A. V.; Lopez, A. M.; Modrego, J.;
́
I.G.d.l.A. thanks the Spanish Ministerio de Educacion Cultura y
Deporte for a scholarship.
Onate, E. Organometallics 1997, 16, 5826−5835.
̃
(10) (a) Serrano-Ruiz, M.; Lidrissi, C.; Manas, S.; Peruzzini, M.;
̃
Romerosa, A. J. Organomet. Chem. 2014, 751, 654−661. (b) Talavera,
M.; Bolano, S.; Bravo, J.; Castro, J.; García-Fontan, S.; Hermida-
́
REFERENCES
̃
■
Ramon
Jimenez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 2011,
30, 726−737. (d) Bernard, D. J.; Esteruelas, M. A.; Gomez, A. V.;
Lopez, A. M.; Puerta, M. C.; Valerga, P. Organometallics 1999, 18,
4995−5003. (e) Bruce, M. I. Chem. Rev. 1998, 98, 2797−2858.
(11) (a) Bolano, S.; Rodríguez-Rocha, M. M.; Bravo, J.; Castro, J.;
́
, J. M. Organometallics 2013, 32, 4402−4408. (c) Hyder, I.;
(1) (a) Herndon, J. W. Coord. Chem. Rev. 2013, 257, 2899−3003.
(b) Cadierno, V.; Gimeno, J. Chem. Rev. 2009, 109, 3512−3560.
(c) Che, C.−M.; Ho, C.−M.; Huang, J. S. Coord. Chem. Rev. 2007,
251, 2145−2166. (d) Winter, R. F.; Zalis, S. Coord. Chem. Rev. 2004,
́ ̌
248, 1565−1583. (e) Fisher, H.; Szesni, N. Coord. Chem. Rev. 2004,
248, 1659−1677.
́
́
́
̃
Onate, E.; Peruzzini, M. Organometallics 2009, 28, 6020−6030.
̃
(2) For recent examples see: (a) Alkhaleeli, D. F.; Baum, K. J.; Rabus,
J. M.; Bauer, E. B. Catal. Commun. 2014, 47, 45−48. (b) Lichtenheldt,
M.; Kress, S.; Blechert, S. Molecules 2012, 17, 5177−5186.
(c) Antonucci, A.; Bassetti, M.; Bruneau, C.; Dixneuf, P. H.;
Pasquini, C. Organometallics 2010, 29, 4524−4531. (d) Diesendruck,
C. E.; Tzur, E.; Lemcoff, N. G. Eur. J. Inorg. Chem. 2009, 4185−4203.
(e) Sauvage, X.; Borguet, Y.; Zaragoza, G.; Demonceau, A.; Delaude,
L. Adv. Synth. Catal. 2009, 351, 441−455. (f) Kopf, H.; Holzberger, B.;
(b) Esteruelas, M. A.; Go
́ ́ ́
mez, A. V.; Lopez, A. M.; Olivan;
Modrego, J.; Onate, E. Organometallics 1998, 17, 5434−5437.
̃
(12) (a) Pino-Chamorro, J. A.; Bustelo, E.; Puerta, M. C.; Valerga, P.
Organometallics 2009, 28, 1546−1557. (b) Bustelo, E.; Jimenez-
Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 2007, 26,
4300−4309. (c) Esteruelas, M. A.; Gomez, A. V.; Lopez, A. M.; Onate,
́
́
́
̃
E.; Ruiz, N. Organometallics 1999, 18, 1606−1614. (d) Le Lagradec,
R.; Roman, E.; Toupet, L.; Muller, U.; Dixneuf, P. H. Organometallics
Pietraszuk, C.; Hubner, E.; Burzlaff, N. Organometallics 2008, 27,
̈
̈
1994, 13, 5030−5039. (e) Pirio, N.; Touchard, D.; Dixneuf, P. H. J.
5894−5905. (g) Metal Vinylidenes and Allenylidenes in Catalysis: From
Reactivity to Applications in Synthesis; Bruneau, C., Dixneuf, P. H., Eds.;
Wiley−VCH: Weinheim, Germany, 2008. (h) Valyaev, D. A.;
Peterleitner, M. G.; Semeikin, O. V.; Utegenov, K. I.; Ustynyuk, N.
Organomet. Chem. 1993, 462, C18−C20.
(13) Bustelo, E.; Jimen
́
ez−Tenorio, M.; Puerta, M. C.; Valerga, P.
Organometallics 1999, 18, 4563−4573.
1352
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353

Organometallics
Article
(14) (a) Jimen
Valerga, P. J. Organomet. Chem. 2004, 689, 2776−2785. (b) Cadierno,
V.; Gamasa, M. P.; Gimeno, J.; Lopez-Gonzalez, M. C.; Borge, J.;
́
ez-Tenorio, M.; Palacios, M. D.; Puerta, M. C.;
́
́
García-Granda, S. Organometallics 1997, 16, 4453−4463.
(15) Cadierno, V.; Crochet, P.; Gimeno, J. Preparation and
Stoichiometric Reactivity of Metal Allenylidene Complexes. In Metal
Vinylidenes and Allenylidenes in Catalysis; Bruneau, C.; Dixneuf, D.,
Eds.; Wiley-VCH: Weinheim, Germany, 2008; p 61.
(16) Albertin, G.; Antoniutti, S.; Castro, J.; Da Lio, S. Organometallics
2013, 32, 3651−3661.
(17) C* = centroid of C(34), C(35), C(36), C(37), C(42). C** =
centroid of C(37), C(38), C(39), C(40), C(41), C(42).
(18) Selegue, J. P. Organometallics 1982, 1, 217−218.
(19) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Lastra, E.; Borge, J.;
García−Granda, S. Organometallics 1994, 13, 745−747 and references
therein.
(20) Analytically pure samples for complexes 5a−c could not be
1
obtained. H, 31P{1H}, and 13C{1H} NMR spectra of the complexes
can be found in the Supporting Information.
(21) Pregosin, P. S.; Kunz, R. W. 31P and 13C of Transition Metal
Phosphine Complexes; Springer-Verlag: Berlin, 1979.
́
(22) Alvarez, P.; Lastra, E.; Gimeno, J.; Brana, P.; Sordo, J. A.;
̃
́
Gomez, J.; Falvello, L. R.; Bassetti, M. Organometallics 2004, 23,
2956−2966.
(23) C* = centroid of C(31), C(32), C(33), C(34), C(39). C** =
centroid of C(34), C(35), C(36), C(37), C(38), C(39).
(24) Hansen, H. D.; Nelson, J. H. Organometallics 2000, 19, 4740−
4755.
(25) Clark, P. W.; Curtis, J. L. S.; Garrou, P. E.; Hartwell, G. E. Can. J.
Chem. 1974, 52, 1720.
(26) This complex can be obtained by stirring a THF solution of
complex [Ru(η5-C9H7){CCC(PMe3)Ph2}{P(OEt)3}(PPh3)][PF6]
(6) at room temperature overnight.
(27) CrysAlisPro CCD and CrysAlisPro RED; Oxford Diffraction Ltd.:
Abingdon, Oxfordshire, UK, 2008.
(28) Farrugia, L. J. J. Appl. Crystallogr. 2012, 45, 849−854.
(29) SIR2004: Burla, M. C.; Caliandro, R.; Camalli, M.; Carrozzini,
B.; Cascarano, G. L.; De Caro, L.; Giacovazzo, C.; Polidori, G.;
Spagna, R. J. Appl. Crystallogr. 2005, 38, 381−388.
(30) Beurskens, P. T.; Beurskens, G.; de Gelder, R.; Smits, J. M. M.;
García-Granda, S.; Gould, R. O.; Smykalla, C. The DIRDIF Program
System; Technical Report of the Crystallographic Laboratory;
University of Nijmegen: Nijmegen, The Netherlands, 2008.
(31) Sheldrick, G. M. SHELXL97, Program for the Refinement of
Crystal Structures; University of Gottingen: Gottingen, Germany, 2014.
̈
̈
(32) Tables for X-Ray Crystallography; Kynoch Press: Birmingham,
U.K., 1974; Vol. IV (present distributor: Kluwer Academic Publishers:
Dordrecht, The Netherlands).
(33) Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;
University of Utrecht: The Netherlands, 2008.
1353
DOI: 10.1021/acs.organomet.5b00060
Organometallics 2015, 34, 1345−1353