A study of the coordination ability of 2,5-di(2-pyridyl)phospholes on Ru centres

Article abstract of DOI:10.1016/S0022-328X(02)01803-X

The coordination behaviour of the readily available 1-phenyl-2,5-di(2-pyridyl)phosphole (NPN) toward Ru centres was investigated. Neutral and ionic compounds of formula [RuCl(p-cymene)(NPN)]TfO (TfO = CF₃SO₃)... (1), [RuCl(p-cymene)(

Full text of DOI:10.1016/S0022-328X(02)01803-X

Journal of Organometallic Chemistry 663 (2002) 118ꢂ126
/
www.elsevier.com/locate/jorganchem
A study of the coordination ability of 2,5-di(2-pyridyl)phospholes on
Ru centres
Agust´ın Caballero a, Fe´lix A. Jalo´n a,ꢀ, Blanca R. Manzano a, Mathieu Sauthier b,
Loıc Toupet c, Re´gis Re´au b
¨
a
´ ´ ´ ´ ´
Departamento de Quımica Inorganica, Organica y Bioquımica, Facultad de Quımicas, Universidad de Castilla-La Mancha, Avda. Camilo J. Cela 10,
13071 Ciudad Real, Spain
Organometalliques et Catalyse, Chimie et Electrochimie Mole`culaires, UMR 6509 CNRS-Universite de Rennes 1, Institut de Chimie de Rennes,
b
´
Campus de Beaulieu, 35042 Rennes Cedex, France
´
c
´ ´
Groupe Matie`re Condensee et Materiaux, UMR 6626, CNRS-Universite de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
Received 24 May 2002; accepted 1 August 2002
Dedicated to Professor P. Royo on the occasion of his 65th birthday and for his outstanding contribution to organometallic chemistry
Abstract
The coordination behaviour of the readily available 1-phenyl-2,5-di(2-pyridyl)phosphole (NPN) toward Ru centres was
investigated. Neutral and ionic compounds of formula [RuCl(p-cymene)(NPN)]TfO (TfOꢁCF3SO3). . . (1), [RuCl(p-cyme-
ne)(NPN)]BF4 (2), [RuCl(C6Me6)(NPN)]TfO (3), RuCp?Cl(NPN) [Cp?ꢁ
C5H5 (4), C5Me5 (5)], Ru(C5Me5)(s1-C8H13)(NPN) (6),
RuCl2(NPN)2 (7) and RuClH(cod)(NPN) (codꢁ1,5-cyclooctadiene) (8) were obtained. Two diastereomers were obtained for 1, 2
and 4, (a, b) while three were found in the case of 8 (aꢂc). According to NMR spectroscopy, the 2,5-bis(2-pyridyl)phosphole acts as
/
/
/
/
a 1,4-P,N chelate ligand in all cases. This behaviour was confirmed by an X-ray diffraction study performed on complex 1a. Proton
transfer studies on complex 8 demonstrated the influence of the molecular structure on the ability to form dihydrogen bridges.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium complexes; Phospholes; Hydrides
1. Introduction
behaviour. This compound can act as a monodentate P-
donor toward W(CO)5 [4a], as an N,P-chelate toward
Pd(II) centres [5a] or as a tridentate N,P,N-ligand on a
Phospholes have been extensively used as ligands in
coordination chemistry and homogeneous catalysis [1].
They act as classical two-electron donor tertiary phos-
phines towards transition metals due to the lack of
endocyclic delocalization of the phosphorus lone pair
[2]. Functionalisation of the heterocyclic phosphole ring
in 2- or 2,5-positions by coordinative moieties offers the
possibility to obtain polydentate ligands [3]. 1-Phenyl-
2,5-di(2-pyridyl)phosphole (NPN, Scheme 1) is a stable
dicationic Pd(I)ꢂPd(I) fragment [5b] (Scheme 1). The
/
chelate P,N-coordination offers a free basic pyridyl
group close to the metal centre. This feature can allow
performing ligandꢂ
dihydrogen bridges through interaction between metalꢂ
hydride and pyridylꢂproton moieties, processes that
/
metal hydrogen transfer or to force
/
/
give rise to interesting reactivity properties [6]. Such
phenomena have been observed with different transition
metals including ruthenium [7]. Herein, we report a
study on the coordination ability of 2,5-di(2-pyri-
dyl)phosphole NPN with different Ru-containing frag-
ments and protonation experiments of one of the
resulting complexes.
derivative, readily available via the ‘one pot’ Faganꢂ
Nugent route [4], which presents a versatile coordination
/
ꢀ Corresponding author. Fax: ꢃ
E-mail address: felix.jalon@uclm.es (F.A. Jalo´n).
/34-926-295-318
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 8 0 3 - X

A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ
/126
119
Scheme 1.
2. Results and discussion
was formed upon coordination on an ‘(arene)RuCl’
moiety [8]. In marked contrast, according to the 1H- and
13C{1H}-NMR data, complexes with 2,5-di(2-pyri-
dyl)phosphole ligand are obtained as a mixture of two
diastereoisomers noted a and b (Scheme 3: 1a/1b and 2a/
2b, 5/1 ratio; 4a/4b, 3/2 ratio). These isomers differ in the
orientation of the phosphole Ph substituent with respect
to the Ru-coordinated arene or Cp group and it is very
likely that an anti orientation that diminishes the steric
hindrance (isomers a, Scheme 3) is more favourable. The
following experimental features support this hypothesis.
Complexes 1ꢂ
known Ru starting materials according to standard
methods of fragmentation (1ꢂ3), ligand substitution
(4,5,7,8, codꢁ1,5-cyclooctadiene, bpzmꢁbis(pyrazol-
/
8 (Scheme 2) were prepared using
/
/
/
1-yl)methane) or insertion reaction (6). In all cases, with
the exception of 7, the NPN/metal ratio was 1/1 and the
corresponding stoichiometry was obtained for each of
the reaction products. Complexes 1ꢂ8 were charac-
/
terised by elemental microanalysis, IR-, H-, 31P{1H}-
and 13C{1H}-NMR spectroscopy excepted derivative 7
which evolves in the time required to record a 13C{1H}-
NMR. In all cases, a large 31P-NMR coordination shift
1
effect was observed (Dd ꢀ
/
49 ppm). This high shift effect
is characteristic of P,N-chelating coordination of 2-
pyridylphospholes on transition metal centres [5,8]. Two
sets of signals are recorded for the pyridine moieties in
the 1H- and 13C{1H}-NMR spectra. The chemical shifts
of the resonances for the protons H6? and C6? (see
Scheme 2 for numbering) are particularly useful because
they are usually markedly different for the coordinated
and uncoordinated pyridine rings.
2.1. Complexes with a piano-stool structure
Coordination of 2-(2-pyridyl)phospholes to ‘(are-
ne)RuCl’ or ‘Cp?RuCl’ fragments can give rise to two
diastereoisomeric complexes possessing a piano-stool
structure. In the case of 2-(2-pyridyl)-5-(2-thie-
nyl)phosphole, only one of the possible diastereoisomers
Scheme 3.
Scheme 2.

120
A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ126
/
At room temperature, a 5/1 solution of diastereisomers
1a and 1b evolves to complex 1a after several days. This
observation clearly shows that complexes are in equili-
brium and that derivative 1a is thermodynamically more
stable than its isomer 1b. The molecular structure of
complex 1a was determined by an X-ray diffraction
study (Fig. 1, Table 1). As anticipated, the p-cymene
and the P-Ph substituent of the phosphole point in
opposite direction (anti conformer). The bond lengths
Table 1
˚
Selected bond lengths (A) and bond angles (8) for complex 1a
Bond lengths
Ru(1)-P(1)
2.315(2)
2.139(5)
2.389(2)
2.227(6)
2.161(6)
2.181(5)
2.264(6)
2.238(6)
2.185(6)
N(1)ꢂ
C(14)ꢂ
C(1)ꢂ
C(1)ꢂ
C(2)ꢂ
C(7)ꢂ
C(8)ꢂ
C(8)ꢂ
C(9)ꢂ
/
C(14)
1.351(7)
1.470(7)
1.780(5)
1.355(7)
1.479(7)
1.363(7)
1.816(5)
1.457(7)
1.345(7)
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
/
N(1)
/C(1)
/
Cl(1)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
/
P(1)
C(2)
C(7)
C(8)
P(1)
C(9)
N(2)
/
/
/
/
/
/
/
/
/
/
and angles around the Ru centre [Ru(1)ꢂ
/
P(1), 2.315(2)
˚
˚
/
/
A; Ru(1)ꢂ
/
N(1), 2.139(5) A; P(1)ꢂ
/
Ru(1)ꢂ
/
N(1), 79.9(1)8]
Bond angles
Cl(1)ꢂRu(1)ꢂ
Cl(1)ꢂRu(1)ꢂ
P(1)ꢂRu(1)ꢂ
Ru(1)ꢂN(1)ꢂ
N(1)ꢂC(14)ꢂC(1)
C(14)ꢂC(1)ꢂP(1)
C(1)ꢂP(1)ꢂRu(1)
are consistent with known literature values [8] and
reveal the absence of strain due to the formation of
the five-membered metallacycle. The inter-ring twist
angle between the phosphole ring and the coordinated
pyridine (49.18) is superior to that involving the free
pyridine group (25.28). It is noteworthy that the
uncoordinated nitrogen atom points toward the Ru-
centre. However, the distance between these two atoms
/
/
P(1)
88.9(1)
84.5(1)
79.9(1)
120.8(3)
113.3(5)
115.6(4)
96.3(2)
Ru(1)ꢂ
P(1)ꢂC(8)ꢂ
C(8)ꢂC(9)ꢂ
P(1)ꢂC(8)ꢂC(7)
C(8)ꢂC(7)ꢂ
C(7)ꢂC(2)ꢂ
C(7)ꢂC(8)ꢂ
/
P(1)ꢂ
C(9)
N(2)
/
C(8)
127.4(2)
119.2(4)
114.4(5)
109.3(4)
114.5(5)
113.1(5)
131.5(5)
/
/
N(1)
/
/
/
/
N(1)
C(14)
/
/
/
/
/
/
/
/
/
/
C(2)
C(1)
C(9)
/
/
/
/
/
/
/
/
˚
reaches 4.09 A revealing the absence of any interaction.
Ru centre. The chemical shift of this signal (4.22 ppm) is
similar to that found in a cycloheptatrienyl ligand with a
s1-allyl moiety bonded to Ru [9]. These data strongly
suggest that the three aforementioned 1H resonances
correspond to a s1-allyl moiety. The formation of 6
(Scheme 3) involves the insertion of one alkene function
The steric hindrance around the ruthenium atom has
a dramatic influence on the diastereoselectivity of 2,5-
di(2-pyridyl)phosphole coordination. With Ru centres
bearing bulky arene ligands such as C6Me6 or C5Me5, a
diastereoselective coordination occurred and complexes
3, 5 and 6 were isolated as single diastereomers.
The reaction leading to complex 6 warrants a separate
discussion. In contrast to its precursor Ru(C5-
Me5)H(cod) (Scheme 2), complex 6 does not show any
hydride resonance in the 1H-NMR spectrum. Three
resonances are observed between 3.2 and 5.3 ppm, each
signal integrates for one proton and they are correlated
by COSY (see Fig. 2). One of these protons (H1) is
of the cod group into the Ruꢂ
coordination of the NPN ligand, followed by an internal
isomerisation of the remaining CÄC double bond of the
/H bond, induced by the
/
cyclooctenyl fragment. The migration of a hydride
group to cod has precedents for Ru [10] and even for
CpRu derivatives [10e]. However, a h3-allyl or a vinyl
group were shown to be the final products depending on
whether the incoming ligand was a monodentate or a
bidentate donor. Consequently, carbene intermediates
such as those considered responsible for the formation
of vinyl products in the reaction of CpRuH(cod) with
diphosphines [10e] seem to be of only minor importance
in the reaction of Ru(C5Me5)H(cod) with the hetero-
ditopic 2-pyridylphosphole ligand.
coupled to phosphorus (JHP
a direct bonding of the corresponding CH group to the
ꢁ32.7 Hz), which suggests
/
2.2. Octahedral complexes
Complexes 7 and 8 were obtained through ligand
displacement (PPh3, cod) from the corresponding Ru
starting material by NPN (Scheme 2). Complex 7 was
obtained by reacting RuCl2(PPh3)3 with two equivalents
of NPN at 40 8C. When the reaction was carried out
with only one equivalent of NPN or at room tempera-
ture with two equivalents, the 31P{1H}-NMR spectrum
of the reaction mixture showed the presence of 7 and of
an intermediate that was not isolated. This intermediate
is very probably a RuCl2(PPh3)(NPN) complex since its
31P{1H}-NMR spectrum exhibits two mutually coupled
doublets (JPP
coordinated PPh3 (54.7 ppm) and an N,P-chelate 2-
ꢁ
/
34.9 Hz) with chemical shifts typical of a
Fig. 1. ORTEP view of complex 1a with atom-labeling. Thermal
ellipsoids show 30% probability levels.

A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ
/126
121
Fig. 2. 1Hꢂ1
H COSY spectrum for complex 6 showing the correlations on the allyl group.
/
pyridylphosphole (74.3 ppm). The 31P{1H}-NMR spec-
trum of compound 7 contains two doublets at low field
(d: 75.6, 79.8) with a low coupling constant (33.6 Hz)
characteristic of phosphorus atoms in a mutually cis
specific pair of olefinic cod resonances (the observed
NOE interactions are indicated with arrows in Scheme
4). This behaviour is characteristic of a fac disposition
of the donor groups in the RuH(cod) moiety [11].
1
2
disposition. In the H spectra, a pair of H6? resonances
Furthermore, the doublets of the hydrides exhibit JHP
are observed indicating the presence of two coordinated
(d: 10.26, 1H; 9.92, 1H) and two free (d: 8.57, 2H)
pyridyl groups. Taking into account these data, we
propose that the most reasonable structure for complex
7 is that presented in Scheme 3. Only one diastereomer
was observed, which indicates a high selectivity in the
orientation of the Ph substituents of the two phosphole
ligands. The orientation of the P-phenyl substituent
towards the Cl ligand is probably the least sterically
demanding.
values of ca. 20ꢂ30 Hz, which is typical of a mutually cis
/
disposition of the coordinated P and H atoms. The
doublet for 8c shows a hyperfine coupling of 3.2 Hz and
this does not disappear upon 31P decoupling. This small
splitting could be due to a coupling with one cod proton
(olefinic) as a consequence of a possible distortion in the
octahedral geometry of the complex. Such a distortion
has been frequently observed in X-ray structures of Ru
complexes bearing the RuH(cod) unit [10d,12]. Lastly,
1
as observed for the precedent complexes, the H and
13C{1H}-NMR spectra of the different isomers of
compound 8 contain the characteristic pair of reso-
nances for the pyridine CH6? groups, indicating a N,P-
chelate coordination. Note that the 31P-NMR chemical
The NMR spectra of complex 8 (Scheme 2) show the
presence of three isomers (aꢂc in this discussion), as
/
deduced from the observation of three different singlets
in the 31P{1H}-NMR spectrum and three doublets in the
1
hydride region (1:2:1 ratio) of the H-NMR spectrum.
shifts of complexes 8aꢂ
consistent with N,P-coordination.
It can be seen that the structural difference between
the pairs IꢂII and IIIꢂIV (Scheme 4) is the distribution
/
c (d, 38.9ꢂ
/
52.14 ppm) are also
The H6? pyridine resonances and several of the olefinic
cod protons were assigned after COSY and NOE
experiments. The rest of the resonances are obscured
by the complexity of the 1H-NMR spectrum. The
/
/
of the coordinated pyridine and Cl groups, whereas the
difference between the components of each pair is the
relative orientation of the phosphole Ph substituent. The
only hydride resonance that shows an NOE with an
structures of the three isomers 8aꢂc (Scheme 4) are
/
proposed on the basis of the following points. NOE
irradiation of each hydride signal leads to an effect on a

122
A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ
/126
Scheme 4.
ortho phenyl proton is that of 8b, to which we assign
structure II (Scheme 4). The electronic character of the
ligand in the trans position determines mainly the
chemical shift of a hydride. Thus, since similar chemical
shifts are recorded for 8a and 8b, we propose structure I
for 8a. The assignment of structure IV for complex 8c is
based on steric considerations.
resonances was observed (Fig. 3). Although a general
decrease in the resolution of these resonances was
observed, hydride signals for 8a and 8b were still
doublets whereas the corresponding resonance for 8c
became very broad (Fig. 3). This broadening becomes
less marked as the temperature is increased and at room
temperature the doublet pattern reappears. T1 min values
for the hydride resonances of 8a and 8b change only
slightly after protonation (350 msꢄ1 at 223 K in a 300
2.3. Protonation experiment on isomers 8aꢂc
/
MHz for 8aꢂ
c and 300 msꢄ1 at 213 K after the
/
protonation for 8a,b). Unfortunately, the T1 min value
for 8c after the protonation could not be accurately
determined because of the broadening of this resonance,
but a general inspection of the corresponding spectra
indicates that it is not very different from those of the
isomers 8a and 8b. On the basis of this information, we
propose that the proton is directly transferred from the
acid to the uncoordinated pyridine unit. The unsuitable
orientation of this group rules out any other step in the
proton transfer in 8a and 8b (Scheme 4) whereas in 8c a
The three isomers of complex 8 bear an hydride ligand
and, in order to study the influence of the structure on a
proton transfer process, they were allowed to react with
one equivalent of CF3CO2H in acetone-d6 solution. The
addition of the acid was carried out in an NMR tube at
ꢄ
/
80 8C and the temperature was then slowly increased
in the NMR probe in order to observe the different steps
in the proton transfer. Comparison of the spectra at ꢄ
/
80 8C before and after the addition shows a slight shift
to lower field of the H6? resonance for the three isomers.
For 8a and 8b, a shift to higher field of the hydride
protonꢂhydride interaction that leads to the broadening
/
of the hydride signal is observed, probably as a result of
the formation of a dihydrogen bridge. This interaction
appears to be weak and is broken when the temperature
is increased, in accordance with the low relaxation effect
on the hydride and with the redefinition of the hydride
as the temperature rises. Thus, we can conclude that the
structures of the three isomers remain unaffected by the
protonation reaction. Complex 8c is the only one that is
susceptible to undergo a second intramolecular proton
transfer step due to the proximity of the uncoordinated
pyridine group and of the RuꢂH bond (Scheme 4). Note
/
that we have recently demonstrated that the protonation
of neutral Ru hydrides can lead to an isomerisation
process that improves the formation of an intramole-
cular dihydrogen bridge [7d].
3. Conclusions
We have prepared new families of [2,5-di(2-pyri-
dyl)phosphole]Ru complexes with either a piano-stool
or octahedral structure. In all cases, the heteroditopic
N,P,N-ligand acts as an 1,4-chelate. A stereoselective
coordination is observed when bulky ligands are present
in the Ru-coordination sphere. Three isomers are
formed in the case of the complex RuClH(cod)(NPN)
and the structure of these isomers was elucidated by
Fig. 3. High frequency region of the 1H-NMR spectra (hydride
resonances) of 8aꢂc and the respective protonated species.
/

A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ
/126
123
NMR data. The first step in the reaction of these
isomers with CF3CO2H is the protonation of the
uncoordinated pyridine group. A second step, involving
the possible formation of a weak dihydrogen bridge, is
also observed for only one of the isomeric forms,
reflecting the influence of the structure on the formation
of this type of interaction.
range hkl: hꢁ
0.5%) gave 8400 unique reflection of which 4750 had
I ꢀ2.0s(I). After Lorentz and polarization corrections
[19] the structure was solved with SIR-97 [20] which
revealed the non hydrogen atoms of the structure (one
cation, one anion and a dichloromethane molecule).
After anisotropic refinement most hydrogen atoms were
found in a difference map. The whole structure was
refined with SHELXL-97 [21]: 437 variables, 4750 reflec-
/
0/16, kꢁ
/
0/23, lꢁ
/
ꢄ
/
19/19, (decay B
/
/
4. Experimental
tions with I ꢀ
4.19P] where Pꢁ
/
2.0s(I), wꢁ
(F2oꢃ2F2c)/3 with the resulting R1ꢁ
0.134, Sꢁ
/
1/[s2(F2o)ꢃ
/
(0.0705P)2ꢃ
/
/
/
/
4.1. Starting materials and general conditions
0.0567, wR2ꢁ
/
/
1.022, and residual Dr B
/
0.089 e Aꢄ3. An ORTEP plot was generated with
PLATON-98 [22].
4.1.1. General comments
All manipulations were carried out under an atmo-
sphere of dry oxygen-free nitrogen using standard
Schlenk techniques. Solvents were distilled from the
appropriate drying agents and degassed before use.
AgTfO and AgBF4 were used as purchased from
Aldrich. Ru starting materials were prepared as reported
in the literature: [RuCl2(h6-p-cymene)]2 and [RuCl2(h6-
C6Me6)]2 [13], Ru(h5-C5H5)Cl(cod) and Ru(h5-
C5H5)H(cod) [14] Ru(h5-C5Me5)Cl(cod) [15], Ru(h5-
4.2. Preparations
4.2.1. [RuCl(p-cymene)(NPN)]TfO (1)
Phosphole NPN (0.150 g, 0.41 mmol) and AgTfO
(0.105 g, 0.41 mmol) were added to a solution of [Ru(p-
cymene)Cl2]2 (0.125 g, 0.20 mmol) in dichlorometane (20
ml). The reaction mixture was stirred at room tempera-
ture (r.t.) for 2 h. The precipitate of AgCl was filtered off
and the solution obtained was evaporated to dryness. A
brown solid of 1 was obtained after washing with
pentane (10 ml). Yield, 252.1 mg (80%). Anal. Calc.
for C35H35ClF3N2O3PRuS (787.87): C, 53.35; H, 4.48;
N, 3.55. Found: C, 52.98; H, 4.48; N, 3.41%. IR (cmꢄ1):
1599, 1580 (nCNphosphole); 1271 (TfO). 1a: 31P{1H}-
C5Me5)H(cod)
[16],
RuCl2(PPh3)3
[17]
RuClH(bpzm)(cod)
[18].
1-phenyl-2,5-di(2-pyri-
dyl)phosphole (NPN) was prepared according with a
previously reported method [4]. Elemental analyses were
performed with a Thermo Quest FlashEA 1112 micro-
analyzer. IR spectra were recorded as KBr pellets with a
1
Perkinꢂ
/
Elmer PE 883 IR spectrometer. 1H, 13C{1H}
NMR (CDCl3): d 65.9 (s). H-NMR (CDCl3): 9.15 (d,
3
and 31P{1H} spectra were recorded on a Varian Unity
300 spectrometer. Chemical shifts (ppm) are given
relative to TMS (1H and 13C) or H3PO4 (31P). The
signals in the 13C{1H}-NMR spectra are singlets unless
specified. COSY spectra: standard pulse sequence with
an acquisition time of 0.214 s, pulse width 10 ms,
relaxation delay 1 s, number of scans 16, number of
increments 512. The NOE difference spectra were
recorded with the following acquisition parameters:
spectral width 5000 Hz, acquisition time 3.27 s, pulse
ꢁ
/
5.3 Hz, H6?); 8.70 (d, 1H, JHH
7.86 (m, Ph and pyridine); 6.00 (d, 1H,
ꢁ
/
4.7 Hz,
3
1H, JHH
H6?); 8.18ꢂ
/
3JHH
3JHH
3JHH
ꢁ
/
6.6 Hz, arom. CHp-cymene); 5.90 (d, 1H,
6.1 Hz, arom. CHp-cymene); 5.81 (d, 1H,
5.4 Hz, arom. CHp-cymene); 5.41 (m, 1H, arom.
ꢁ
/
ꢁ
/
CHp-cymene); 3.21 (m, 2H, Ä
CH2); 2.10ꢂ1.81 (m, 4H, Ä
Mep-cymene); 1.26 (d, JHH
/
Cꢂ
Cꢂ
6.7 Hz, 3H, CHMe2,p-
/
CH2); 2.70 (m, 2H, Ä
CH2ꢂCH2); 1.64 (3H,
/
Cꢂ
/
/
/
/
/
3
ꢁ
/
3
cymene); 1.21 (d, JHH
13C{1H}-NMR (CDCl3): 159.09 (s, C6?); 149.57 (s, C6?);
139.67 (s, C4?); 137.75 (s, C4?); 132.85 (d, JCP
ꢁ7.1 Hz, 3H, CHMe2,p-cymene).
/
2
width 908, relaxation delay 5 s, dpwrꢁ
scans 240. For variable temperature spectra the probe
temperature (91 K) was controlled by a standard unit
/1, number of
ꢁ9.1 Hz,
/
4
C
ortho-Ph); 131.36 (d, JCP
ꢁ2.5 Hz, Cpara-Ph); 128.31 (d,
/
/
3JCP
3JCP
(s, C5?); 110.11 (s, Cipso
so ꢂi
Prp-cymene); 94.08 (m, arom. CHp ꢂcymene); 93.63 (d,
2JCP
7.5 Hz, arom. CHp-cymene); 88.24 (s, arom. CHp-
cymene); 84.12 (s, arom. CHp-cymene); 31.08 (s, CHMe2,p-
ꢁ
/
11.1 Hz, Cmeta-Ph); 124.76 (s, C5?); 124.35 (d,
7.5 Hz, C3?); 124.0 (d, 3JCP 7.5 Hz, C3?); 123.71
CH3,p-cymene); 97.27 (s, Cip-
calibrated with a methanol reference.
ꢁ
/
ꢁ
/
ꢂ
/
4.1.2. X-ray structural determination of 1a
/
C34H35N2PRu, CF3SO3, CH2Cl2, Mꢁ
/
873.13, mono-
15.263(5)
4, Dcalc 1.567
0.71073 A, mꢁ
7.94 cmꢄ1
293 K. The sample (0.35ꢅ0.32ꢅ
0.28 mm3) was studied on an automatic diffractometer
CAD4 NONIUS with graphite monochromatized Moꢂ
ꢁ
/
clinic, P21/c, aꢁ13.047(6), bꢁ18.589(8), cꢁ
/
/
/
3
˚
˚
A, bꢁ
Mg mꢄ3, l(Moꢂ
F(000)ꢁ1776, Tꢁ
/
90.69(3)8, Vꢁ
/
3701(3) Aꢄ3, Zꢁ
/
ꢁ
/
cymene); 29.60 (d, JCP
3JCP
6.0 Hz, ÄCꢂCH2); 23.78 (s, CHMe2,p-cymene);
22.68 (s, CHMe2,p-cymene); 21.75 (s, ÄCꢂCH2ꢂCH2);
ꢁ
/
9.1 Hz, Ä
/
Cꢂ
/
CH2); 27.56 (d,
˚
/
Ka)ꢁ
/
/
,
ꢁ
/
/
/
/
/
/
/
/
/
/
20.54 (s,
Ä
/
Cꢂ
/
CH2ꢂCH2); 17.99 (Mep-cymene). 1b:
/
1
/
31P{1H}-NMR (CDCl3): d 69.6 (s). H-NMR (CDCl3,
3
only assigned resonances): 9.61 (d, 1H, JHH
Ka radiation. The cell parameters were obtained by
fitting a set of 25 high-theta reflections. The data
ꢁ5.1 Hz,
/
H6?); 8.82 (d, 1H, JHH
ꢁ
/
4.7 Hz, H6?); 6.25 (d, 1H,
3
3
6.3 Hz, arom. CHp-cymene); 6.10 (d, 1H, JHH
collection (2umax
ꢁ
/
548, scan v/2uꢁ/1, tmax
ꢁ/60 s,
3JHH
ꢁ
/
ꢁ
/

124
A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ126
/
5.6 Hz, arom. CHp-cymene); 1.87 (s, 3H, Mep-cymene); 1.10
(d, 3JHH 6.7 Hz, 3H, CHMe2,p-cymene); 0.94 (d, 3JHH
7.1 Hz, 3H, CHMe2,p-cymene).
C37H39ClF3N2O3PRuS (815.89): C, 54.46; H, 4.82; N,
3.43. Found: C, 54.64; H, 4.92; N, 3.23%. 31P{1H}-
ꢁ
/
ꢁ
/
1
NMR (CDCl3): d 61.2 (s). H-NMR (CDCl3): 8.63 (d,
3
3
1H, JHH
H6?); 7.98ꢂ
CꢂCH2); 1.85ꢂ
4JHP 0.9 Hz, 18H, C6Me6). 13C{1H}-NMR (CDCl3):
ꢁ
ꢁ
/
5.4 Hz, H6?); 8.42 (d, 1H, JHH
ꢁ
/
4.6 Hz,
2.81 (m, 4H,
CH2); 1.82 (d,
4.2.2. [RuCl(p-cymene)(NPN)]BF4 (2)
/
7.54 (m, Ph and pyridine); 3.32ꢂ
/
Phosphole NPN (0.150 g, 0.41 mmol) and AgBF4
(0.079 g, 0.41 mmol) were added to a solution of [Ru(p-
cymene)Cl2]2 (0.125 g, 0.20 mmol) in dichloromethane
(20 ml). The reaction mixture was stirred at r.t. for 1 h.
The precipitate of AgCl was filtered off and the obtained
solution was evaporated to dryness. A brown solid of 2
Ä
/
/
/
2.20 (m, 4H, ÄCꢂCH2ꢂ
/
/
/
/
155.00 (s, C6?); 150.00 (s, C6?); 140.85 (s, C4?); 139.37 (s,
C4?); 133.52 (d, JCP
ꢁ9.0 Hz, Cortho-Ph); 131.98 (d,
2.6 Hz, Cpara-Ph); 127.35 (d, JCP
/
2
4JCP
meta-Ph); 125.71 (s, C5?); 124.10 (s, C5?); 123.80 (d,
3JCP 7.4 Hz, C3?); 123.44 (d, 3JCP 7.4 Hz, C3?); 98.74
(s, C6Me6); 29.95 (d, 3JCP
6.5 Hz, ÄCꢂCH2); 27.41 (d,
3JCP
8.3 Hz, ÄCꢂCH2); 22.21 (s, ÄCꢂCH2ꢂCH2);
21.90 (s, ÄCꢂCH2ꢂCH2); 15.42 (s, C6Me6).
ꢁ
/
ꢁ
/
10.6 Hz,
3
C
was obtained after washing with pentane (2ꢅ
Yield, 238.0 mg (82%). Anal. Calc.
/
10 ml).
for
ꢁ
/
ꢁ
/
ꢁ
/
/
/
C34H35BClF4N2PRu (725.67): C, 56.27; H, 4.82; N,
3.86. Found: C, 56.55; H, 4.76; N, 3.96%. IR (cmꢄ1):
1570 (nCNphosphole); 1055 (BF4). 2a: 31P{1H}-NMR
ꢁ
/
/
/
/
/
/
/
/
/
1
(CDCl3): d 65.6 (s). H-NMR (CDCl3): 9.16 (d, 1H,
5.2 Hz, H6?); 8.70 (d, 1H, JHH
4.2.4. Ru(C5H5)Cl(NPN) (4)
3
3JHH
ꢁ
/
ꢁ
/
4.2 Hz, H6?);
Phosphole NPN (0.149 g, 0.40 mmol) was added to a
solution of Ru(C5H5)Cl(cod) (0.125 g, 0.40 mmol) in
THF (20 ml). The reaction mixture was stirred at 40 8C
for 2 h. After evaporation to dryness and washing with
pentane (10 ml), 4 was obtained as a brown solid. Yield,
182.3 mg (80%). Anal. Calc. for C29H26ClN2PRu
(569.81): C, 61.12; H, 4.56; N, 4.91. Found: C, 61.07;
H, 4.64; N, 4.86%. IR (cmꢄ1): 1560, 1525
(nCNphosphole). 31P{1H}-NMR ((CD3)2CO): d 82.2 (s,
7.95 ꢂ
/
7.53 (m, Ph and pyridine); 5.97 (d, 1H, 3JHH
ꢁ
/
6.1
5.6 Hz,
5.6 Hz, arom.
CHp-cymene); 5.47 (m, 1H, arom. CHp-cymene); 2.47 (sept.,
1H, CHMe2,p-cymene); 3.22ꢂ2.73 (m, 4H, ÄCꢂCH2);
1.95ꢂ1.84 (m, 4H, ÄCꢂCH2ꢂCH2); 1.61 (3H, Mep-
cymene); 1.22 (d, JHH 7.1 Hz, 3H, CHMe2,p-cymene);
3
Hz, arom. CHp-cymene); 5.92 (d, 1H, JHH
ꢁ
/
3
arom. CHp-cymene); 5.78 (d, 1H, JHH
ꢁ
/
/
/
/
/
/
/
/
3
ꢁ
/
3
1.27 (d, JHH
NMR (CDCl3): 159.54 (s, C6?); 150.00 (s, C6?); 140.00 (s,
ꢁ
6.8 Hz, 3H, CHMe2,p-cymene). 13C{1H}-
/
1
4b); 68.6 (s, 4a); H-NMR ((CD3)2CO): 9.53 (d, 1H,
C4?); 137.00 (s, C4?); 133.10 (d, JCP
ꢁ
/
8.1 Hz, Cortho-Ph);
3JHH
ꢁ
/
5.6 Hz, H6?, 4b); 9.34 (d, 1H, 3JHH
ꢁ
5.6 Hz, H6?,
/
2
4
131.98 (d, JCP
3
2 Hz, Cpara-Ph); 128.12 (d, JCP
ꢁ
/
ꢁ/10.0
4b); 8.65 (m, 2H, H6?, 4a); 7.9ꢂ
4a and 4b); 4.6 (s, C5H5, 4a); 4.1 (C5H5, 4b); 3.32ꢂ
(m, 4H, ÄCꢂCH2, 4a and 4b); 2.05ꢂ1.61 (m, 4H, Ä
/
6,8 (m, Ph and pyridine,
2.80
Cꢂ
Hz, Cmeta-Ph); 125.15 (s, C5?); 124.10 (s, C5?); 123.80 (d,
/
3
3JCP
110.85 (s, Cipso
cymene); 94.75 (m, CHp-cymene); 94.15 (d, JCP
ꢁ
/
7.5 Hz, C3?); 123.44 (d, JCP
ꢁ
/
7.5 Hz, C3?);
/
/
/
/
/
ꢂ
/
CH3,p-cymene); 97.15 (s, Cipso ꢂi
/
Prp-
7.5 Hz,
CH2ꢂ
CH2, 4a and 4b). 13C{1H}-NMR ((CD3)2CO):
/
2
ꢁ
/
159.29 (s, C6?, 4b); 159.27 (s, C6?, 4a); 150.31 (s, C6?, 4b);
CHp-cymene); 87.81 (s, CHp-cymene); 83.68 (s, CHp-
150.30 (s, C6?, 4a); 137.20 (s, 2C), 135.36 (s) and 134.34
3
cymene); 31.5 (s, CHMe2,p-cymene); 29.95 (d, JCP
2
ꢁ
/
10.0
CH2);
CH2);
(s) (C4?, 4a and 4b); 134.25 (d, JCP
ꢁ11.0 Hz, Cortho-Ph,
/
3
CH2); 27.84 (d, JCP
2
4b); 132.84 (d, JCP
Hz, Ä
/
Cꢂ
/
ꢁ
/
7.5 Hz, Ä
/
Cꢂ
/
ꢁ11.0 Hz, Cortho-Ph, 4a); 130.26 (d,
/
3
1.9 Hz, Cpara-Ph, 4a and 4b); 129.02 (d, JCP
24.12 (s, CHMe2,p-cymene); 23.00 (s, Ä
/
CꢂCH2ꢂ
/
/
4JCP
10.0 Hz, Cmeta-Ph, 4a); 128.18 (d, JCP
ꢁ
/
ꢁ
/
3
22.00 (s, Ä
/
Cꢂ
/
CH2ꢂ
/
CH2); 21.22 (s, CHMe2,p-cymene);
18.36 (s, Mep-cymene). 2b: 31P{1H}-NMR (CDCl3): d
ꢁ10.1 Hz, Cmeta-
/
3
Ph, 4b); 125.04 (d, JCP
3JCP
4b); 122.32 (d, 3JCP
(s), 121.85 (s) and 120.81 (s) (C5?, 4a and 4b); 75.44 (s,
C5H5, 4a); 73.45 (s, C5H5, 4b); signal of ÄCꢂCH2 of 4a
must be overlapped with the solvent signal; 27.40 (2C, Ä
CꢂCH2, 4b) 23.85 (2C, ÄCꢂCH2ꢂCH2, 4a); 23.12 (2C,
CꢂCH2ꢂCH2, 4b).
ꢁ
/
7.0 Hz, C3?, 4a); 124.91 (d,
1
69.6 (s). H-NMR (CDCl3, only assigned resonances):
3
ꢁ
/
8.0 Hz, C3?, 4a); 124.87 (d, JCP
ꢁ
7.0 Hz, C3?,
/
9.59 (d, 1H, 3JHH
ꢁ
/
5.1 Hz, H6?); 8.70 (d, 1H, 3JHH
ꢁ
/4.3
ꢁ
7.0 Hz, C3?, 4b); 122.17 (s), 122.12
/
Hz, H6?); 6.27 (d, 1H, JHH
ꢁ6.8 Hz, CHp-cymene); 6.05
/
3
(d, 1H, 3JHH
6.3 Hz, CHp-cymene); 1.86 (3H, Mep-cymene); 1.07 (d,
3JHH 6.8 Hz, 3H, CHMe2,p-cymene); 0.96 (d, 3JHH
7.1
ꢁ
/
6.3 Hz, CHp-cymene); 5.85 (d, 1H, 3JHH
ꢁ
/
/
/
/
ꢁ
/
ꢁ
/
/
/
/
/
Hz, 3H, CHMe2,p-cymene).
Ä
/
/
/
4.2.3. [RuCl(C6Me6)(NPN)]TfO (3)
4.2.5. Ru(C5Me5)Cl(NPN) (5)
Phosphole NPN (0.165 g, 0.45 mmol) and AgTfO
(0.116 g, 0.45 mmol) were added to a solution of
[Ru(C6Me6)Cl2]2 (0.150 g, 0.22 mmol) in dichlorome-
tane (20 ml). The reaction mixture was stirred at r.t. for
2 h. The precipitate of AgCl was filtered off and the
obtained solution was evaporated to dryness. A orange
Phosphole NPN (0.208 g, 0.57 mmol) was added to a
solution of Ru(C5Me5)Cl(cod) (0.215 g, 0.57 mmol) in
THF (20 ml). The reaction mixture was stirred at 40 8C
for 3 h. After evaporation to dryness and washing with
pentane (10 ml), 5 was obtained as a brown solid. Yield,
310.0 mg (85%). Anal. Calc. for C34H36ClN2PRu
(639.86): C, 63.82; H, 5.62; N, 4.37. Found: C, 64.01;
H, 5.64; N, 4.42%. IR (cmꢄ1): 1555, 1510
solid of 3 was obtained after washing with pentane (2ꢅ
/
10 ml). Yield, 305.1 mg (85%). Anal. Calc. for

A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ
/126
125
1
(nCNphosphole). 31P{1H}-NMR (CDCl3): d 64.9 (s). H-
thf (25 ml). The mixture was stirred at r.t. for 5 h. After
evaporation to dryness and washing with hexane (2ꢅ10
ml), 8 was obtained as a red solid. Yield, 142.7 (75%).
Anal. Calc. for C32H34ClN2PRu (613.84): C, 62.61; H,
5.54; N, 4.56 Found: C, 62.47; H, 6.01; N, 4.66%. IR
(cmꢄ1): 1595, 1578 (nCNphosphole); 2006 (nRuH). 31P
{1H}-NMR ((CD3)2CO): d 8a: 52.14 (s); 8b: 44.2 (s); 8c:
3
NMR (CDCl3): 8.87 (d, 1H, JHH
ꢁ
/
4.8 Hz, H6?); 8.57
6.98 (m, Ph and
CH2); 2.71 (m, 2H, ÄCꢂ
CꢂCH2ꢂCH2); 1.30 (15H,
/
3
(d, 1H, JHH
pyridine); 3.23 (m, 2H, Ä
CH2); 2.01ꢂ
ꢁ
/
3.9 Hz, H6?); 7.65ꢂ
Cꢂ
2.23 (m, 4H, Ä
/
/
/
/
/
/
/
/
/
C5Me5). 13C{1H}-NMR (CDCl3): 156.0 (s, C6?); 149.27
(s, C6?); 136.0 (s, C4?); 135.0 (s, C4?); 134.09 (bs, Cortho-
Ph); 129.56 (bs, Cpara-Ph); 127.97 (bs, Cmeta-Ph); 124.36
(s), 122.11 (bs); 121.35 (bs) and 120.91 (s) (C5? and C3?);
1
3
38.9 (s). H-NMR ((CD3)2CO): 9.32 (d, 1H, JHH
3
ꢁ
/
5.1
Hz, H6?, 8b); 8.61 (d, 1H, JHH
ꢁ
/
3.9 Hz, H6?, 8a or 8c);
3
83.19 (bs, C5Me5); 30.63 (bs, Ä
CH2); 23.51 (s, ÄCꢂCH2ꢂCH2); 22.93 (s, Ä
CH2); 9.44 (s, C5Me5).
/
Cꢂ
/
CH2); 27.57 (bs, Ä
/
Cꢂ
/
8.58 (d, 1H, JHH
ꢁ
/
5.1 Hz, H6?, 8a or 8c); 8.37 (d,
5.7 Hz, 1H,
5.9 Hz, H6?, 8a or 8c);
7.0 (m, Ph and pyridine, 8a, 8b and 8c); 4.67 (m, ꢂ
CH Ä/cod, 8a); 4.45 (m, ꢂCHꢁ/cod, 8b); 4.37 (m, ꢂ
CHꢁ/cod, 8b); 4.05 (ꢂCHꢁ/cod, 8a or 8c); 3.73 (ꢂ
CHꢁ/cod, 8c); 3.33 (ꢂCH Ä/cod, 8c); 2.80 (CH2,cod, 8a);
3.41ꢂ3.0 (m, 4H, CꢂCH2,phosphole); 2.95ꢂ1.57
(CH2,cod); 1.64ꢂ2.1 (m, 4H, ÄCꢂCH2ꢂCH2,phosphole),
6.94 (8a, RuH); ꢄ7.04 (8b, RuH); ꢄ8.16 (8c, RuH).
/
/
/
/
CꢂCH2ꢂ
/
/
3JHH
H6?, 8a or 8c); 8.09 (d, 1H, 3JHH
8.06ꢂ
ꢁ
/
4.7 Hz, 1H, H6?, 8b); 8.35 (d, 3JHH
ꢁ
/
ꢁ
/
/
/
4.2.6. Ru(C5Me5)(s1-C8H13)(NPN) (6)
/
/
Phosphole NPN (0.133 g, 0.36 mmol) was added to a
solution of Ru(C5Me5)H(cod) (0.125 g, 0.36 mmol) in
thf (20 ml). The reaction mixture was stirred at r.t. for 3
h. After evaporation to dryness and washing with
pentane (10 ml), 6 was obtained as a red solid. Yield,
167.0 mg (65%). Anal. Calc. for C42H49N2PRu (713.49):
C, 70.70; H, 6.87; N, 3.92 Found: C, 70.27; H, 6.63; N,
4.01%. IR (cmꢄ1): 1563, 1599 (nCNphosphole). 31P{1H}-
/
/
/
/
Ä
/
/
/
/
/
/
/
ꢄ
/
/
/
13C{1H}-NMR ((CD3)2CO): 8b: 154.98 (s, C6?); 154.51
(s, C6?); 145.36 (s, C4?); 141.80 (s, C4?); 138.04 (d, 2JCP
ꢁ
/
4
11.5 Hz, Cortho-Ph); 135.16 (d, JCP
ꢁ3.0 Hz, Cpara-Ph);
/
1
NMR ((CD3)2CO): d 117.2 (s). H-NMR (C6D6): 8.63
133.40 (d, 3JCP
ꢁ
/
9.4 Hz, Cmeta-Ph); 129.93 (d, 3JCP
ꢁ7.5
/
(d, 1H, 3JHH
H6?); 8.0ꢂ
CH ÄCHcyclooct); 4.22 (1H, m, JHP
CH ꢂCHÄ/cyclooct); 3.25 (m, 1H, ꢂCHꢂ
2.67 (m, 4H, ÄCꢂCH2); 2.24ꢂ2.0 (m, 4H, Ä
CH2); 2.32ꢂ1.22 (CH2,cyclooct); 1.35 (15H, C5Me5).
13C{1H}-NMR (C6D6): 156.87 (s, C6?); 148.29 (s, C6?);
133.97 (s, C4?); 133.48 (d, 2JCP
9.5 Hz, Cortho-Ph); 126.5
ꢁ
/
6.2 Hz, H6?); 7.54 (d, 1H, 3JHH
ꢁ
/
5.6 Hz,
7.5 (m, Ph and pyridine); 5.31 (m, 1H, ꢂCHꢂ
32.7 Hz, Ruꢂ
CHÄCHcyclooct);
CꢂCH2ꢂ
Hz, C3?); 127.15 (d, JCP
ꢁ
6.0 Hz, C3?); 126.47 (s, C5?);
/
3
/
/
/
126.53 (s, C5?); 88.69 (d, 2JCP
(d, 2JCP
9.0 Hz, ÄCHcod); 73.56 (s, Ä
CHcod); 43.13 (d, JCP
CH2,cod); 37.68 (s, ꢂCH2,cod); 35.15 (s, ꢂ
5.5 Hz, ÄCꢂCH2,phosphole); 28.36 (s, Ä
CꢂCH2ꢂCH2,phosp-
ꢁ
/
17.2 Hz, Ä
CHcod); 72.11 (s,
CH2,cod); 38.33 (s, ꢂ
CH2,cod);
/
CHcod); 84.49
3
/
ꢁ
/
/
ꢁ
/
/
/
3
/
/
/
/
Ä
/
ꢁ
/
3.5, ꢂ
/
/
/
/
/
/
/
/
/
/
3
/
32.50 (d, JCP
ꢁ
/
/
/
/
CꢂCH2ꢂ
/
/
CH2,phosphole); 27.69 (s, Ä
/
/
/
ꢁ
/
hole). 8a and 8c (only resonances assigned): 159.46 (s,
C6?); 158.00 (s, C6?); 154.77 (s, C6?); 154.67 (s, C6?);
(m, Cpara-Ph or Cmeta-Ph, the other signal must be
overlapped with that of the solvent);131.74 (s, C4?);
147.76 (s, C4?); 142.71 (s, C4?); 142.11 (s, C4?); 138.87 (d,
126.42 (s, 2C, C5?); 120.56 (2C, d, JCP
ꢁ
/
3.0 Hz, C3?);
CHꢂ/cyclooct) 104.34 (ꢂ
2JCP
ꢁ
/
ꢁ10.5 Hz,
ꢁ2.0 Hz, Cpara-Ph); 132.83 (d,
/
2
2
9.5 Hz, Cortho-Ph); 138.78 (d, JCP
3
112.53 (d, JCP
4
ortho-Ph); 134.41 (d, JCP
ꢁ
/
15 Hz, ꢂ
/
CHÄ
/
/
C
3JCP
/
2
CHÄ
15.1
(CH2,phosphole
/
CHꢂ/cyclooct); 91.49 (s, C5Me5); 48.87 (d, JCP
Hz, RuꢂCHꢂCHÄ/cyclooct); 30.5ꢂ23.4
CH2,cyclooct); 8.40 (C5Me5).
ꢁ
/
ꢁ
/
9.7 Hz, Cmeta-Ph); 132.27 (d, 3JCP
ꢁ9.7 Hz, Cmeta-
/
/
/
/
Ph); 128.80 (d, 3JCP
ꢁ
/
8.3 Hz, C3?); 128.48 (s, C5?); 127.92
3
ꢃ
/
(s, C5?); 127.84 (s, C5?); 127.65 (d, JCP
ꢁ
8.0 Hz, C3?);
/
2
90.34 (d, JCP
ꢁ
/
16.5 Hz, Ä
CHcod); 74.44 (s, Ä
CH2,cod); 41.11ꢂ27.45 (ꢂ
CꢂCH2ÄCH2,phosphole).
/
CHcod); 94.24ꢂ
CHcod); 40.62 (d,
CH2,cod
/
93.35 (3C, Ä
/
4.2.7. RuCl2(NPN)2 (7)
CHcod); 75.77 (s, Ä
3JCP
3.2 Hz, ꢂ
CꢂCH2,phosphole
/
/
Phosphole NPN (0.161 g, 0.44 mmol) was added to a
suspension of RuCl2(PPh3)3 (0.210 g, 0.22 mmol) in
dichloromethane (20 ml). The mixture was stirred at
40 8C for 3 h. After evaporation to dryness and
ꢁ
/
/
/
/
ꢃ
/
Ä
/
/
ꢃ
/
Ä
/
/
/
4.2.9. Protonation of 8aꢂ
To a solution of 8aꢂ
(CD3)2CO at ꢄ80 8C prepared in a NMR tube, 1.9 ml
/
c
washing with diethylether (2ꢅ
/
10 ml), 7 was obtained
/c (0.015 g, 0.025 mmol) in
as a brown solid. Yield, 179.9 mg (90%). Anal. Calc. for
C48H42Cl2N4P2Ru (908.45): C, 63.46; H, 4.62; N, 6.16
Found: C, 63.51; H, 4.94; N, 5.89%. IR (cmꢄ1): 1595,
1583 (nCNphosphole). 31P{1H}-NMR (CDCl3): d 79.8 (d,
/
(0.025 mmol) of CF3COOH were added. The tube was
introduced in the NMR probe previously cooled at
ꢄ
80 8C. The 1H-NMR spectra were registered at
different temperatures.
/
1
2JPP
ꢁ
/
33.6 Hz), 75.6 (d). H-NMR (CDCl3): 10.26 (d,
H6?), 9.92 (d, H6?) and 8.57 (d, 2H, H6?); 8.20ꢂ
Ph and pyridine); 3.44ꢂ1.24 (m, 16H, CꢂCH2ꢂ
/
7.52 (m,
CH2).
/
/
/
5. Supplementary material
4.2.8. RuClH(cod)(NPN) (8)
Phosphole NPN (0.116 g, 0.31 mmol) was added to a
solution of RuClH(cod)(bpzm) (0.124 g, 0.31 mmol) in
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic

126
A. Caballero et al. / Journal of Organometallic Chemistry 663 (2002) 118ꢂ126
/
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