Synthesis of Ru(II) complexes of the new 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethylpyrazole ligand and study of their reactivity toward terminal alkynes

Article abstract of DOI:10.1016/S0022-328X(02)02156-3

The reaction between [RuCl₂(PPh₃)₃] and one or two equivalent amounts of 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethylpyrazole (1) in dichloromethane gave [RuCl₂(PPh₃)(1)] (2) or [RuCl₂(1)

Full text of DOI:10.1016/S0022-328X(02)02156-3

Journal of Organometallic Chemistry 667 (2003) 126ꢀ134
/
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Synthesis of Ru(II) complexes of the new
1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethylpyrazole ligand
and study of their reactivity toward terminal alkynes
Glo`ria Esquius a,b, Josefina Pons a, Ramo´n Ya´nez a, Josep Ros a,*, Rene´ Mathieu b,*,
˜
Noel Lugan b, Bruno Donnadieu b
¨
a Departament de Qu´ımica, Universitat Auto`noma de Barcelona, 08193 Bellaterra-Cerdanyola, Barcelona, Spain
b Laboratoire de Chimie de Coordination du CNRS, 250 Route de Narbonne, 31077 Toulouse Cedex 4, France
Received 28 November 2002; received in revised form 5 December 2002; accepted 5 December 2002
Abstract
The reaction between [RuCl2(PPh3)3] and one or two equivalent amounts of 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethylpyr-
azole (1) in dichloromethane gave [RuCl2(PPh3)(1)] (2) or [RuCl2(1)2] (3), respectively, in good yields. Activation of propargylic
alcohol derivatives by 3 in refluxing dichloromethane and in the presence of NaBPh4 lead to the new allenylidene ruthenium
complexes [RuCl(1)2(Cꢀ
/
Cꢀ
/
CPhCH3)][BPh4] ([4][BPh4]) and [RuCl(1)2(Cꢀ
/
Cꢀ
/
CPh2)][BPh4] ([5][BPh4]). The reaction between 3 and
CHPh)][PF6]
phenylacetylene in dichloromethane and in the presence of KPF6 affords the vinylidene complex [RuCl(1)2(Cꢀ
/
([6][PF6]). The X-ray diffraction studies of 2, 3, and [5][BPh4] are reported.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; PꢁN ligands; Hemilabile ligands; Vinylidenes; Allenylidenes
/
1. Introduction
polymerization (ROMP) or ring closing metathesis
(RCM) of cyclic or acyclic olefins [9].
Transition-metal complexes with polydentate ligands
containing both hard and soft donor groups have been
extensively used in coordination and organometallic
chemistry. The majority of such ligands are functiona-
lized phosphines, where the phosphorus is the soft donor
and either oxygen or nitrogen is the hard donor [1,2].
We have recently shown that the new Pꢁ
/
N bidentate
ligand 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethyl-
pyrazole (1) exhibits hemilabile properties when asso-
ciated to rhodium(I) [10]. So it was tempting to extend
our studies of the complexing properties of 1 to the case
of ruthenium(II). In this paper we report the synthesis
and full characterization*
/
including the X-ray crystal
Furthermore, complexes with Pꢁ
/
O and Pꢁ
/
N ligands
structures*of two new ruthenium(II) complexes con-
/
have been found to facilitate several stoichiometric
transformations of organic molecules, including acety-
lene to vinylidene tautomerization [3].
taining this ligand, and the study of their reactivity
toward phenylacetylene and propargyl alcohols in the
direction of vinylidene and allenylidene complexes. The
The increasing attention brought to the chemistry of
ruthenium(II) complexes containing carbene or vinyli-
X-ray crystal structure of a new allenylideneꢀruthenium
/
is also presented.
dene ligands [4ꢀ
promote selective carbonꢀ
/
7] is due to their potential ability to
carbon coupling reactions
/
and to their activity in catalytic transformations invol-
ving terminal alkynes [8], ring opening metathesis
2. Results and discussion
* Corresponding authors.
E-mail addresses: josep.ros@uab.es (J. Ros), mathieu@lcc-
toulouse.fr (R. Mathieu).
1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethylpyra-
zole was synthesized as we described earlier [10] by
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(02)02156-3

G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ
/
134
127
reaction of 1-(chloroethyl)-3,5-dimethylpyrazole [11]
and PPh2Li in tetrahydrofuran.
The reaction of one equivalent amount of 1-[(P-
diphenyl)-2-phosphinoethyl]-3,5-dimethylpyrazole (1)
with one equivalent amount of [RuCl2(PPh3)3] in
ligand, and two chlorine atoms. The arrangement
around the ruthenium atom is intermediate between a
square pyramid and a trigonal-bipyramid. Reedijk index
of trigonality [14] leads to a square pyramid geometry
for the complex with a 19% distortion toward a trigonal
bipyramid. In this distorted square pyramid the phos-
phorus atom P(1) occupies the apical position, while the
mean plane containing N(1), P(2), and the two chlorine
atoms constitutes the base of the pyramid. The ruthe-
dichloromethane
at
room
temperature
gave
[RuCl2(PPh3)(1)] (2) in 86% yield (Scheme 1). The
complex was analytically and spectroscopically (IR
1
and H-, 13C{1H}-, and 31P{1H}-NMR) characterized
˚
nium atom is 0.327 A above the base of the pyramid.
(see Section 4). 1H- and 13C{1H}-NMR spectra are
consistent with the proposed formulation and give
evidence for the coordination of the ligand 1 to the
Ru(II) atom. Indeed, the 31P{1H}-NMR spectrum
exhibits the expected AX pattern: two doublets at 84.6
This allows the N(1)ꢁRu(1)ꢁP(1) angle to be larger than
/
/
observed for the same ligand in square-planar rhodium
complexes (94.24(6)8 as compared with 89.13(7)8 for the
rhodium complex [Rh(1)2]ꢂ) [10]. Due to the steric bulk
of the triphenylphosphine ligand, the P(2)ꢁ
and the N(1)ꢁRu(1)ꢁP(2) angles are greater than 908*
94.09(3) and 92.32(6)8, respectively*and this minimizes
the interaction with the methyl group of the pyrazolyl
cycle. As a consequence, the N(1)ꢁRu(1)ꢁCl(1) and the
C(l2)ꢁRu(1)ꢁCl(1) angles are lower than 908, 82.99(6)
and 86.92(3)8, respectively. The bond lengths Ru(1)ꢁ
/
Ru(1)ꢁ
/
Cl(2)
and 48.0 ppm (2JPꢁP
ꢁ44.0 Hz) due to the phosphorus
/
/
/
/
atom of the ligand 1 and the one of the triphenylphos-
phine ligand. The value of the coupling constant is in
agreement with two phosphine ligands in a cis position
[12,13].
The structure of 2 was determined by an X-ray
diffraction study. Crystal and refinement data are
summarized in Table 1. Selected interatomic distances
and angles are provided in Table 2. A perspective view
of the complex is shown in Fig. 1.
/
/
/
/
/
/
˚
˚
N(1) (2.105(2) A), Ru(1)ꢁ
/
Cl(1) (2.3979(7) A) and
˚
Cl(2) (2.3767(7) A) are in the range of those
found in similar complexes [12,15].
Ru(1)ꢁ
/
The reaction of [RuCl2(PPh3)3] with two equivalent
amounts of 1 in dichloromethane solution at room
temperature led to [RuCl2(1)2] (3) in 90% yield (Scheme
1). The analytical and spectroscopic data for this
complex are consistent with this formulation. The
31P{1H}-NMR spectrum shows one signal only at 36.2
ppm for the PPh2 groups of ligand 1 indicating that the
two phosphino groups are magnetically equivalent. The
structure of complex 3 was established by an X-ray
diffraction analysis. Crystal and refinement data are
given in Table 1. Selected bond lengths and angles are
provided in Table 2. The complex crystallizes with two
independent molecules per unit cell. The two molecules
are almost superimposable, the corresponding bond
distances and angles being equal within the experimental
error. A perspective view of one of the two independent
molecules, molecule A, is shown in Fig. 2.
The ruthenium atom is pentacoordinated through the
nitrogen atom N(1) and phosphorus atom P(1) of ligand
1, the phosphorus atom P(2) of the triphenylphosphine
The coordination geometry around Ru consists of a
distorted octahedron, the two phosphorus atoms and
the two nitrogen atoms being respectively in a cis
position, and the chlorine atoms being in a trans
position.
The distortion from an idealized octahedral geometry
can be attributed to the steric repulsion between of the
two bulky PPh2 and the two close 3,5-dimethylpyrazole
groups. The more sterically demanding group is PPh2
and as a consequence the P(2)ꢁ
/
Ru(1)ꢁ
/
P(1) angle is the
largest (103.73(6)8). The Ruꢁ
/
N distances of 2.216(5) and
P bond lengths of 2.2986(16)
˚
2.214(5) A and the Ruꢁ
/
˚
and 2.3023(16) A are larger than those found in
[RuCl2(PPh3)(1)] complex but fall between the experi-
mental values reported for similar complexes [19,22].
Scheme 1.

128
G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ134
/
Table 1
Crystal data for compounds [RuCl2(PPh3)(1)] (2), [RuCl2(1)2] (3), and [RuCl(1)2(Cꢀ
/
CꢀCPh2)][BPh4] ([5][BPh4])
/
2
3
[5][BPh4]
Empirical formula
Formula weight (g)
Temperature (K)
C
37H36Cl2N2P2Ru
C76H84Cl4N8P4Ru2
1577.33
163(2)
C154H144B2Cl2N8P4Ru2
2525.31
180(2)
742.59
293(2)
˚
Wavelength (A)
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/c
Crystal system
Space group
˚
a (A)
10.5566(11)
22.1294(18)
14.849(2)
90
10.9168(9)
43.867(5)
15.5946(12)
90
23.526(3)
18.6030(14)
30.224(3)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
105.010(14)
90
106.289(9)
90
105.869(11)
90
3
˚
Volume (A )
Z
3350.6(7)
4
1.472
7168.2(11)
4
1.462
12 724(2)
4
1.318
Dcalc (g cmꢃ3
)
m (mmꢃ1
F(000)
)
0.752
1520
0.710
3248
0.387
5264
uRange (8)
Index ranges
2.20ꢀ
125
l 518
24 644
Independent reflections 6414 [Rint
/
25.91
1.95ꢀ
125
l 516
41 978
/
24.25
1.80ꢀ
255
l 532
65 382
/
22.60
ꢃ/
/h 5
/
12, ꢃ
/
275
/
k 5
/
27, ꢃ
/
185
/
ꢃ/
/h 5
/
12, ꢃ
/
505
/
k 5
/
50, ꢃ
/
175
/
ꢃ/
/
h 5
/
25, ꢃ
/
205
/
k 5
/
19, ꢃ
/
325
/
/
/
/
Reflections collected
ꢁ
/
0.0520]
10 785 [Rint
93.0
ꢁ
/
0.1136]
16 562 [Rint
98.2
ꢁ/0.1205]
Completeness to umax
(%)
98.4
Refinement method
Data/restraints/para-
meters
Full-matrix least-squares on F2
6414/0/399
10 785/0/852
16 562/0/1309
˚
N distances of 2.216(5) and 2.214(5) A and the
The Ruꢁ
/
NaBPh4 [20,21] afforded the dark red allenylideneꢀ
ruthenium complexes, [RuCl(1)2(CꢀCꢀCPhCH3)]-
[BPh4] ([4][BPh4]) and [RuCl(1)2(CꢀCꢀCPh2)][BPh4]
([5][BPh4]) in 82 and 80% yield, respectively (Scheme
1). Both allenylidene complexes were characterized by
elemental analysis, IR and NMR spectroscopies. The
presence of the allenylidene ligand in complexes [4]ꢂ
and [5]ꢂ was readily established by IR spectroscopy
with the observation of strong bands at 1923 and 1936
/
˚
RuꢁP bond lengths of 2.299(2) and 2.302(2) A are larger
/
/
/
than those found in complex 2 but fall between the
experimental values reported for similar complexes
[16,17]. Each of the six-membered rings formed by the
bidentate ligands coordinated to ruthenium adopts a
boat conformation, the atoms Ru(1) and C(6), and
Ru(1) and C(13), respectively, being the apexes of the
boats. In addition, in agreement with the NMR data,
the apexes are oriented in such a way that the molecule
exhibits in the solid state a [non-crystallographic] C2
symmetry, the C2 axis passing through the Ru atom and
/
/
cmꢃ1, attributable to the n(Cꢀ
/
Cꢀ
/
Cas) vibration mode
[20]. The NMR spectra of [4]ꢂ and [5]ꢂ display two
different sets of resonances for the two ligands 1. In
1
particular, H-NMR spectra exhibit eight multiplets for
bisecting the Pꢁ
/
Ruꢁ
/
P angle. The present structure thus
the four pairs of diastereotopic protons. On the other
hand, the 31P{1H}-NMR spectra shows two doublets
corresponding to the non-equivalent phosphorus atoms.
corresponds the (ll(dd)) diastereomers.
The reactivity of the complexes 2 and 3 toward
terminal alkynes has been investigated. Reactions of
the 16eꢃ complex 2 with propargylic alcohol or terminal
alkynes failed to give any isolatable complexes. Decom-
position to metallic ruthenium and free ligands was
apparent after prolonged stirring in dichloromethane at
room temperature. This is a quite unexpected result as
there are precedent for the formation of neutral
vinylidene complexes from the 16eꢃ complexes
2
The JPꢁP coupling constant value of 31 Hz (for both
complexes) is consistent with the two phosphorus atoms
being in a cis position. As compared with 3, these data
suggests a lowering of the global symmetry of the
complex to the C1 symmetry. The 13C{1H}-NMR
spectra of complexes [4]ꢂ and [5]ꢂ display low-field
2
signals at 305.4 ppm (dd, JCꢁP
ꢁ16 and 19 Hz) and
/
2
RuCl2(PPh3)3 or RuCl2(PPh3)(Pꢁ
/
N) by reaction with
303.5 (dd, JCꢁP
ꢁ17 and 19 Hz), respectively, clearly
/
terminal alkynes or propargylic alcohols [18,19].
By contrast, the reaction of the 18eꢃ complex 3 with
2-phenyl-3-butyn-2-ol or 1,1-diphenyl-2-propyn-1-ol in
refluxing dichloromethane and in the presence of
attributable to the Ca of the allenylidene ligands.
Resonances due to the Cb carbon atoms and Cg carbon
atoms appear as triplets at 210.8 ppm (3JCꢁP
ꢁ
/
3.7 Hz)
and 157.1 ppm (4JCꢁP
ꢁ
/
1.8 Hz), respectively, for [4]ꢂ,

G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ
/
134
129
Table 2
Selected bond distances (A) and angles (8) for compounds 2, 3 and [5] [BPh4]
˚
2
3
Cation 5A
Cation 5B
Bond lengths
N(1)ꢁRu(1)
P(1)ꢁ
P(2)ꢁ
/
2.105(2)
2.189(1)
2.270(1)
2.398(1)
2.377(1)
N(1)ꢁ
N(3)ꢁ
P(1)ꢁ
P(2)ꢁ
Cl(1)ꢁ
Cl(2)ꢁ
/
Ru(1)
2.216(5)
2.214(5)
2.299(2)
2.302(2)
2.431(2)
2.431(2)
N(1)ꢁ
N(3)ꢁ
P(1)ꢁ
P(2)ꢁ
Cl(1)ꢁ
C(15)ꢁ
C(15)ꢁ
C(16)ꢁ
C(17)ꢁ
C(17)ꢁ
/
Ru(1)
Ru(1)
2.171(5)
2.207(5)
2.313(2)
2.363(2)
2.448(2)
1.878(5)
1.250(8)
1.384(8)
1.464(6)
1.494(6)
2.173(5)
2.216(5)
2.333(2)
2.356(2)
2.469(2)
1.877(6)
1.252(9)
1.364(9)
1.462(7)
1.502(6)
/
Ru(1)
/Ru(1)
/
/
Ru(1)
/
Ru(1)
/
Ru(1)
Cl(1)ꢁ
/
Ru(1)
/
Ru(1)
/
Ru(1)
Cl(2)ꢁ
/
Ru(1)
/
Ru(1)
Ru(1)
/Ru(1)
/
/
Ru(1)
C(16)
C(17)
C(48)
C(42)
/
/
/
/
Bond angles
N(1)ꢁRu(1)ꢁ
N(1)ꢁRu(1)ꢁ
P(1)ꢁRu(1)ꢁ
N(1)ꢁRu(1)ꢁ
P(1)ꢁRu(1)ꢁ
P(2)ꢁRu(1)ꢁ
Cl(2)ꢁ
N(1)ꢁRu(1)ꢁ
P(1)ꢁRu(1)ꢁ
P(2)ꢁRu(1)ꢁ
C(11)ꢁP(1)ꢁ
C(7)ꢁP(1)ꢁ
C(7)ꢁP(1)ꢁ
C(7)ꢁP(1)ꢁ
C(11)ꢁ
C(21)ꢁ
C(51)ꢁ
C(51)ꢁ
C(41)ꢁ
C(51)ꢁ
C(41)ꢁ
C(31)ꢁ
/
/
P(1)
94.24(6)
92.32(6)
95.11(3)
N(1)ꢁ
N(3)ꢁ
N(1)ꢁ
N(3)ꢁ
N(3)ꢁ
P(1)ꢁRu(1)ꢁ
N(1)ꢁRu(1)ꢁ
N(3)ꢁRu(1)ꢁ
P(1)ꢁRu(1)ꢁ
P(2)ꢁRu(1)ꢁ
Cl(2)ꢁ
N(1)ꢁRu(1)ꢁ
N(3)ꢁRu(1)ꢁ
P(1)ꢁRu(1)ꢁ
P(2)ꢁRu(1)ꢁ
C(31)ꢁP(1)ꢁ
C(21)ꢁP(1)ꢁ
C(7)ꢁP(1)ꢁ
C(41)ꢁP(2)ꢁ
C(51)ꢁP(2)ꢁ
C(14)ꢁP(2)ꢁ
/
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
/
P(1)
P(2)
P(2)
P(1)
N(1)
86.32(13)
87.60(14)
167.41(14)
167.05(14)
83.35(18)
103.73(6)
87.21(15)
97.40(15)
89.85(6)
85.29(5)
173.22(5)
97.89(15)
87.67(15)
86.03(6)
90.45(6)
123.4(2)
116.7(2)
111.1(2)
123.0(2)
119.7(2)
111.2(2)
N(1)ꢁ
N(3)ꢁ
N(1)ꢁ
N(3)ꢁ
N(1)ꢁ
P(1)ꢁRu(1)ꢁ
N(1)ꢁRu(1)ꢁ
N(3)ꢁRu(1)ꢁ
P(1)ꢁRu(1)ꢁ
P(2)ꢁRu(1)ꢁ
C(15)ꢁ
C(15)ꢁ
C(15)ꢁ
C(15)ꢁ
C(15)ꢁ
C(16)ꢁ
C(15)ꢁ
/
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
/
P(1)
P(2)
P(2)
P(1)
N(3)
91.27(13)
87.86(14)
164.56(13)
172.09(13)
86.43(18)
96.20(6)
89.29(14)
85.42(14)
165.31(14)
169.10(14)
83.04(19)
103.30(6)
88.45(13)
97.48(13)
90.02(5)
/
/P(2)
/
/
/
/
/
/
P(2)
Cl(1)
/
/
/
/
/
/
82.99(6)
/
/
/
/
/
/
Cl(1)
Cl(1)
108.39(3)
156.28(3)
86.92(3)
/
/
/
/
/
/
/
/
P(2)
/
/
P(2)
/
Ru(1)ꢁ
/
Cl(1)
Cl(2)
/
/
Cl(1)
Cl(1)
/
/
Cl(1)
85.19(13)
96.29(13)
91.04(5)
/
/
167.66(6)
95.67(3)
/
/
/
/
Cl(1)
/
/
Cl(2)
Cl(2)
/
/Cl(1)
/
/
Cl(1)
Cl(1)
/
/
94.09(3)
/
/Cl(1)
/
/
81.19(6)
84.06(5)
/
/
C21
99.73(12)
104.60(12)
103.58(12)
110.45(9)
123.03(9)
113.33(8)
106.46(13)
100.21(12)
99.50(12)
116.04(9)
103.74(9)
128.23(9)
/
Ru(1)ꢁ
/Cl(1)
/
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
Ru(1)ꢁ
C(15)ꢁ
C(16)ꢁ
/
Cl(1)
178.97(18)
94.9(2)
84.7(2)
173.40(19)
97.5(2)
86.1(2)
/
/
C(11)
C21
/
/
Cl(2)
Cl(2)
/
/
N(1)
N(3)
P(1)
P(2)
/
/
/
/
/
/
/
/
Ru(1)
/
/Cl(2)
/
/
87.93(17)
98.87(17)
178.0(5)
87.19(18)
90.76(18)
178.1(5)
/
P(1)ꢁ
P(1)ꢁ
P(2)ꢁ
P(2)ꢁ
P(2)ꢁ
P(2)ꢁ
P(2)ꢁ
P(2)ꢁ
/
Ru(1)
Ru(1)
C41
/
/Cl(2)
/
/
/
/
/
/Ru(1)
/
/Ru(1)
/
/
/
/Ru(1)
/
/C(17)
176.9(6)
176.5(7)
/
/
C(31)
C(31)
Ru(1)
Ru(1)
Ru(1)
/
/Ru(1)
/
/
/
/
Ru(1)
Ru(1)
Ru(1)
/
/
/
/
/
/
/
/
/
/
comparable to those reported for other allenylideneꢀ
/
ruthenium complexes [21ꢀ25].
/
The molecular structure of complex [5]ꢂ has been
established by X-ray diffraction. Crystal and refinement
data are summarized in Table 1. [5][BPh4] crystallizes
with two independent ion pairs per unit cell. Selected
interatomic bond distances and angles are provided in
Table 2. A perspective view showing one of the two
cations, cation A, is shown in Fig. 3. The corresponding
bond distances within cation A and cation B are equal
within the experimental error. Although most of the
corresponding bond angles are significantly different,
they remain similar.
Fig. 4 shows a superimposition of the skeleton of the
two cations. It appears that the main structural differ-
ences lie in the orientation of the phenyl rings attached
Fig. 1. A perspective view of complex 2 (the thermal ellipsoid are
shown at the 50% probability level).
to
{Ru(1b)ꢁ
P(2a)ꢁC(36a)ꢁ
C(36b)ꢁC(37b)}ꢁ
distorted octahedral complex, the angles around Ru
P2
P(2b)ꢁ
C(37a)}ꢁ
13.48). Each cation consists of a
({Ru(1a)ꢁ
C(30b)ꢁC(31b)}ꢁ
104.48,
/
P(2a)ꢁ
/
C(30a)ꢁ
77.18; {Ru(1a)ꢁ
{Ru(1b)ꢁP(2b)ꢁ
/
C(31a)}ꢁ7.18,
/
/
/
/
/
ꢃ
/
/
/
/
/
/
/
and at 217.9 ppm (3JCꢁP
(4JCꢁP 1.8 Hz), respectively, for [5]ꢂ. These data are
ꢁ/3.4 Hz) and 156.6 ppm
/
/
ꢁ
/

130
G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ134
/
Fig. 4. A superimposition of the skeleton of two independent cations
of [5]ꢂ, in the solid state.
Fig. 2. A perspective view of complex 3 (molecule A) (the thermal
ellipsoid are shown at the 50% probability level).
form is maintained in both cations. The C(15)ꢁ
Cl(1) angle is significantly larger for cation
(178.97(18)8) than for cation B (173.40(19)8). Due to
steric crowding around the P atoms, the PꢁRuꢁP angle
(96.20(6) and 103.30(6)8 for cation A and B, respec-
tively) is larger than 908, while the NꢁRuꢁN angle
/
Ruꢁ
/
A
/
/
/
/
(86.43(18) and 83.04(19)8 for cation A and B, respec-
tively) are smaller than 908. The diphenylallenylidene
ligand is bonded to ruthenium in a nearly linear fashion:
Ru(1)ꢁ
C(16)ꢁC(17)ꢁ
B, respectively. The bond lengths compare well with
those reported for other allenylideneꢀruthenium com-
/
C(15)ꢁ
/
C(16)ꢁ
/
178.0(5) and 178.1(5)8, C(15)ꢁ
/
/
/
176.9(6) and 176.5(7)8 for cation A and
/
˚
plexes (Ruꢁ
/
C(15) 1.878(5) and 1.877(6) A, C(15)ꢁ
/
C(16)
˚
1.250(8) and 1.252(9) A, and C(16)ꢁ
/
C(17) 1.384(8) and
˚
1.364(9)
A
for cations
A
and B), respectively
[23,24,26,27]. In each cation, the Ruꢁ
/
P and Ruꢁ
/N
bond lengths fall into the expected values for this type of
complexes [25,26].
The dynamic properties of complex 5 were assessed a
1
variable-temperature H-NMR experiments. No signifi-
cant change was observed in the 293ꢀ320 K range. The
/
solvent and the thermal stability of the complex did not
allow acquisition of spectra at higher temperature.
Nevertheless, a fluxional behavior was evidenced by
phase-sensitive NOESY experiments that indeed clearly
showed a dynamic exchange between the corresponding
methylene and methyne protons of the two ligands 1.
This observation can be rationalized in terms of a
conformational equilibrium between the two six-mem-
bered rings allowing the averaging of all isomers of [5]ꢂ,
Fig. 3. A perspective view of complex [5]ꢂ (cation A) (the thermal
ellipsoid are shown at the 30% probability level).
being in the range 81.2ꢀ
/
98.9 and 164.6ꢀ
/
179.08 for
cation A, and 83.1ꢀ97.5 and 165.3ꢀ
/
/
173.48 for cation
B. The geometry around the ruthenium atom is similar
to that of complex 3, for which one of the two chlorine
atoms would have formally been substituted by the
allenylidene ligand. It is worth noting that the ll(dd)
ll(dd)=
/
dl(ld)=/dd(ll).

G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ
/
134
131
The reaction of phenylacetylene with complex 3 in
dichloromethane at room temperature and in the
presence of KPF6 leads to the vinylidene complex
previously reported [10]. The reactions were carried
out under dinitrogen atmosphere using vacuum line and
Schlenk techniques. Solvents were dried and distilled
according to standard procedures and stored under
dinitrogen. NMR spectra were run on Bruker AC200,
AC250, Avance DPX250 or Avance DRX500 spectro-
meters in CDCl3 solutions at room temperature (r.t.).
All the chemical shift values are given in ppm and are
referenced with respect to residual protons in the solvent
for 1H spectra, to solvent signals for 13C spectra, to
external H3PO4 for 31P spectra and to external C6H5F
[RuCl(1)2(Cꢀ/CHPh)][PF6] ([6][PF6]), which was isolated
as a green solid in 86% yield [16,28]. The salt [6][PF6]
was characterized by microanalysis, and IR and NMR
spectroscopies. Strong infrared absorptions were found
at 1623 and 841 cmꢃ1 corresponding to the n(Cꢀ
/
C)
band of the vinylidene ligand, and to the [PF6]ꢃ anion,
respectively [16,23,28,29]. As for [5]ꢂ, the NMR spectra
indicate that the two ligands 1 in [6]ꢂ are not
magnetically equivalent. The most remarkable feature
for 19F spectra. IR spectra were recorded on a Perkinꢀ
/
1
in the H-NMR spectrum of [6]ꢂ is the presence of a
Elmer 2000 spectrophotometer with KBr pellets or in
CH2Cl2 solutions with CaF2 cells. Elemental analysis
were performed at the Laboratoire de Chimie de
triplet signal at 2.97 ppm (4JPꢁH
ꢁ
/
4.3 Hz) attributable
CHPh proton [23,28]. The 31P{1H}-NMR
spectrum exhibits two doublets at 24.4 ppm (2JPꢁP
31.4 Hz) and 22.0 ppm (2JPꢁP
31.4 Hz) due to the
to the Cꢀ
/
ꢁ
/
Coordination on a PerkinꢀElmer 2400 CHN analyzer
/
ꢁ
/
or at the Universitat Auto`noma de Barcelona on a Carlo
Erba CHNS EA-1108 apparatus.
two non equivalent phosphorus atoms and the small
shift difference is consistent with a structure similar to
the structure of [5]ꢂ (Scheme 1). The 13C{1H}-NMR
data clearly indicate the presence of the vinylidene
moiety. Significantly, the typical low-field resonance
for the Ca carbon atom of the vinylidene moiety appears
4.2. Synthesis of [RuCl2(PPh3)(1)] (2)
The ligand 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-di-
methylpyrazole (1) (0.049 g, 0.160 mmol) was added to a
solution of 0.153 g (0.160 mmol) of [RuCl2(PPh3)3] in 20
ml of dichloromethane. The green solution was stirred
for 5 h. After evaporation of the solvent under vacuum,
the addition of 5 ml of acetone gave the compound as a
red precipitate, which was filtrated and washed with
pentane. The complex was then crystallized in a
as a double doublet at 356.8 ppm (2JCꢁP
ꢁ16.4 and 19.2
/
Hz) while the Cb appears as a singlet at 111.3 ppm.
These data are in full agreement, which those reported
for other octahedral ruthenium(II) vinylidene deriva-
tives [16,23,28,29].
dichloromethaneꢀ
Calc. for C37H36N2P2Cl2Ru×
4.75; N, 3.57. Found: C, 57.81; H, 4.78; N, 3.43%. IR
(KBr) n (cmꢃ1): 3050 (nCꢁ
Har), 2980ꢀ2918 (nCꢁHal),
1554 (nCꢀCar, nCꢀNar), 1482ꢀ1464 (dCH3as), 1434
(dCꢀCar, dCꢀNar), 1394ꢀ1157 (nCꢁN), 1090ꢀ998
(dCꢁHip), 872 (dꢁCHoop), 719 (nPꢁC, dCꢁHoop).
1H-NMR (200 MHz) d (ppm): 7.56ꢀ
7.07 [m, 25H,
/
acetone mixture. Yield: 86%. Anal.
3. Conclusion
/
1/2CH2Cl2: C, 57.37; H,
In conclusion, we have shown that the bidentate
ligand 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-dimethyl-
pyrazole (1) reacts with [RuCl2(PPh3)3] in a straightfor-
ward manner to afford either the 16eꢃ complex
[RuCl2(PPh3)(1)] (2) or the 18eꢃ complex [RuCl2(1)2]
(3), depending on the stoichiometry of the reactants.
Contrary to our observations in the case of complexa-
tion to rhodium [10], no evidences for a hemilabile
character of the ligand 1 was obtained when associated
to ruthenium in complexes 2 or 3. On the other hand, in
the presence of chloride abstractors, the complex 3
readily activates terminal alkynes to afford in a classical
manner cationic cumulene complexes.
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
PPh2, PPh3], 5.93 [s, 1H, CH pyrazole], 4.17 [m, 2H,
CH2CH2PPh2], 2.57 [m, 2H, CH2CH2PPh2], 2.24 [s, 3H,
CCH3], 2.19 [s, 3H, CCH3]. 13C{1H}-NMR (50 MHz) d
(ppm): 148.1 [CCH3], 140.8 [CCH3], 140.2ꢀ
/
127.3 [PPh2,
PPh3], 106.9 [CH pyrazole], 41.9 [CH2CH2PPh2], 31.6
1
[d, JCꢁP
ꢁ33.6 Hz, CH2CH2PPh2], 15.1 [CCH3], 11.5
/
[CCH3]. 31P{1H}-NMR (81 MHz) d (ppm): 84.6 [d,
2JPꢁP
2
ꢁ
/
44.0 Hz, PPh2], 48.0 [d, JPꢁP
ꢁ44.0 Hz, PPh3].
/
4.3. Synthesis of [RuCl2(1)2] (3)
4. Experimental
The ligand 1-[(P-diphenyl)-2-phosphinoethyl]-3,5-di-
methylpyrazole (0.211 g, 0.684 mmol) was added to a
solution of 0.306 g (0.320 mmol) of [RuCl2(PPh3)3] in 20
ml of dichloromethane. The brown solution was stirred
for 5 h. After evaporation of the solvent under vacuum,
the addition of 5 ml of acetone gave the compound as a
red precipitate, which was filtrated and washed with
4.1. General
All chemicals were used as received from commercial
suppliers, unless otherwise indicated. The complex
RuCl2(PPh3)3 was prepared according to literature
methods [30] and 1-[(P-diphenyl)-2-phosphinoethyl]-
3,5-dimethylpyrazole ligand was synthesized as we
pentane. The complex was crystallized in
a

132
G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ134
/
dichloromethaneꢀ
Calc. for C38H42Cl2N4P2Ru: C, 57.87; H, 5.37; N, 7.10.
Found: C, 57.14; H, 4.65; N, 6.73%. IR (KBr) n (cmꢃ1):
/
acetone mixture. Yield: 90%. Anal.
[CCH3], 12.2 [2ꢄ
/
CCH3]. 31P{1H}-NMR (101 MHz)
2
d (ppm): 30.2 [d, JPꢁP
ꢁ31.4 Hz, PPh2], 28.1 [d,
/
2JPꢁP
ꢁ31.4 Hz, PPh2].
/
3054 (nCꢁ
nCꢀNar), 1480 (dCH3as), 1435 (dCꢀ
1371ꢀ1154 (nCꢁN), 1096ꢀ1030 (dCꢁHip), 717 (nPꢁ
dCꢁ 7.02 [m,
Hoop). 1H-NMR (250 MHz) d (ppm): 7.26ꢀ
20H, PPh2], 5.84 [s, 2H, CH pyrazole], 5.17 [m, 4H,
CH2CH2PPh2], 2.72 [m, 4H, CH2CH2PPh2], 2.27 [s, 6H,
CCH3], 1.99 [s, 6H, CCH3]. 13C{1H}-NMR (63 MHz) d
/
Har), 2964ꢀ
/
2919 (nCꢁ
/
Hal), 1554 (nCꢀ
Car, dCꢀNar),
C,
/
Car,
/
/
/
4.5. Synthesis of [RuCl(1)2(Cꢀ
/
Cꢀ
/
CPh2)][BPh4]
/
/
/
/
/
[5][BPh4]
/
/
1,1-Diphenyl-2-propyn-1-ol (0.046 g, 0.222 mmol) in
dichloromethane and 0.030 g (0.089 mmol) of NaBPh4
dissolved in the minimum of methanol were added to a
solution of 0.070 g (0.089 mmol) of [RuCl2(1)2] in 10 ml
of dichloromethane. The mixture was heated under
reflux for 1 h. After cooling at r.t., the solvents were
removed under vacuum. The residue was extracted with
dichloromethane and the salts were separated by filtra-
tion. The red solution was then evaporated under
vacuum and the remaining complex was crystallized in
(ppm): 155.0 [CCH3], 140.3 [CCH3], 134.3ꢀ
/
126.9
[PPh2], 108.4 [CH pyrazole], 43.8 [CH2CH2PPh2], 33.5
1
[d, JCꢁP
ꢁ25.7 Hz, CH2CH2PPh2], 15.5 [CCH3], 12.0
/
[CCH3]. 31P{1H}-NMR (101 MHz) d (ppm): 36.2 [b,
PPh2].
4.4. Synthesis of [RuCl(1)2(Cꢀ
/
Cꢀ/CPhCH3)][BPh4]
[4][BPh4]
dichloromethaneꢀdiethyl ether. Yield: 80%. Anal. Calc.
/
for C77H72BClN4P2Ru: C, 73.24; H, 5.75; N, 4.44.
Found: C, 73.07; H, 5.87; N, 4.42%. IR (KBr) n
2-Phenyl-3-butyn-2-ol in dichloromethane (0.034 g,
0.231 mmol)) and 0.032 g (0.093 mmol) of NaBPh4 in
the minimum of methanol were added to a solution of
0.073 g (0.093 mmol) of [RuCl2(1)2] in 10 ml of
dichloromethane. The mixture was heated under reflux
for 1 h. The solvents were evaporated under reduced
pressure. The residue was dissolved in 10 ml of
dichloromethane and the salts were separated by filtra-
tion. After evaporation, the remaining red solid was
washed with diethyl ether and dried under vacuum. The
(cmꢃ1): 3051 (nCꢁ
/
Har), 2996ꢀ
Cas), 1558 (nCꢀCar, nCꢀ
1433 (dCꢀCar, dCꢀNar), 1374ꢀ1129 (nCꢁ
1030 (dCꢁHip), 720 (nBꢁC, nPꢁC, dCꢁ
Hoop). 1H-
NMR (250 MHz) d (ppm): 7.41ꢀ6.82 [m, 50H, PPh2,
/
2931 (nCꢁ
Nar), 1480 (dCH3as),
N), 1093ꢀ
/
Hal), 1923
(nCꢀ
/
Cꢀ
/
/
/
/
/
/
/
/
/
/
/
/
/
CPh2, BPh4], 6.36 [m, 1H, CHHCH2PPh2], 5.89 [s, 2H,
CH pyrazole], 4.79 [m, 1H, CHHCH2PPh2], 4.34 [m,
1H, CHHCH2PPh2], 4.07 [m, 1H, CHHCH2PPh2], 2.90
[m, 1H, CH2CHHPPh2], 2.66 [m, 1H, CH2CHHPPh2],
2.61 [m, 1H, CH2CHHPPh2], 2.27 [s, 3H, CCH3], 2.14
[m, 1H, CH2CHHPPh2], 2.06 [s, 3H, CCH3], 2.02 [s, 3H,
complex was crystallized in a dichloromethaneꢀdiethyl
/
ether. Yield: 82%. Anal. Calc. for C72H70BClN4P2Ru:
C, 72.03; H, 5.88; N, 4.67. Found: C, 71.94; H, 6.13; N,
CCH3], 1.37 [s, 3H, CCH3]. 13C{1H}-NMR (63 MHz) d
2
4.70%. IR (KBr) n (cmꢃ1): 3050ꢀ
/
3034 (nCꢁ
Cas), 1557 (nCꢀ
Nar), 1479 (dCH3as), 1434 (dCꢀCar, dCꢀNar), 1370ꢀ
1161 (nCꢁN), 1095ꢀ1030 (dCꢁHip), 721 (nBꢀC, nPꢁ
C, dCꢁ 6.79
Hoop). 1H-NMR (250 MHz) d (ppm): 7.38ꢀ
/
Har), 2994ꢀ
/
(ppm): 303.5 [dd, JCꢁP
ꢁ
/
17.5 and 19.3 Hz, Ruꢀ
/
C],
C], 164.3 [q, JCꢁ11B
49.4 Hz, BPh4], 164.3 [sept, JCꢁ10B 16.6 Hz, BPh4],
CꢀC], 155.6 [d,
2.5 Hz, CCH3], 154.1 [CCH3], 144.8 [CCH3],
3
1
2922 (nCꢁ
/
Hal), 1936 (nCꢀ
/
Cꢀ
/
/
Car, nCꢀ
/
217.9 [t, JCꢁP
ꢁ
/
3.4 Hz, Ruꢀ
/
Cꢀ
/
ꢁ
/
1
/
/
/
ꢁ
/
4
/
/
/
/
/
156.6 [t, JCꢁP
3JCꢁP
142.8 [d, JCꢁP
CPh2, BPh4], 109.6 [d, JCꢁP
108.8 [d, 4JCꢁP
28.8 Hz, 2ꢄ
CH2CH2PPh2],
ꢁ
/
1.8 Hz, Ruꢀ
/
Cꢀ
/
/
/
/
ꢁ
/
4
[m, 45H, PPh2, CPhCH3, BPh4], 6.39 [m, 1H,
CHHCH2PPh2], 5.90 [s, 1H, CH pyrazole], 5.87 [s,
1H, CH pyrazole], 4.53 [m, 1H, CHHCH2PPh2], 4.43
[m, 1H, CHHCH2PPh2], 4.02 [m, 1H, CHHCH2PPh2],
2.90 [m, 1H, CH2CHHPPh2], 2.74 [m, 1H,
CH2CHHPPh2], 2.70 [m, 1H, CH2CHHPPh2], 2.31 [s,
3H, CCH3], 2.12 [m, 1H, CH2CHHPPh2], 2.07 [s, 3H,
CCH3], 2.01 [s, 3H, CCH3], 1.31 [s, 3H, CCH3], 1.26 [s,
3H, CPhCH3]. 13C{1H}-NMR (63 MHz) d (ppm): 305.4
ꢁ
/
1.8 Hz, CCH3], 136.3ꢀ
/121.6 [PPh2,
4
ꢁ/2.5 Hz, CH pyrazole],
ꢁ
/
1.8 Hz, CH pyrazole], 43.9 [d, 2JCꢁP
ꢁ
/
1
/
CH2CH2PPh2], 33.0 [d, JCꢁP
ꢁ
/
31.9 Hz,
Hz,
32.2 [d, 31.9
1JCꢁP
ꢁ
/
CH2CH2PPh2], 15.7 [CCH3], 14.3 [CCH3], 12.1 [2ꢄ
/
CCH3]. 31P{1H}-NMR (101 MHz) d (ppm): 31.2 [d,
2
2JPꢁP
ꢁ
/
31.4 Hz, PPh2], 26.6 [d, JPꢁP
ꢁ31.4 Hz, PPh2].
/
[dd, 2JCꢁP
3.7 Hz, Ruꢀ
ꢁ
/
16.5 and 19.6 Hz, Ruꢀ
/
C], 210.8 [t, 3JCꢁP
C], 164.3 [q, JCꢁ11B 49.4 Hz, BPh4],
164.3 [sept, JCꢁ10B 16.6 Hz, BPh4], 157.1 [t, JCꢁP
1.8 Hz, RuꢀCꢀCꢀC], 155.7 [d, JCꢁP
154.2 [CCH3], 142.9 [CCH3], 142.5 [d, JCꢁP
CCH3], 136.4ꢀ121.7 [PPh2, CPhCH3, BPh4], 109.5 [d,
4JCꢁP
2.5 Hz, CH pyrazole], 108.8 [d, JCꢁP
CH pyrazole], 43.8 [CH2CH2PPh2], 32.5 [d, JCꢁP
ꢁ
/
4.6. Synthesis of [RuCl(1)2(Cꢀ
/CHPh)][PF6]
1
/
Cꢀ
/
ꢁ
/
[6][PF6]
1
4
ꢁ
/
ꢁ
/
3
/
/
/
ꢁ
/
2.5 Hz, CCH3],
Phenylacetylene (19.5 ml, 0.178 mmol) and 0.033 g
(0.178 mmol) of potassium hexafluorophosphate were
added to a solution of 0.070 g (0.089 mmol) of
[RuCl2(1)2] in 25 ml of dichloromethane. After 4 h
under stirring, the salts were separated off by filtration
and the solution was evaporated under vacuum. The
green residue was washed with diethyl ether and dried in
4
ꢁ
/
1.8 Hz,
/
4
ꢁ
/
ꢁ
/
1.8 Hz,
1
ꢁ
/
1
33.1 Hz, CH2CH2PPh2], 31.5 [d, JCꢁP 33.1 Hz,
CH2CH2PPh2], 15.7 [CCH3], 15.4 [CPhCH3], 14.0
ꢁ
/

G. Esquius et al. / Journal of Organometallic Chemistry 667 (2003) 126ꢀ
/
134
133
vacuo. Yield: 86%. Anal. Calc. for C46H48ClF6N4P3Ru×
O(CH2CH3)2: C, 55.89; H, 5.44; N, 5.21. Found: C,
55.94; H, 5.84; N, 4.94%. IR (KBr) n (cmꢃ1): 3054 (nCꢁ
Har), 2978ꢀ2924 (nCꢁHal), 1623 (nCꢀC), 1559 (nCꢀ
Car, nCꢀNar), 1487 (dCH3as), 1434 (dCꢀCar, dCꢀ
Nar), 1378ꢀ1159 (nCꢁN), 1096ꢀ1039 (dCꢁHip), 841
(nPꢁF), 720 (nPꢁC, dCꢁ
Hoop). 1H-NMR (250 MHz) d
(ppm): 7.43ꢀ6.78 [m, 25H, PPh2, CHPh], 6.35 [m, 1H,
/
5. Supplementary material
The crystallographic CIF files have been deposited
with the Cambridge Crystallographic Data Centre
(deposition numbers: CCDC 195652 (2), CCDC
195653 (3), CCDC 195654 ([5][BPh4]). Copies of this
information may be obtained free of charge from: The
Director, CCDC, 12 Union Road, Cambridge, CB2
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
1EZ, UK (Fax: ꢂ44-1223-336033; e-mail: deposit@
/
CHHCH2PPh2], 5.96 [s, 1H, CH pyrazole], 5.92 [s, 1H,
CH pyrazole], 5.74 [m, 1H, CHHCH2PPh2], 4.76 [m,
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
1H, CHHCH2PPh2], 4.57 [m, 1H, CHHCH2PPh2], 3.06
4
[m, 1H, CH2CHHPPh2], 2.97 [t, JHꢁH
ꢁ4.3 Hz, 1H,
/
Ruꢀ
/
Cꢀ
/
CHPh], 2.84 [m, 1H, CH2CHHPPh2], 2.80 [m,
1H, CH2CHHPPh2], 2.44 [s, 3H, CCH3], 2.36 [s, 3H,
Acknowledgements
CCH3], 2.25 [m, 1H, CH2CHHPPh2], 2.00 [s, 3H,
CCH3], 1.45 [s, 3H, CCH3]. 13C{1H}-NMR (63 MHz)
Support by the CNRS and the Ministerio de Educa-
cio´n y Cultura of Spain (Projects PB96-1146 and
BQU200-0238 and grant to G.E.) are gratefully ac-
knowledged.
2
d (ppm): 356.8 [dd, JCꢁP
ꢁ
/
16.4 and 19.2 Hz, Ruꢀ
/
C],
3
156.9 [d, JCꢁP
[CCH3], 144.1 [CCH3], 134.7ꢀ
111.3 [RuꢀCꢀCHPh], 110.0 [CH pyrazole], 108.9 [CH
pyrazole], 43.8 [d, JCꢁP
ꢁ/2.1 Hz, CCH3], 154.6 [CCH3], 144.6
/126.2 [PPh2, CHPh],
/
/
2
ꢁ
/
34.1 Hz 2ꢄ
/CH2CH2PPh2],
1
32.2 [d, JCꢁP
1JCꢁP
[CCH3], 12.1 [2ꢄ
ꢁ
/
32.7 Hz, CH2CH2PPh2], 29.9 [d,
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˚
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¨
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