Synthesis, reactivity and catalytic properties of the allenylidene [Ru(C=C=CPh2)Cp(PTA)(PPh3)](CF3SO3) (PTA = 1,3,5-triaza-7-phosphaadamantane)

Article abstract of DOI:10.1016/j.jorganchem.2013.08.040

The reactivity of [RuCpCl(PTA)(PPh₃)] with HC≡CPh and HC≡CC(OH)PPh₂ has been studied. The reaction with the phenylacetylene did not provide the desired vinylidene ruthenium complex but as a collateral result the complex [RuCp(DMSO-κS)(PTA)(PPh ₃)](CF₃SO₃) (1) was obtained by reaction of [RuCpCl(PTA)(PPh₃)] with Ag(CF₃SO₃) in DMSO. Reaction of [RuCpCl(PTA)(PPh₃)] with HC≡CC(OH)PPh₂ provided the Ruthenium(II) diphenyl-allenylidene complex [Ru(C=C=CPh ₂)Cp(PTA)(PPh₃)](CF₃SO₃) (2) that was characterized by NMR, IR spectroscopy and elemental analysis. The chemistry of the new diphenyl-allenylidene ruthenium complex has been studied towards a variety of small molecules such as water, O₂, n-propylamine, cyclohexylamine and ethanethiol. From the reaction of 2 with the amines and thiol, two isomers are obtained respectively but only one of them could be isolated and characterized. The allenylidene complex was found to be a useful catalyst for the trans-etherification of 1,4-butanedioldivinyl-ether, ethoxyethene and 1-methoxycyclohexa-1,3-diene

Full text of DOI:10.1016/j.jorganchem.2013.08.040

Journal of Organometallic Chemistry xxx (2013) 1e8
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, reactivity and catalytic properties of the allenylidene
[Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (PTA ¼ 1,3,5-triaza-7-
phosphaadamantane)
Manuel Serrano-Ruiz a, Chaker Lidrissi a, Sonia Mañas a, Maurizio Peruzzini b,
,
Antonio Romerosa a
*
a Área de Química Inorgánica, Universidad de Almería, 04120 Almería, Spain
b Istituto di Chimica dei Composti Organometallici, CNR, Via Madonna del Piano 10, 50019 Sesto , FI, Italy
a r t i c l e i n f o
a b s t r a c t
Article history:
The reactivity of [RuCpCl(PTA)(PPh3)] with HC^CPh and HC^CC(OH)PPh2 has been studied. The
Received 1 July 2013
Received in revised form
21 August 2013
reaction with the phenylacetylene did not provide the desired vinylidene ruthenium complex but as a
collateral result the complex [RuCp(DMSO-kS)(PTA)(PPh3)](CF3SO3) (1) was obtained by reaction of
[RuCpCl(PTA)(PPh3)] with Ag(CF3SO3) in DMSO. Reaction of [RuCpCl(PTA)(PPh3)] with HC^CC(OH)PPh2
provided the Ruthenium(II) diphenyl-allenylidene complex [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2)
that was characterized by NMR, IR spectroscopy and elemental analysis. The chemistry of the new
diphenyl-allenylidene ruthenium complex has been studied towards a variety of small molecules such as
water, O2, n-propylamine, cyclohexylamine and ethanethiol. From the reaction of 2 with the amines and
thiol, two isomers are obtained respectively but only one of them could be isolated and characterized.
The allenylidene complex was found to be a useful catalyst for the trans-etherification of 1,4-butanediol-
divinyl-ether, ethoxyethene and 1-methoxycyclohexa-1,3-diene
Accepted 22 August 2013
Keywords:
Ruthenium
Water-soluble complexes
Allenylidenes
PTA
Catalysis in water
Catalytic trans-etherification
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
biphasic water/organic solvent conditions, including the ring
opening metathesis (ROM) of cyclic olefins [3], the selective trans-
The development of catalytic processes in biphasic water/
organic solvent conditions by using hydrosoluble catalytically
active coordination compounds may provide an attractive solution
to most of the problems of the homogeneous catalysis such as
metal-product contamination and metal loss with the resulting
environmental contamination [1]. The lack of catalyst contamina-
tion in the reaction product is particularly important in all appli-
cations associated to human health, such as drug synthesis and
delivery.
Unsaturated carbenes, particularly the lower members, vinyli-
denes and allenylidenes now constitute a well-established class of
organometallic compounds that have proved useful properties for
the stoichiometric and catalytic synthesis of organic compounds
[2]. Despite the ubiquitous character of transition-metal vinyli-
denes and allenylidenes, only a few examples of water-soluble
complexes containing such ligands have been reported. These
have been shown to be capable of catalysing several processes in
etherification of substituted vinyl ethers to acetals and aldehydes
[4] and the isomerization of enols [5]. Water-soluble allenylidene
complexes are still scarce [6], which is quite surprising given the
intense research activity centred on these species and the pressing
demands for environmentally benign technologies in the manu-
facture of fine chemicals.
On continuing our research activity aimed at synthesizing new
ruthenium hydrosoluble catalysts, we focused our interest on
the reactivity of the water soluble cyclopentadienyl ruthenium
derivatives containing the 1,3,5-triaza-7-phosphaadamantane
(PTA) [7,8]. Within this research strategy, the synthesis of stable
{RuCp(PTA)} vinylidenes and allenylidenes was considered
mandatory to investigate their potential application in catalytic
reactions and to prepare a new class of hydrosoluble unsaturated
carbenes. Therefore, we thought that phenylacetylene and diphe-
nylpropargylic alcohol could easily react with the water soluble
precursor [RuCpCl(PTA)2] to afford respectively the targeted
hydrosoluble metal vinylidene and allenylidene complexes. Sur-
prisingly, the analogous reaction with phenylacetylene did not
produce the anticipated phenylvinylidene complex; instead, an
unexpected silvereruthenium polymer, the first example of a rich
* Corresponding author. Fax: þ34 950 015008.
E-mail address: romerosa@ual.es (A. Romerosa).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.08.040
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

2
M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
family of new hetero-metal-polymers soluble in water, was ob-
2.3. Synthesis of [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2)
tained [9]. To avoid the possible formation of the AgeRu-polymer,
the complex [RuCpCl(PTA)(PPh3)] that contains only
a
PTA
A solution of Ag(CF3SO3) (0.03 g, 0.12 mmol) in 2 mL of CHCl3
was added to a stirred solution of [RuCpCl(PTA)(PPh3)] (0.072 g,
0.12 mmol) in 30 mL of CHCl3 under nitrogen. The resulting mixture
was reacted with 1,1-diphenyl-2-propyn-1-ol (0.18 g, 0.81 mmol)
for 5 min at room temperature and for 2 h at refluxing temperature.
The suspension was filtered to eliminate the formed AgCl and the
solvent evaporated to dryness to leave a purple solid, which was
washed with Et2O (2 ꢂ 5 mL) and dried under vacuum.
was tested as starting complex. Herein we describe the reactivity
of the complex [RuCpCl(PTA)PPh3)] with HC^CPh and HC^CC(OH)
PPh2, the synthesis and characterization of the allenylidene com-
plex containing the {CpRu(PTA)(PPh3)} moiety, its reactivity against
small molecules and its catalytic activity for the trans-etherification
of diol-vinyl-ether derivatives.
Yield: 0.10 g, 94%. S25 C(H2O)(mg mLꢁ1): 0.1. Elemental analysis
ꢀ
2. Experimental section
for C45H42F3N3O3P2RuS (924.91): Found C, 58.75; H, 4.83; N, 4.39; S,
All chemicals were reagent grade and, unless otherwise stated,
were used as received by commercial suppliers. The solvents were
degassed and distilled according to standard procedures. All re-
agents were obtained from commercial sources, checked by NMR
and used as received. PTA [8], [RuCpCl(PPh3)2] [7], [RuCpCl(P-
TA)(PPh3)] [10] were prepared according to the literature pro-
cedures. CD3OD and (CD3)2CO for NMR measurements (Cortec-
Euriso-top) were dried over molecular sieves (0.4 nm). 1H and 13C
{1H} NMR spectra were recorded on a Bruker DRX300 spectrometer
operating at 300.13 MHz (1H) and 75.47 MHz (13C), respectively.
Peak positions are relative to tetramethylsilane and were calibrated
against the residual solvent resonance (1H) or the deuterated sol-
vent multiplet (13C). 31P{1H} and 19F{1H} NMR spectra were recor-
ded on the same instrument operating at 121.49 MHz and
282.40 MHz, respectively. Chemical shifts for 31P{1H} NMR were
measured relative to external 85% H3PO4 while the 19F{1H} NMR
resonances were referred to CFCl3 with downfield values taken as
positive. Infrared spectra were recorded on KBr discs using an FT-IR
ATI Mattson Infinity Series. Elemental analysis (C, H, N, S) were
performed on a Fisons Instruments EA 1108 elemental analyser.
3.39%; calcd. C, 58.44; H, 4.58; N, 4.54; S, 3.47%. IR (KBr, cmꢁ1):
n
(C]C]C) 1930 (vs). 1H NMR (300.13 MHz, acetone-d6):
d 3.80e
3.96 (m, 6 H, PTACH2P); 4.32e4.50 (m, 6 H, PTACH2N), 5.46 (s, 5 H, Cp),
7.25e7.80 (m, 25 H, aromatic). 13C{1H} RMN (75.467 MHz, acetone-
d6):
d 55.43 (bs, NCH2P), 71.91 (s, NCH2N), 91.14 (s, Cp), 128.57e
143.56 (m, aromatic), 158.56 (s, Ru]C]C]C), 207.70 (s, Ru]C]
2
C]C), 293.73 (t, JCP ¼ 17.3 Hz, Ru]C]C]C). 31P{1H} NMR
(121.49 MHz, acetone-d6):
2JCP ¼ 31.9 Hz, PPh3).
d
ꢁ32.03 (d, 2JCP ¼ 31.9 Hz, PTA), 51.25 (d,
2.4. Synthesis of [Ru(]C(NHPr)CH]CPh2)Cp(PTA)(PPh3)](CF3SO3)
(3)
A solution of n-propylamine (39.6 mL, 0.48 mmol) in 2 mL of
CHCl3 was reacted under nitrogen with 2 (0.20 g, 0.22 mmol) in
10 mL of CHCl3. After 2 h the solvent was removed at 1 mL and 5 mL
of Et2O was added. The precipitate was filtered, washed with Et2O
(2 ꢂ 5 mL) and dried under vacuum. The crude product (120 mg)
was dissolved into 5 mL of CHCl3. The small crystals obtained by
slow diffusion of Et2O during 5 days were filtered and air dried.
Yield: 0.07 g, 33%. Elemental analysis for C48H51F3N4O3P2RuS
(984.02): Found C, 58.41; H, 5.38; N, 5.51; S, 3.17%; calcd. C, 58.59;
2.1. Reactivity of [RuCpCl(PTA)(PPh3)] with HC^CPh
H, 5.22; N, 5.69; S, 3.26%. IR (KBr, cmꢁ1):
n
(C]C) 1621 (s). 1H NMR
3
General procedure: Into a 5 mm NMR tube was introduced
0.5 mL of the used solvent (CD3OD, CDCl3, D2O, CD2Cl2, DMSO-d6,
acetone-d6) and [RuCpCl(PTA)(PPh3)] (15 mg, 0.024 mmol) and
(300.13 MHz, CDCl3):
d
0.50 (t, JHH ¼ 7.35 Hz, 3 H, CH3CH2CH2N),
0.62e1.11 (m, 2 H, CH3CH2CH2N), 2.45e3.05 (m, 2 H, CH3CH2CH2N),
3.68e4.80 (m, 12 H, PTA), 4.71 (s, 5 H, Cp), 5.76 (s, 1 H, HC]CPh2),
6.96e7.61 (m, 25 H, aromatic), 9.28 (bs, 1 H, NH). 13C{1H} NMR
HC^CPh (8,9 mL, 0.08 mmol). The solutions were studied by NMR at
room and refluxing temperature. In all solvents but in DMSO-d6 no
transformation of the starting compound was observed after 2 h.
Addition of NaBF4 and NEt3 does not produce a significant trans-
formation of the starting compound. Addition of Ag(CF3OSO2) into
the DMSO-d6 solution led to the complete transformation of the
(75.467 MHz, CDCl3): d 11.20 (s, CH3CH2CH2N), 15.22 (s,
CH3CH2CH2N); 52.68 (s, CH3CH2CH2N), 57.76 (bs, NCH2P), 65.81 (s,
NCH2N), 83.15 (s, Cp), 125.85e131.20 (m, aromatic), 134.86 (s, Ru]
CeC]C), 134.93 (s, Ru]CeC]C), 241.13 (bt, 2JCP ¼ 12.2 Hz, Ru]Ce
C]C). 31P{1H} NMR (121.49 MHz, CDCl3):
d
ꢁ40.20 (d,
starting complex into [RuCp(DMSO-
kS)(PTA)(PPh3)] but addition of
2JPP ¼ 36.63 Hz, PTA), 53.56 (d, 2JPP ¼ 36.61 Hz, PPh3). 19F{1H} NMR
the Ag salt into the other solutions provided a mixture of com-
pounds that could not be characterized.
(282.40 MHz, CDCl3):
d
ꢁ78.07 (s, CF3SO3).
2.5. Reactivity of [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2) with
2.2. Synthesis of [RuCp(DMSO-
kS)(PTA)(PPh3)](CF3SO3) (1)
n-PrNH2
Into 3 mL of DMSO was introduced [RuCpCl(PTA)(PPh3)] (0.100
gr, 0.161 mmol) and Ag(CF3SO3) (0.041 gr, 0.161 mmol) the sus-
pension kept at 50 ꢀC for 20 min. The resulting solution was cooled
slowly at room temperature overnight. The obtained orange crys-
tals were filtered and dried under air, being good enough for single
crystal X-ray diffraction.
Into a NMR tube was dissolved 2 (0.018 g, 0.019 mmol) in 0.5 mL
of CDCl3 and then added n-propylamine (3.5 mL, 0.042 mmol). The
solution was analysed by NMR. The starting compound was
completely transformed in 3 and another compound that was
characterized as its isomer (3-isomer). The solution was studied by
NMR in the range from ꢁ40 to 60 ꢀC. The ratio between the 31P{1H}
NMR signals assigned to the two isomers was unchanged in the
temperature range studied.
Yield: 0.090 g, 69%. Elemental analysis for C32H38F3N3O4P2RuS2
(812.81): Found C, 47.01; H, 4.68; N, 4.85, S, 7.51%; calcd. C, 47.29; H,
4.71; N, 5.17; S, 7.89%. IR (KBr, cmꢁ1):
n
(OSO): 1250. 1H NMR
1H NMR (300.13 MHz, CDCl3):
d
0.91 (t, J ¼ 7.35 Hz, 3 H,
(300.13 MHz, CDCl3):
d
4.06e4.21 (m, 6 H, PTACH2P), 4.40e4.58 (m,
CH3CH2CH2N, 3-isomer), 0.62e1.11 (m, 2 H, CH3CH2CH2N, 3D3-
isomer), 2.45e3.05 (m, 2 H, CH3CH2CH2N, 3D3-isomer), 3.62e
4.90 (m, 24 H, PTA, 3D3-isomer), 4.97 (s, 5 H, Cp, 3-isomer), 6.37
(s, 1 H, HC]CPh2, 3-isomer), 6.96e7.61 (m, 30 H, aromatic, 3D3-
isomer), 9.56 (bs, 1 H, NH, 3-isomer). 13C{1H} NMR (75.467 MHz,
CDCl3): 244.12 (bt, 2JCP ¼ 11.9 Hz, Ru]CeC]C, 3-isomer). 31P{1H}
6 H, PTACH2N), 5.40 (s, 5 H, Cp), 7.60e7.82 (m, 15 H, aromatic). 13
C
{1H} NMR (75.467 MHz, CDCl3):
d
55.21 (d, JCP ¼ 15.25, NCH2P),
1
71.97 (d, 1JCP ¼ 6.09, NCH2N); 85.10 (s, Cp), 129.18e133.86 (m, ar-
omatic). 31P{1H} NMR (121.49 MHz, CDCl3):
d
ꢁ39.46 (d,
2JPP ¼ 37.77 Hz, PTA), 44.23 (d, 2JPP ¼ 37.78 Hz, PPh3).
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
3
NMR (121.49 MHz, CDCl3):
d
ꢁ40.20 (d, 2JPP ¼ 36.6 Hz, PTA, 29.5%,
C]C), 300.58 (bs, Ru]CeC]C). 31P{1H} NMR (121.49 MHz,
2
2
3), ꢁ38.66 (d, JPP ¼ 36.1 Hz, PTA, 20.5%, 3-isomer), 53.56 (d,
acetone-d6):
d
:
ꢁ40.15 (d, JPP ¼ 35.2 Hz, PTA), 44.19 (d,
2JPP ¼ 36.6 Hz, PPh3, 29.5%, 3), 55.50 (d, 2JPP ¼ 38.1 Hz, PPh3, 20.5%,
2JPP ¼ 35.2 Hz, PPh3). 19F{1H} NMR (282.40 MHz, acetone-d6):
3-isomer). 19F{1H} NMR (282.40 MHz, CDCl3):
d
ꢁ78.07 (s, CF3SO3).
d
ꢁ77.95 (s, CF3SO3).
2.6. Synthesis of [Ru(]C(NHCy)CH]CPh2)Cp(PTA)(PPh3)](CF3SO3)
(4)
2.9. Reactivity of [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2) with
EtSH
Using a similar procedure to that for 3, the complex 2 (0.20 g,
0.22 mmol) in 10 mL of CHCl3 was reacted with cyclohexylamine
(61.6 mL, 0.53 mmol) in 2 mL of CHCl3.
In an NMR tube EtSH (5.8 mL, 0.081 mmol) was added into a
solution of 2 (0.030 g, 0.032 mmol) in CDCl3 at room temperature
yielding in 5 min two compounds: complex 5 and 5-isomer. The
ratio between the 31P{1H} NMR signals assigned to the two iso-
mers was unchanged in the temperature range from ꢁ40 to
60 ꢀC.
Yield: 0.09 g, 41%. Elemental analysis for C51H55F3N4O3P2RuS
(1024.09): Found C, 59.86; H, 5.56; N, 5.24; S, 2.93%; calcd. C, 59.81;
H, 5.41; N, 5.47; S, 3.13%. IR (KBr, cmꢁ1): (C]C) 1641 (s). 1H NMR
n
(293 K, 300.13 MHz CDCl3):
d 0.52e1.80 (bm, 10 H, (CH2eCH2)2e
1H NMR (300.13 MHz, acetone-d6):
d
1.29 (t, 3JHH ¼ 7.26 Hz, 3 H,
CH2eN), 2.64 (bm, 2 H, CH2eN), 3.69e4.44 (m, 12 H, PTA), 5.00 (s,
5 H, Cp), 5.93 (s, 1 H, HC]CPh2), 6.98e7.68 (m, aromatic, 25 H),
8.98 þ 9.05 (bs þ bs, 2H, CyNH2-C]Ru). 13C{1H} NMR (75.467 MHz,
3
CH3CH2S, 5-isomer), 2.71 (q, JHH ¼ 7.26 Hz, 2 H, CH3CH2S, 5-
isomer), 4.36e4.54 (m, 12 H, PTA, 5D5-isomer), 5.41 (s, 5 H, Cp,
5-isomer), 5.90 (s, 1 H, HC]CPh2, 5-isomer), 7.04e7.68 (m, 25 H,
aromatic, 5D5-isomer). 13C{1H} NMR (75.467 MHz, CDCl3): 305.78
(bs, Ru]CeC]C, 5-isomer). 31P{1H} NMR (121.49 MHz, acetone-
CDCl3):
d 25.03 (s, NCy), 36.55 (s, NCy), 50.45 (s, NCy), 56.12 (bs,
PTACH2P), 72.48 (s, PTACH2N), 85.16 (s, Cp), 122.92 (q, CF3SO3),
125.92e135.88 (m, aromatic), 137.03 (s, Ru]CeC]C), 141.00 (s,
d6):
d
: ꢁ40.15 (d, 2JPP ¼ 35.2 Hz, PTA, 5), ꢁ38.90 (d, 2JPP ¼ 34.6 Hz,
2
Ru]CeC]C), 239.09 (bt, JCP ¼ 12.2 Hz, Ru]CeC]C). 31P{1H}
2
PTA, 5-isomer), 44.19 (d, JPP ¼ 35.2 Hz, PPh3, 5), 49.66 (d,
2
NMR (121.49 MHz, CDCl3):
d
ꢁ41.36 (d, JPP ¼ 36.4 Hz, PTA), 53.87
2JPP ¼ 34.6 Hz, PPh3, 5-isomer). 19F{1H} NMR (282.40 MHz,
(d, 2JPP ¼ 36.4 Hz, PPh3). 19F{1H} NMR (282.40 MH, CDCl3):
ꢁ78.76
d
acetone-d6):
d
ꢁ77.95 (s, CF3SO3).
(s, CF3SO3).
2.7. Reactivity of [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2) with
2.10. Reactivity of [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2)
CyNH
with H2O in acetone-d6
An NMR tube was filled with 2 (0.020 g, 0.022 mmol) and
Into a 5 mm NMR tube under N2 atmosphere was added 10 mg
0.5 mL of CDCl3, after that cyclohexylamine (6.16
m
L, 0.054 mmol)
of 2 (0.01 mmol), 0.5 mL of acetone-d6 and 50 mL of H2O (2.8 mmol).
was added. The starting compound was transformed after 10 min
at room temperature into two compounds: 4 and 4-isomer. The
ratio between the 31P{1H} NMR signals assigned to the two iso-
mers was unchanged in the temperature range from ꢁ40 to
60 ꢀC.
The resulting solution was kept at room temperature. No significant
changes were observed by 13P{1H} NMR after 48 h. The temperature
was increased at 50 ꢀC. After 36 h the starting complex was fully
transformed into a mixture of compounds that could not be
identified.
1H NMR (293 K, 300.13 MHz CDCl3):
d 0.50e1.85 (m, 20 H, (CH2e
CH2)2eCH2eN, 4D4-isomer), 2.65 (bm, 4 H, CH2eN, 4D4-isomer),
3.64e4.48 (m, 24 H, PTA, 4D4-isomer), 4.86 (s, 5 H Cp, 4-isomer),
5.93 (s, 1 H, HC]CPh2, 4-isomer), 6.38 (s, 1 H, HC]CPh2, 4-
isomer), 6.98e7.68 (m, aromatic, 50 H, 4D4-isomer), 8.33 þ 8.38
(bs þ bs, 2H, CyNH2-C]Ru, 4-isomer). 13C{1H} NMR (75.467 MHz,
2.11. Reactivity of [Ru(C]C]CPh2)Cp)(PTA)(PPh3](CF3SO3) (2)
with O2
Into an NMR tube was introduced 2 (0.016 g, 0.017 mmol) and
0.5 mL of CDCl3. The solution was chilled in an ice-acetone bath and
O2 was bubbled through for 10 min. The tubes were sealed and
studied using 31P{1H} NMR. No significant change was observed
after 1 day at room temperature.
CDCl3):
d
241.08 (bt, 2JCP ¼ 11.2 Hz, Ru]CeC]C, 4-isomer). 31P{1H}
NMR (121.49 MHz, CDCl3):
d
ꢁ39.82 (d, 2J ¼ 38.9 Hz, PTA, 4-
isomer), ꢁ41.36 (d, 2J ¼ 36.4 Hz, PTA, 4), 53.87 (d, 2J ¼ 36.4 Hz,
PPh3, 4), 54.83 (d, 2J ¼ 38.9 Hz, PPh3, 4-isomer). 19F{1H} NMR
(282.40 MH, CDCl3):
d
ꢁ78.76 (s, CF3SO3).
2.12. Synthesis of [Ru(C]C]CPh2)Cp(HPTA)(PPh3)](BF4)2 (6)
2.8. Synthesis of [Ru(]C(SEt)CH]CPh2)Cp(PTA)(PPh3)](CF3SO3)
(5)
Reaction of 2 (0.050 g, 0.054 mmol) with HBF4$Et2O (15
mL,
0.11 mmol) in 10 mL of CHCl3 for 2 h led to a purple solution that
was evaporated to 1 mL. Addition of 5 mL of Et2O gave rise to a
purple powder that was filtered, washed with Et2O (2 ꢂ 2 mL) and
dried under vacuum.
Complex 5 was prepared by using a similar procedure to that of
3 and 4, a solution of EtSH (38.7 mL, 0.53 mmol) in 2 mL of CHCl3
was added into a solution of 2 (0.20 g, 0.22 mmol) in 10 mL of
CHCl3.
Yield: 0.08 g, 37%. Elemental analysis for C47H49F3N3O3P2RuS
(988.06): Found C, 56.96; H, 5.11; N, 4.18; S, 6.21%; calcd. C,
Yield: 0.046 g, 89%. Elemental analysis for C44H43B2F8N3P2Ru
(950.46): Found C, 55.41; H, 4.87; N, 4.28%; calcd. C, 55.60; H, 4.56;
N, 4.42%. IR (KBr, cmꢁ1):
n
(PTANHþ) 2587 (bm),
n
(C]C]C) 1947
57.13; H, 5.00; N, 4.25; S, 6.49%. IR (KBr, cmꢁ1):
n
(C]C) 1635 (s).
(vs). 1H NMR (300.13 MHz, CDCl3):
d 3.8e4.02 (m, 6 H, PTACH2P),
3
1H NMR (300.13 MHz, acetone-d6):
d
1.20 (t, JHH ¼ 7.4 Hz, 3 H,
4.55e4.68 (m, 6 H, PTACH2N), 5.45 (s, 5 H, Cp), 6.35 (bs, NH), 7.28e
3
CH3CH2S), 2.53 (q, JHH ¼ 7.4 Hz, 2 H, CH3CH2S), 3.83e4.50 (m,
12 H, PTA), 5.08 (s, 5 H, Cp), 5.52 (s, 1 H, HC]CPh2), 7.04e7.68
(m, 25 H, aromatic). 13C{1H} NMR (75.467 MHz, acetone-d6):
7.61 (m, 25 H, aromatic). 13C{1H} NMR (75.467 MHz, CDCl3):
d
52.47
1
(d, JCP ¼ 17.5 Hz, NCH2P), 65.79 (s, NCH2N), 71.47 (s, NCH2NHþ),
91.09 (s, Cp), 128.96e135.24 (m, aromatic), 163.07 (s, Ru]C]C]C),
d
24.77 (s, CH3CH2S), 39.78 (s, CH3CH2S), 54.84 (d, 1JCP ¼ 13.0 Hz,
200.51 (s, Ru]C]C]C), 292.86 (t, 2JCP ¼ 17.3 Hz, Ru]C]C]C). 31
P
2
NCH2P, 72.07 (s, NCH2N), 89.45 (s, Cp), 119.15 (s, CF3SO3), 127.86e
133.48 (m, aromatic), 137.45 (s, Ru]CeC]C), 141.34 (s, Ru]Ce
{1H} NMR (121.49 MHz, CDCl3):
d
ꢁ21.44 (d, JPP ¼ 33.0 Hz, PTA),
50.10 (d, 2JPP ¼ 33.0 Hz, PPh3).
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

4
M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
2.13. X-ray structure determinations
after 5 h (90% transformation). A similar reaction was made using
10 equiv of ethoxyethene and 1-methoxycyclohexa-1,3-diene,
obtaining the stoichiometric conversion of the compounds
respectively into deuteroacetaldehyde and EtOD, and 2,2-
dideuterocyclohex-3-enone and MeOD in 2 h.
Data for compound 1 were collected on a Bruker APEX CCD
diffractometer (XDIFRACT service of the University of Almería)
ꢀ
using graphite monochromated Mo K
a
radiation (
l
¼ 0.7107 A) at
100 K. The crystal parameters and experimental details of the data
collection are summarized in Table 1. The structures were solved by
direct methods with SIR92 [11] and refined by full-matrix least
squares methods with SHEL-XTL [12] and refined by least-squares
procedures on F2. Final geometrical calculations and graphical
manipulations were carried out with the SHELXS-XTL package [12].
All the non-hydrogen non-disordered atoms were refined with
anisotropic atomic displacement parameters. All hydrogen atoms
were included in calculated positions and refined using a riding
model.
3. Results and discussion
3.1. Reactivity of [RuCpCl(PTA)(PPh3)] with HC^CPh and HC^Ce
CH2eC(OH)Ph2. Synthesis and characterization of [Ru(C]C]CPh2)
Cp(PTA)(PPh3)](CF3SO3) (2)
The reaction of the hydrosoluble complex [RuCpCl(PTA)(PPh3)]
with phenylacetylene in different solvents (CD3OD, CDCl3, D2O,
CD2Cl2, DMSO-d6, acetone-d6) did not afford the expected ruthe-
nium vinylidene complexes. Addition of mild (NaBF4) or strong,
Ag(CF3SO3), halide scavengers or bases (NEt3) also did not produce
the desired unsaturated carbene. Reaction of [RuCpCl(PTA)(PPh3)]
with Ag(CF3SO3) and HC^CPh in DMSO provided crystals suitable
for single crystal X-ray diffraction determination of the complex
2.14. Catalytic cleavage of 1,4-butanediol-divinyl-ether in water
2.9 mg of 2 (3.14 ꢂ 10ꢁ3 mmol) were introduced in a 5 mm
NMR tube that was repeatedly evacuated and filled with nitro-
[RuCp(DMSO-kS)(PTA)(PPh3)] (1). To check the role of HC^CPh in
gen. The substrate 1,4-butanediol-vinyl-ether (10 equiv, 5.8
ml,
the reaction the complex [RuCpCl(PTA)(PPh3)] was reacted with
Ag(CF3SO3) in DMSO. The reaction provided 1 in good yield,
showing that the presence of HC^CPh in the reaction media is not
necessary for its synthesis (Scheme 1).
7.5e9
m
l, 50 ꢂ 10ꢁ3 mmol) was then added together with 0.5 mL
of D2O and 0.5 mL of CDCl3 to obtain a purple homogeneous
mixture, which was checked by 1H NMR spectroscopy at room
temperature. After 2 h the complete cleavage of the substrate Oe
Cvinyl bond was observed to give ethanal and 2-methyl-[1,3]
dioxepane in quantitative yield. After this time, CDCl3 (1 mL) was
added to extract the organic soluble species. The organic solution
was analysed by 1H NMR spectroscopy that showed the complete
transformation of 1,4-butanediol-divinyl-ether. After separation
of the organic phase, the aqueous layer, which partially retains
the catalyst, was proved to be catalytically active during 4
ꢁ
The crystal structure of 1 (Fig. 1) is constituted by a CF3SO3
anion and a cationic piano-stool complex made by a ruthenium
bonded to one
h
5-Cp, a DMSO by the S atom, one PTA and PPh3
molecules bonded by their P atom. Distances and angles into the
crystal are in the range found for similar complexes (Fig. 1) [13].
At variance with the reaction with HC^CPh, treatment of the
same ruthenium precursor [RuCpCl(PTA)(PPh3)] with 1,1-diphenyl-
2-propyn-1-ol in the presence of silver triflate follows the expected
Selegue’s reaction [14] and provides an easy access to the allenyli-
dene ruthenium complex 2 (Scheme 2). The metal allenylidene 2 is
soluble in common organic solvents in which it has been charac-
terized by conventional IR and NMR spectroscopic techniques.
additional runs carried out by adding each time 5.8
mL of 1,4-
butanediol-divinyl-ether. A complete (100%) substrate conver-
sion was achieved after 2.8 h in the second and third catalytic
test, while only 60% was converted in the fourth run and the
complete transformation of the substrate was not achieved
Complex 2 is slightly soluble also in water (S25 C(mg mLꢁ1) ¼ 0.1),
ꢀ
reflecting the presence of only one PTA ligand in the coordination
pocket around ruthenium.
Table 1
Crystallographic data for 1.
Analysis of the 13C{1H} NMR spectrum of 2 provides the most
important evidence to confirm the formation of ruthenium alle-
nylidene complex. A neat triplet slightly below 293.73 ppm, char-
1
Formula
Mr
C32H38F3N3O4P2RuS2
812.78
P 2(1)/c
Monoclinic
9.4616(7)
21.2244(17)
16.6505(12)
90.00
92.550(2)
90.00
3340.4(4)
4
1.616
1664
acteristic of the allenylidene
phosphines P-atoms, is observed for the complex as well as signals
ascribable to both - and -carbons, which have the expected
chemical shift for this kind of carbon atoms ( -C: 207.70 ppm -C:
158.56 ppm). The allenylidene complex maintains its nature in the
solid state, as confirmed by the strong characteristic allenylidene
a-carbon coupled to the two
Space group
Cryst system
b
g
ꢀ
b
g
a/A
ꢀ
b/A
ꢀ
c/A
a/deg
stretching absorption band observed in their solid IR spectra (n(C]
b/deg
C]C) cmꢁ1: 1930 cmꢁ1).
g
/deg
3
ꢀ
V/A
Z
3.2. Reactivity of the allenylidene [Ru(C]C]CPh2)
Cp(PTA)(PPh3)](CF3SO3) (2) with nucleophiles
Dc/g cmꢁ3
F(000)
m
(Mo K
a
)/cmꢁ1
7.13
The allenylidene [Ru(C]C]CPh2)Cp(PTA)(PPh3)](CF3SO3) (2)
is stable under O2 in CDCl3 and in the presence of H2O in
acetone-d6 at room temperature for more than 1 day but their
reactivity against nucleophiles n-propylamine, cyclohexylamine
and ethanethiol was studied under an inert atmosphere in order
to avoid the possible effects of the H2O and O2 mixture on both
reaction intermediates and final products. Following the well-
known reactivity of allenylidene complexes, which is different
along the three carbons chain [15], complex 2 conforms to the
classical behaviour expected for such class of unsaturated
Measd reflcns
Unique reflcns
Rint
12,444
4710
0.0335
4436
2.15e23.28
ꢁ10, 10; ꢁ23, 23; ꢁ15, 18
0.0392
0.0766
434
Obsd reflcns [I ꢃ 2
s(I)]
ꢀ
qmin
e
qmax
/
hkl ranges
R(F2) (obsd reflcns)
wR(F2) (all reflcns)
No. of variables
Goodness of fit
1.045
ꢁ0.394, 0.575
ꢀꢁ3
rmin
,
rmax/e A
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
5
Scheme 1. Reactivity of [RuCpCl(PTA)(PPh3)] with HC^CPh in different solvents and synthesis of 1.
carbenes [16]. Thus, it reacts with soft bases (n-propylamine,
cyclohexylamine and ethanethiol) giving the respective amino-
and thio-carbene complexes. The resonance structure with a
The resulting amino and thio-carbene complexes were fully
characterized by spectroscopic methods including multinuclear
NMR and IR spectroscopies. The infrared spectra of 3, 4 and 5 do not
double bond between the C
a
carbon and the nitrogen atom
display the
medium intensity absorption about 1620 cmꢁ1 due to the charac-
teristic
(C]C) for rutheniumecarbene complexes [18]. The 1H
NMR spectra support the proposed structure i.e. the typical features
of the unsaturated Fischer carbene moieties. 13C{1H} NMR spec-
troscopy provides also a further support to these structural as-
n(C]C]C) band featuring the IR of the precursor 2 but
(azoniabutadienyl) used to be more important in metal amino-
carbenes than a single bond between both atoms [17]. Never-
theless, this last possible structure was supported for complexes
3 and 4 as NH-resonances were observed in their 1H NMR
(Scheme 3), which were not significantly changed when the
temperature was modified in the range from ꢁ40 to 40 ꢀC. In the
same temperature range no substantial changes were observed
in the 31P{1H} NMR of the three ruthenium carbene complexes.
Therefore, the basic NPTA atoms do not interfere with the reac-
tivity of the allenylidene ligand. This fact is important as it in-
dicates that it could be possible to use the PTA ligand in presence
of allenylidene ligands without loss of its known properties.
n
signments with
observed for the
a
a
characteristic multiplet around 240 ppm
-carbon in each complex, produced by the
coupling of the carbene a-carbon with the phosphorus atoms.
Two isomers should be obtained by reaction of the allenylidene
2, containing PPh3 and PTA phosphine ligands, with nucleophiles.
In fact, depending on the face where the nucleophilic reagent in-
teracts with the allenylidene, two different carbene complexes
should be obtained, for example by reaction of 2 with n-propyl-
amine (Fig. 2). A rationale to account for the existence of two iso-
mers is related with the occurrence of a high rotational barrier
around the ruthenium-a-carbon that confines the two phosphines
in different hemi-spaces.
Pathways A and B have different probability of occurring,
reflecting the different bulkiness of PPh3 and PTA and therefore a
different proportion of the two isomers should be expected. In
contrast with this expectation, 31P{1H} NMR studies of isolated
samples of complexes 3, 4 and 5 dissolved in CDCl3 show only one
AB spin system thus pointing out that a single isomer is always
formed from the reaction of 2 with each of the three nucleophiles.
Fig. 1. The diagram shows the complex cation of 1 with atom labelling for the metal
coordination environments (hydrogens have not been included for clarity). Selected
ꢀ
bond distances (A) and angles (deg) for 1: Ru e P1 ¼ 2.3330(9), Ru e P2 ¼ 2.3076(9), Ru
e S ¼ 2.2617(9), Ru ꢁ Cp(centroid) ¼ 1.888; P1 e Ru e P2 ¼ 94.16(3), P1 e Ru1 e
S ¼ 95.18(3), P2 e Ru1 e S ¼ 90.71(3).
Scheme 2. Synthesis of the allenylidene ruthenium complex 2.
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

6
M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
Scheme 3. Synthesis of 3, 4 and 5, and their respective isomers.
However, repeating the reaction of 2 with n-propylamine in an
NMR tube discloses the formation of two AB spin systems (two
doublets of doublets) with an integral ratio of ca. 41e59% (Fig. 3),
which clearly indicates that two different isomers of ruthenium n-
propylamine-carbene containing PTA and PPh3 are formed. The
synthesis of two isomers is also supported by the 13C{1H} NMR
where two multiplets at ca. 244 and 241 ppm are evident (Fig. 3).
The obtained solution containing both isomers was studied by NMR
spectroscopy in the temperature range from ꢁ40 to 60 ꢀC. The re-
sults obtained showed as in CDCl3 both isomers do not interconvert
each other in the studied temperature range. No attempt was made
to isolate the complexes 3-isomer as well as those of the other
Fischer carbenes 4-isomer and 5-isomer.
and 3-isomer. Although such evidence is only qualitative and needs
further support by other experimental and theoretical studies, it is
conceivable that steric requirements mainly drive the reaction
between the nucleophile and the ruthenium allenylidene complex
2, favouring the formation of the less crowded isomer that, even-
tually, can be isolated in the solid state.
Finally, the reaction of the allenylidene complex 2 with HBF4 led
to the protonation of the PTA ligand instead of the expected
ruthenium carbyne complex (Scheme 4). The complex [Ru(C]C]
CPh2)Cp(HPTA)(PPh3)](BF4)2 (6) was still obtained from the reac-
tion even in high excess of acid, temperature and solvents used.
This result shows that in 2 the PTA ligand displays a more basic
character than the allenylidene ligand.
As commented previously the reaction of [RuCpCl(PTA)(PPh3)]
with Ag(CF3SO3) in DMSO provided crystals suitable for X-ray
determination of the structure of complex [RuCp(DMSO-
3.3. Catalytic tests: study of the catalytic activity of 2 to the trans-
etherification of 1,4-butanediol-divinyl-ether, ethoxyethene and 1-
methoxycyclohexa-1,3-diene
kS)(PTA)(PPh3)] (1). The cone angle of the PPh3 and PTA phosphines
obtained from the structure of 1 may be indicative for the parent
ruthenium allenylidene complex 2 [19]. The calculated values are
133ꢀ for the PPh3 and 109ꢀ for the PTA, which are in agreement
with those found for others PTA and PPh3 ruthenium complexes. As
an interesting coincidence, the calculated ratio between the cone
angles of the two ligands is 1.22, which is similar to the 31P{1H}
NMR integral ratio (1.43) for the two rutheniumecarbene isomers 3
The allenylidene complex 2 was evaluated for the trans-ether-
ification of 1,4-butanediol-vinyl-ether [4]. The experimental results
showed that this complex is a very good catalyst for the selective
and stoichiometric cleavage of the vinyl-ether bond of the substrate
at room temperature in D2O/CDCl3 in 2 h. Complex 2 is therefore a
rival for the only previously known active catalyst [{RuCl(m-Cl)(C]
Fig. 2. Carbene isomers resulting from the reaction of 2 with n-propylamine.
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
7
3
3 -isomer
Fig. 3. 31P{1H} NMR and 13C{1H} NMR spectra of the in situ reaction at room temperature of 1 with n-propylamine in CDCl3 and the assignation with the isomeric pair 3 and 3-
isomer.
C]CPh2)(TPPMS)2}2]Na4 [TPPMS
¼
Ph2P{C6H4-3-OS(O)ꢁ2 }] for
4. Conclusions
this reaction, which needs 2.5 h at 47 ꢀC in D2O=CDCl3 ½4ꢄ. Both
catalysts catalyse the reaction providing the same final compounds
in almost stoichiometric yield: the ethanal and 1,4-butandiol,
which condense intermolecularly to generate 2-methyl-[1,3]diox-
epane (Scheme 5 a). Moreover, complex 2 remains catalytically
active after additional catalytic runs. Indeed, after extraction of the
organic phase, the aqueous phase, which contained the catalyst,
was shown to be catalytically active during 3 additional runs with
100% substrate conversion after 2.8 h in the second and third cat-
alytic test, while a decrease activity to a moderate 60% trans-
formation was measured in the fourth run when the transformation
of the substrate was not yet completed after 5 h (90%). The
substrates ethoxyethene and 1-methoxycyclohexa-1,3-diene
were selected to assess the possible use of 2 as a general
catalyst for the cleavage of vinyl-ethers. Both substrates were
quantitatively transformed in 2 h at room temperature into the
corresponding acetaldehyde-d1 and EtOD (Scheme 5 b), and 2,2-
dideuterocyclohex-3-enone and EtOD (Scheme 5 c), showing that
2 is a general catalyst for the trans-etherification of vinyl-ethers in
mild conditions.
An allenylidene ionic complex incorporating the hydrosoluble
phosphine PTA has been synthezised and properly characterized in
solution by NMR and IR techniques. The complex is soluble in
organic solvents and shows low but some solubility in water. The
metal allenylidene complex is air and water stable in both solid
state and solution at room temperature and reacts with n-propyl-
amine, ethanethiol and cyclohexylamine through a classical route
providing two isomers of the expected amino- and thio-carbenes. A
rationale to account for the existence of two isomers is related with
the occurrence of a high rotational barrier around the ruthenium-a-
carbon that confines the two phosphines in different hemi-spaces.
Complex 2 is actually the best catalyst for the trans-etherification of
1,4-butanediol-divinyl-ether and also uses the mildest conditions.
The ligand PTA, which contains nucleophilic N atoms, does not
affect significantly the known reactivity of the allenylidene ligand.
Inclusion into the complex molecule of more than one PTA mole-
cule or more hydrosoluble PTA derivatives should provide new
water-soluble allenylidene complexes with catalytic efficiencies
similar to those of related species soluble in organic solvents.
Scheme 4. Synthesis of 6.
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040

8
M. Serrano-Ruiz et al. / Journal of Organometallic Chemistry xxx (2013) 1e8
(2009) 1546e1557;
(e) C. Bruneau, P.H. Dixneuf (Eds.), Metal Vinylidenes and Allenylidenes in
Catalysis: from Reactivity to Applications in Synthesis, Wiley-VCH, Weinheim,
D, 2008;
(f) H. Katayama, F. Ozawa, Coord. Chem. Rev. 248 (2004) 1703e1715;
(g) C. Bruneau, P.H. Dixneuf, Angew. Chem. Int. Ed. 45 (2006) 2176e2203;
(h) B.M. Trost, Acc. Chem. Res. 35 (2002) 695e705 and references therein;
(i) V. Cadierno, M.P. Gamasa, J. Gimeno, Eur. J. Inorg. Chem. (2001) 571e591;
(j) M.I. Bruce, Chem. Rev. 98 (1998) 2797e2858;
(k) M.I. Bruce, Chem. Rev. 91 (1991) 197e257;
(l) C. Bruneau, P.H. Dixneuf, Acc. Chem. Res. 32 (1999) 311e323.
[3] M. Saoud, A. Romerosa, M. Peruzzini, Organometallics 19 (2000) 4005e4007.
[4] M. Saoud, A. Romerosa, S. Mañas, L. Gonsalvi, M. Peruzzini, Eur. J. Inorg. Chem.
(2003) 1614e1619.
[5] T. Campos-Malpartida, M. Fekete, F. Joó, Á. Kathó, A. Romerosa, M. Saoud,
W. Wojtków, J. Organometal. Chem. 693 (2008) 468e474.
[6] S. Bolaño, M.M. Rodríguez-Rocha, J. Bravo, J. Castro, E. Oñate, M. Peruzzini,
Organometallics 28 (2009) 6020e6030.
[7] D.N. Akbayeva, L. Gonsalvi, W. Oberhauser, M. Peruzzini, F. Vizza,
P. Brüggeller, A. Romerosa, G. Sava, A. Bergamo, Chem. Commun. (2003) 264e
265.
Scheme 5. trans-Etherification of vinyl-ethers catalysed by 2 at room temperature in
D2O/CDCl3.
Experiments are in progress in order to synthesize these new
water-soluble metal complexes and to study their possible catalytic
properties in water.
[8] F. Joó, J. Kovacs, Á. Katho, A.C. Benyei, T. Decuir, D.J. Darensboug, Inorg. Synth.
31 (1998) 2.
[9] C. Lidrissi, A. Romerosa, M. Saoud, M. Serrano-Ruiz, L. Gonsalvi, M. Peruzzini,
Angew. Chem. Int. Ed. 44 (2005) 2568e2572.
Acknowledgements
[10] (a) A. Romerosa, T. Campos-Malpartida, C. Lidrissi, M. Saoud, M. Serrano-Ruiz,
M. Peruzzini, J.A. Garrido-Cárdenas, F. García-Maroto, Inorg. Chem. 46 (2006)
1289e1298;
Financial support co-provided by the EU FEDER: the Spanish
MINECO (CTQ2010-20952) and Junta de Andalucía through PAI
(research teams FQM-317) and Excellence Projects P07-FQM-03092
and P09-FQM-5402. Thanks are also given to COST Action CM0802
PHOSCINET (WG2). M. Serrano-Ruiz is grateful to Excellence proj-
ect P09-FQM-5402 for a postdoctoral contract. We thanks to S.
Callear (ISIS-RAL-U.K.) for reading and correcting the manuscript.
(b) A. Romerosa, M. Saoud, T. Campos-Malpartida, C. Lidrissi, M. Serrano-Ruiz,
M. Peruzzini, J.A. Garrido-Cárdenas, F. García-Maroto, Eur. J. Inorg. Chem.
(2007) 2803e2812.
[11] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M.C. Burla, G. Polidori,
M. Camalli, J. Appl. Crystallogr. 27 (1994) 435.
[12] G.M. Sheldrick, SHELXTL Vesion 6.14, Bruker-AXS, Madison, W1, USA, 2003.
[13] (a) A.D. Phillips, L. Gonsalvi, A. Romerosa, F. Vizza, M. Peruzzini, Coord. Chem.
Rev. 248 (2004) 955e993;
(b) J. Bravo, S. Bolaño, L. Gonsalvi, M. Peruzzini, Coord. Chem. Rev. 254 (2010)
555e607;
Appendix A. Supporting information
(c) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 110 (2010)
4178e4235;
(d) L. Gonsalvi, M. Peruzzini, Phosphorus Compounds, Catalysis by Metal
Complexes, 2011, vol. 37 (Chapter 7), Springer Science.
[14] J.P. Selegue, Organometallics 1 (1982) 217e218.
[15] C. Bruneau, Ruthenium Vinylidenes and Allenylidenes in Catalysis, in: C.
Bruneau, P. Dixneuf, (Eds.), Ruthenium Catalysis and Fine Chemistry, Top.
Organomet. Chem. 11 (2004) 125e153.
[16] (a) H. Kopf, B. Holzberger, C. Pietraszuk, E. Hübner, N. Burzlaff, Organome-
tallics 27 (2008) 5894e5905;
CCDC 948186 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
References
[1] (a) C. Fellay, P.J. Dyson, G. Laurenczy, Angew. Chem. Int. Ed. 47 (2008) 3966e
3968;
(b) A. Asensio, M.L. Buil, M.A. Esteruelas, E. Oñate, Organometallics 23 (2004)
5787e5798;
(c) M.L. Buil, M.A. Esteruelas, A.M. López, E. Oñate, Organometallics 22 (2003)
5274e5284;
(d) M.L. Buil, M.A. Esteruelas, A.M. López, E. Oñate, Organometallics 22 (2003)
162e171.
(b) F. Joó, Á. Kathó, in: J.G. de Vries, C.J. Elsevier (Eds.), Handbook of Homo-
geneous Hydrogenation, Wiley-VCH, Weinheim, D, 2007, p. 1327;
(c) C.J. Li, Chem. Rev. 105 (2005) 3095e3165;
(d) B. Cornils, W.A. Herrmann, I.T. Horváth, W. Leitner, S. Mecking, H. Olivier-
Bourbigou, D. Vogt (Eds.), Multiphase Homogeneous Catalysis, Wiley-VCH, D.
Weinheim, 2005;
(e) D.J. Adams, P.J. Dyson, S.J. Tavener, Chemistry in Alternative Reaction
Media, Wiley, Chichester, UK, 2004;
(f) B. Cornils, W.A. Herrmann, Aqueous-phase Organometallic Catalysis, sec-
ond ed., Wiley-VCH, Weinheim, D, 2004;
[17] D.J. Bernad, M.A. Esteruelas, A.M. López, J. Modrego, M. Carmen Puerta,
P. Valerga, Organometallics 18 (1999) 4995e5003.
[18] C. Bianchini, M. Peruzzini, F. Zanobini, C. López, I. de los Rios, A. Romerosa,
Chem. Commun. (1999) 443e444.
[19] The half cone angle is defined by the angle between the Ru-P bond axis and
the line from Ru to a point tangent to the van der Waals hydrogen radius. The
point tangent to the van der Waals hydrogen radius is obtained by extending
the CeH bond axis from 1.0 Å to 2.1 Å, assuming the van der Waals radius of H
to be 1.1 Å. Doubling this angle gives the Tolman’s steric factor, id est the
ligand cone angle. (a) C.A. Tolman, J. Am. Chem. Soc. 92 (1970) 2956e2965;
(b) J.R. Delerno, L.M. Trefonas, M.Y. Darensbourg, R.J. Majeste, Inorg. Chem. 15
(1976) 816e819.
(g) F. Joó, Aqueous Organometallic Catalysis, Kluwer, Dordrecht, NL, 2001.
[2] (a) A.H. Hoveyda, S.J. Malcolmson, S.J. Meek, A.R. Zhugralin, Angew. Chem. Int.
Ed. 49 (2010) 34e44;
(b) G.C. Voigioukalakis, R.H. Grubbs, Chem. Rev. 110 (2010) 1746e1787;
(c) V. Cadierno, P. Crochet, J. Gimeno, in: Metal Vinylidenes and Allenylidenes
in Catalysis, Wiley-VCH, Weinheim, D, 2008, p. 61;
(d) J.A. Pino-Chamorro, E. Bustelo, M.C. Puerta, P. Valerga, Organometallics 28
Please cite this article in press as: M. Serrano-Ruiz, et al., Journal of Organometallic Chemistry (2013), http://dx.doi.org/10.1016/
j.jorganchem.2013.08.040