Synthesis and characterization of 2-oxacycloalkylideneruthenium(II) complexes: X-ray crystal structure of the 2-oxacycloheptylidene complex [Ru{=COCH2(CH2)3CH2} (η5-C9H7) (PPh3)2] [PF6]·CH2Cl2

Article abstract of DOI:10.1016/S0022-328X(02)01216-0

The oxacyclocarbene complexes [Ru{=COCH₂(CH₂)_nCH₂}(η ⁵-C₉H₇)LL′] [PF₆]·(L = L′ = PPh₃, n = 1 (2a), 2 (3a), (5a); L = L′ = PMe₂Ph, n = 1 (2b), 2 (3b), 3 (5b); LL′ = dppm, n = 1 (2c), 2 (3c), 3 (5c); L = PPh₃, L′ = PMe₃, n = 1 (2d), 2 (3d), 3 (5d), have been prepared by reaction of [RuCl(η⁵-C₉H₇)LL′] with 3-butyn-1-ol, 4-pentyn-1-ol and 5-hexyn-1-ol in refluxing ethanol and in the presence of NaPF₆. The process involves alkyne to vinylidene tautomerization to give hydroxyalkylvinylidene intermediate complexes. The vinylidene complexes [Ru{=C=C(H)(CH₂)₃CH₂OH}(η⁵- C₉H₇)LL′][PF₆ ] (L = L′ = PPh₃ (4a), L = L′ = PMe₂Ph (4 b), L = PPh₃, L′ = PMe₃ (4d) have been isolated from the reaction of [RuCl(η⁵-C₉H₇)LL′] with 5-hexyn-1-ol. The first structure for a 2-oxacycloheptylidene complex, 5a, has been determined by X-ray diffraction methods. The molecular structure shows the typical pseudooctahedral three-legged piano-stool geometry around the ruthenium atom, which is linked to the phosphorus atoms of the triphenylphosphine ligands and to the Cα of the oxacyclic carbene ligand; the coordination around the ruthenium atom is completed by a η-bonded indenyl ligand with the benzo ring orientated nearly trans to the carbene group (CA = 16.6(6)°). The Ru-Cl distance, 1.89(1) A?, is somewhat shorter than that found for other oxacyclic carbene ruthenium(II) complexes. The oxacycloheptylidene ring adopts a 'pseudochair' conformation for the seven member ring and shows an appreciable deviation from vertical orientation (DA = 29.7(5)°).

Full text of DOI:10.1016/S0022-328X(02)01216-0

Journal of Organometallic Chemistry 651 (2002) 22–33
www.elsevier.com/locate/jorganchem
Synthesis and characterization of
2-oxacycloalkylideneruthenium(II) complexes: X-ray crystal
structure of the 2-oxacycloheptylidene complex
¸¹¹¹¹¹¹¹º
[Ru{ꢀCOCH2(CH2)3CH2}(h5-C9H7)(PPh3)2][PF6]·CH2Cl2
M. Pilar Gamasa a,*, Jose´ Gimeno a, Blanca M. Mart´ın-Vaca a,1, Rau´l Isea b,
Angel Vegas b
a Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto de Qu´ımica Organometa´lica ‘‘Enrique Moles’’ (Unidad Asociada al CSIC),
Facultad de Qu´ımica, Uni6ersidad de O6iedo, 33071 O6iedo, Spain
b Instituto de Qu´ımica F´ısica ‘‘Rocasolano’’, CSIC. C/Serrano 119, E-28006 Madrid, Spain
Received 15 November 2001; accepted 30 January 2002
Abstract
¸¹¹¹¹¹¹¹º
The oxacyclocarbene complexes [Ru{ꢀCOCH2(CH2)nCH2}(h5-C9H7)LL%][PF6]·(L=L%=PPh3, n=1 (2a), 2 (3a), 3 (5a); L=
L%=PMe2Ph, n=1 (2b), 2 (3b), 3 (5b); LL%=dppm, n=1 (2c), 2 (3c), 3 (5c); L=PPh3, L%=PMe3, n=1 (2d), 2 (3d), 3 (5d)) have
been prepared by reaction of [RuCl(h5-C9H7)LL%] with 3-butyn-1-ol, 4-pentyn-1-ol and 5-hexyn-1-ol in refluxing ethanol and in
the presence of NaPF6. The process involves alkyne to vinylidene tautomerization to give hydroxyalkylvinylidene intermediate
complexes. The vinylidene complexes [Ru{ꢀCꢀC(H)(CH2)3CH2OH}(h5-C9H7)LL%][PF6] (L=L%=PPh3 (4a), L=L%=PMe2Ph
(4b), L=PPh3, L%=PMe3 (4d)) have been isolated from the reaction of [RuCl(h5-C9H7)LL%] with 5-hexyn-1-ol. The first structure
for a 2-oxacycloheptylidene complex, 5a, has been determined by X-ray diffraction methods. The molecular structure shows the
typical pseudooctahedral three-legged piano-stool geometry around the ruthenium atom, which is linked to the phosphorus atoms
of the triphenylphosphine ligands and to the Ca of the oxacyclic carbene ligand; the coordination around the ruthenium atom is
completed by a h5-bonded indenyl ligand with the benzo ring orientated nearly trans to the carbene group (CA=16.6(6)°). The
,
RuꢁC1 distance, 1.89(1) A, is somewhat shorter than that found for other oxacyclic carbene ruthenium(II) complexes. The
oxacycloheptylidene ring adopts a ‘pseudochair’ conformation for the seven member ring and shows an appreciable deviation
from vertical orientation (DA=29.7(5)°). © 2002 Published by Elsevier Science B.V.
Keywords: Ruthenium; Oxacycloalkylidene complexes; Oxacycloalkenyl complexes; Indenyl complexes
1. Introduction
catalytic [4] processes, has been confirmed [1].
Most of the 2-oxacycloalkylidene complexes hitherto
described contain a five-membered or, to a minor
extent, a six-membered ring carbene ligand [1]. To
The chemistry of 2-oxacycloalkylidene transition
¸¹¹¹¹¹º
metal complexes [M]ꢀCO(CH2)nCH2 has experienced a
remarkable development in the last years due to their
ready accessibility [1] and to the potential usefulness of
the oxacyclic fragment in chemical transformations [2].
Moreover, their utility in stoichiometric [3] as well as in
the best of our knowledge, only two 2-oxacycloheptyli-
¸¹¹¹¹¹º
dene complexes, [(CO)5MnꢁMn(CO)4{ꢀCO(CH2)4CH2}]
¸¹¹¹¹¹º
[5a] and [Re{ꢀCO(CH2)4CH2}(triphos)(CO)2][BF4]
(triphos=MeC(CH2PPh2)3) [5b] have been reported
[5c], although their structures have not been confirmed
by X-ray diffraction.
In the course of our studies on the reactivity of
unsaturated carbene complexes containing indenyl-
ruthenium(II) moieties as metal auxiliary [6] we have
explored the behaviour of the cationic vinylidene com-
* Corresponding author. Tel.: +34-985103460; fax: +34-
985103446.
E-mail address: pgb@sauron.quimica.uniovi.es (M.P. Gamasa).
1 Present address: Laboratoire d%He´te´rochimie Fondamentale et
Applique´e (UPRES-A CNRS 5069), 118 Route de Narbonne, Uni-
versite´ Paul Sabatier (Baˆt 2R1), F-31062 Toulouse, Cedex 04, France.
0022-328X/02/$ - see front matter © 2002 Published by Elsevier Science B.V.
PII: S0022-328X(02)01216-0

M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
23
plexes [Ru(ꢀCꢀCR1R2)(h5-C9H7)L2]+ towards alcohols
2. Results and discussion
[6a] and have examined the effect of the steric and
electronic properties of the vinylidene substituents R1
and R2 and of the ligands L in their reactivity. We
observed that only the unsubstituted vinylidene
[Ru(ꢀCꢀCH2)(h5-C9H7)L2]+ and the monosubstituted
[Ru(ꢀCꢀCHR)(h5-C9H7)(dppm)]+ complexes reacted
with ethanol or methanol to give the corresponding
alkoxycarbene derivatives. In contrast, all disubstituted
vinylidene complexes were unreactive (see Chart 1).
2.1. Synthesis of 2-oxacyclopentylidene (2a–d) and
2-oxacyclohexylidene (3a–d) complexes
The reaction of complexes [RuCl(h5-C9H7)LL%] (L=
L%=PPh3 (1a); PMe2Ph (1b); LL%=dppm (1c); L=
PPh3, L%=PMe3 (1d)) with 3-butyn-1-ol and
4-pentyn-1-ol in refluxing ethanol and in the presence
of NaPF6 gave, after 20–30 min, 2-oxacyclopentylidene
(n=1, 2a–d) and 2-oxacyclohexylidene (n=2, 3a–d)
¸¹¹¹¹¹¹¹¹º
complexes
[Ru{ꢀCOCH2(CH2)nCH2}(h5-C9H7)LL%]-
[PF6]. They were isolated as yellow, air stable hex-
afluorophosphate salts (60–90% yield). The reaction
was monitored at −20 °C, but the expected hydrox-
yvinylidene intermediate could not be detected by 31P-
NMR presumably because of the rapid intramolecular
attack by the hydroxy group.
All the complexes are soluble in chlorinated solvents
and tetrahydrofuran. They have been characterized by
elemental analyses, conductance measurements, IR and
NMR (1H, 31P{1H} and 13C{1H}) spectroscopy (details
are given in the Section 4 and in Tables 1 and 2). A
medium intensity w(COC) absorption [5b] at ca. 1163
(2a–d) and ca. 1246 cm−1 (3a–d) in the IR spectra
(KBr) confirms the presence of the oxacyclic carbene
group (see Section 4).
Chart 1.
On the basis of this reactivity, we believed it to be of
interest to develop the intramolecular version since the
cyclization of v-alkyn-1-ols constitutes one of the most
useful methods for the preparation of oxacycloalkyli-
dene complexes [1] (Scheme 1). It has been observed
experimentally that the intramolecular attack by the
hydroxy group is increasingly disfavoured as the num-
ber of CH2 spacers between the triple bond and the OH
group in the alkynol increases. For instance, the reac-
tion of [Mo(Me2CO)(dppe)(h-C7H7)]+ with 3-butyn-1-
ol led to the oxacyclopentylidene complex, while
mixtures of oxacyclohexylidene and the hydroxyvinyli-
dene complexes were formed when 4-pentyn-1-ol was
employed [7].
In this paper, we report the synthesis and characteri-
zation of a series of 2-oxacycloalkylidene complexes
(2a–d, 3a–d, 5a–d), as well as a number of their
corresponding hydroxyvinylidene precursors (4a–b, 4d),
(see Chart 2). Complexes 5a–d are the first ruthenium
oxacycloheptylidene complexes described to date. In
addition, the X-ray crystal structure of 5a, which to the
best of our knowledge is the first oxacycloheptylidene
transition metal complex crystallographically character-
ized, is also reported.
The 31P{1H}-NMR spectra of the complexes 2a–c
and 3a–c show at room temperature a single resonance
which is consistent with a rapid rotation of the carbene
group around the RuꢀC bond on the NMR time scale.
This is also in agreement with the data reported for
related indenylruthenium(II) Fischer type carbene and
vinylidene complexes [6a]. The 31P{1H}-NMR spectra
of the complexes 2d and 3d exhibit two doublet signals
(2JPP ca. 30 Hz) corresponding to the inequivalent
phosphorus atoms of PPh3 and PMe3 ligands (see Table
1). The typical low-field carbene resonance in the
13C{1H}-NMR spectra appears as a triplet at l 295.06–
308.05 (2JCP=12.0–13.5 Hz), a chemical shift similar
to that reported for other oxacyclic carbene ruthenium
complexes [8]. The values of other oxacycloalkylidene
carbon nuclei are in accordance with those reported for
other oxacyclocarbene ruthenium complexes [8a].
Several 2-(oxacyclopentylidene)ruthenium(II) com-
plexes have been described in the literature [1]. How-
ever, to the best of our knowledge, only the oxacyclo-
¸¹¹¹¹¹º
hexylidene ruthenium complexes [Ru{ꢀCO(CH2)3CH2}-
(h5-C5H5)LL]+ (L=PPh3 [8a], LL=dppe [8d]) are
known to date.
Chart 2.
2.2. Synthesis of the hydroxybutyl6inylidene (4a–b, 4d)
and 2-oxacycloheptylidene (5a–d) complexes
When
a mixture of 5-hexyn-1-ol, NaPF6 and
Scheme 1.
[RuCl(h5-C9H7)LL%] was refluxed in ethanol for 15 min,

24
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M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
25

26
M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33

M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
27
1
are: (a) Complexes 4a–d: (i) in the H-NMR spectra,
the resonance of the vinylidene hydrogen appears as a
triplet in the range of l 4.16–4.32 (JHH=7.3–7.9 Hz);
(ii) the 13C{1H}-NMR spectra display the characteristic
low-field resonance for the carbenic RuꢀCa atom, ca.
344 ppm (2JCP=15.3–16.5 Hz). The Cb resonance ap-
pears as a singlet in the range of l 108.78–112.63. Four
singlet carbon signals which are assigned to the CH2
carbon atoms of the l-hydroxybutyl substituent are
observed. (b) Complexes 5a–d: (i) the IR spectra ex-
hibit the expected w(COC) absorption at 1230–1240
cm−1 and (ii) the 13C{1H}-NMR spectra show the
low-field resonance of the carbene carbon RuꢀCa as a
triplet at l 306.68–312.52 (2JCP=11.7–12.7 Hz) and
five methylene resonances assigned to the CH2 groups
of the 2-oxacycloheptylidene ligand.
It is worth mentioning that the intramolecular attack
of the hydroxy group on the vinylidene group to gener-
ate the oxacyclocarbene complexes (2a–d, 3a–d) takes
place at a rate similar for 3-butyn-1-ol and 4-pentyn-1-
ol (see above) and becomes increasingly disfavoured for
5-hexyn-1-ol, allowing the vinylidene intermediate com-
plexes to be isolated (4a–d).
The solid-state structure of complex 5a was deter-
mined by X-ray diffraction. Complex 5a crystal-
lizes, from a CH2Cl2–hexane solution, as the CH2Cl2
solvate in a monoclinic system. ORTEP views of the
cation complex are shown in Fig. 1. Selected bond
distances, bond angles and indenyl distortion parame-
ters, are listed in Table 5. The molecular structure
shows the typical pseudooctahedral three-legged piano-
stool geometry around the ruthenium atom, which
is linked to the two phosphorus atoms of the
triphenylphosphine ligands and to the Ca of the oxacy-
clocarbene ligand. The values of the interligand angles
P1ꢁRuꢁP2, C1ꢁRuꢁP1 and C1ꢁRuꢁP2 as well as those
between the centroid of five-carbon ring of the in-
denyl ligand and the legs are the ones expected
Fig. 1. ORTEP views of the molecular structure of the cationic
¸¹¹¹¹¹¹¹º
complex
[Ru{ꢀCOCH2(CH2)3CH2}(h5-C9H7)(PPh3)2][PF6]
(5a),
showing the conformation of the oxacycloheptylidene group. For
clarity, only the ipso carbons of aryl groups of the triphenylphosphine
ligands are depicted.
the hydroxybutylvinylidene complexes [Ru{ꢀCꢀC(H)-
(CH2)3CH2OH}(h5-C9H7)LL%][PF6]
(L=L%=PPh3
(4a); L=L%=PMe2Ph (4b); L=PPh3, L%=PMe3 (4d))
were formed in good yield (75–80%). Thermal cycliza-
tion into the thermodynamically more stable 2-oxacy-
cloheptylidene complexes 5a, 5b and 5d occurred when
5-hexyn-1-ol, NaPF6 and [RuCl(h5-C9H7)LL%] were
refluxed in ethanol for a longer time (2–3 h). In con-
trast, the complex 5c (LL%=dppm) is formed in a
shorter time (1 h). This probably indicates the influence
of the small-bite chelating dppm ligand which allows
for
a
pseudooctahedron. The distance RuꢁC1,
,
1.89(1) A, is similar to that found in [Ru-
¸¹¹¹¹¹º
{ꢀCO(CH2)2CH2}(LOEt)(PPh3)2]+
(LOEt=(h5-C5H5)-
,
Co{P(O)(OEt)2}3) (1.870(13)A) [8c], and somewhat
shorter than that found for other ruthenium(II) five-
and six-membered oxacyclocarbene complexes [Ru-
¸¹¹¹¹¹¹¹¹º
{ꢀCOCH2(CH2)nCH2}(h5-C5H5)(dppe)]+ (n=1, 1.92(1)
¸¹¹¹¹¹º
the
intramolecular
cyclization
of
[RuCl(h5-
5
,
and n=2, 1.938(4) A [8d], [Ru{ꢀCO(CH2)2CH2}(h -
C5Me5)(h3-ADPP)]+ (AD¸PP¹=¹¹a¹ll¹ylºdiphenylphosphine)
C9H7)(dppm)] towards 5-hexyn-1-ol to be faster than
that observed in all other cases. All attempts to prepare
selectively the intermediate vinylidene failed, giving in-
stead mixtures of the hydroxybutylvinylidene complex
and the cyclic carbene complex 5c.
5
,
(1.956(4) A) [8b], [Ru{;ꢀCO(CH2)2CH(Ph)}(h -C5H5)-
(CO)(PPh3)]+ (1.946(8) A) [8e]. The cyclic carbene lig-
,
and shows an appreciable deviation from the vertical
orientation: DA=29.7(5)° versus DA=0° calculated
by theoretical studies for carbene complexes [9]. The
oxacycloheptylidene ring adopts a ‘pseudochair’ con-
formation. This is supported by the small torsion angle
C6ꢁO1ꢁC1ꢁC2 (−13(2)°) and the similarity of the rest
torsion angles (see Table 5).
The characterization of complexes 4a–d and 5a–d
has been achieved by means of standard spectroscopic
1
techniques (IR and H-, 31P{1H}- and 13C{1H}-NMR)
and elemental analyses (details are given in the Section
4 and in Tables 1–4). Significant spectroscopic features

28
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M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
29
2

30
M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
The indenyl group is h5-bonded to ruthenium with a
distance between the metal atom and the centroid (C*)
2.3. Reacti6ity of 2-oxacycloalkylidene complexes
As expected, Cb-hydrogen atoms of the oxacy-
cloalkylidene complexes show acidity. Although no hy-
drogen–deuterium exchange processes have been
observed in CDCl3–D2O (excess), the treatment of
oxacycloalkylidene compounds with an equi-
molar amount of LitBu in THF gives rise to the
of the five-membered ring of 1.99(9); this distance lies
,
in the range 1.82–1.99 A found for other ruthenium
and osmium indenyl complexes [10]. The structure
shows a slight distortion of the five-carbon ring from
planarity with hinge angle (HA) and fold angle (FA)
values of 6.0(1) and 11.0(1)°, respectively (Table 5). The
characteristic displacement of the metal atom away
from the C9ꢁC10 ring junction in the indenyl ligand is
forma¸ti¹on¹¹¹¹¹¹¹¹º
of
the
oxacycloalkenyl
complexes
[Ru{CꢀCH(CH2)nCH2O}(h5-C9H7)LL%] (L=L%=PPh3,
n=2 (7a); L=PPh3, L%=PMe3, n=1 (6d), n=2 (7d),
n=3 (8d) (55–60%). They have been isolated as very
air and moisture-sensitive solids and characterized only
by NMR spectroscopy (see Section 4). Significantly, the
1H-NMR spectra of alkenyl complexes show the ꢀCH
alkenyl proton as a broad singlet or a triplet in the l
4.64–5.13 range. The complexes easily give back the
oxacycloalkylidene precursors in the presence of traces
of water. The treatment of a solution of oxacycloalkyli-
dene complexes in CDCl3 with an excess of LitBu leads
to a double deprotonation of the Cb-hydrogens; the
,
also observed with a slip-fold (D) value of 0.22(5) A, the
highest one reported for h5-indenyl complexes [10].
This distortion toward an h3 binding mode appears to
be maintained in solution (Dl(C-3a,7a)= −14.70
ppm) (see 13C-NMR data, Table 2). The preferred
conformation of the indenyl ligand is such that the
benzo ring is orientated nearly trans to the carbene
group with a CA=16.6(6)°. Further CA values for a
series of h5-indenyl ruthenium complexes have been
reported [10].
subsequent addition of D2O produces deuterated com-
¸¹¹¹¹¹¹¹¹º
plexes [Ru{ꢀCOCH2(CH2)nCD2}(h5-C9H7)LL%][PF6] as
1
confirmed by the H-NMR spectra in which the b-CH2
Table 5
b
Selected bond distances, slip parameter D a (A), bond, dihedral, FA ,
resonance of the precursor complexes is no longer
observed.
,
HA c, DA d, and CA e, and torsion angles (°) for complex 5a
Distances
RuꢁC*
RuꢁC1
RuꢁP1
RuꢁP2
C1ꢁC2
C1ꢁO1
1.99(9)
1.89(1)
2.358(4)
2.342(4)
1.53(2)
1.31(2)
C2ꢁC3
C3ꢁC4
C4ꢁC5
C5ꢁC6
C6ꢁO1
D
1.53(2)
1.55(3)
1.47(3)
1.50(3)
1.49(2)
0.22(5)
3. Conclusions
This study reports a general synthetic route for the
preparation of oxacycloalkylidene complexes, contain-
ing the indenylruthenium(II) moiety [Ru(h5-C9H7)LL%],
Angles
starting from v-alkynols. Oxacycloalkylidene com-
¸¹¹¹¹¹¹¹º
plexes
[Ru{ꢀCOCH2(CH2)nCH2}(h5-C9H7)LL%][PF6]
C*ꢁRuꢁC1
C*ꢁRuꢁP1
C*ꢁRuꢁP2
P1ꢁRuꢁP2
P1ꢁRuꢁC1
P2ꢁRuꢁC1
C2ꢁC1ꢁO1
O1ꢁC6ꢁC5
HA
117.5(1)
123.2(1)
119.3(1)
103.4(1)
89.0(4)
90.9(4)
114(1)
116(2)
6(1)
16.6(6)
C6ꢁC5ꢁC4
C5ꢁC4ꢁC3
C4ꢁC3ꢁC2
C3ꢁC2ꢁC1
RuꢁC1ꢁC2
RuꢁC1ꢁO1
C1ꢁO1ꢁC6
FA
115(2)
114(2)
113(2)
116(1)
124(1)
122(1)
126(1)
11(1)
(L=L%=PPh3, n=1 (2a), 2 (3a), 3 (5a); L=L%=
PMe2Ph, n=1 (2b), 2 (3b), 3 (5b); LL%=dppm, n=1
(2c), 2 (3c), 3 (5c); L=PPh3, L%=PMe3, n=1 (2d), 2
(3d), 3 (5d)) are formed regardless of the separation
between the triple bond and the hydroxy group in the
starting alkynol. The formation of these complexes
proceeds via intermediate hydroxyvinylidene complexes
which have been isolated in the case of 5-hexyn-1-ol,
[Ru{ꢀCꢀC(H)(CH2)3CH2OH}(h5-C9H7)LL%][PF6] [(L=
L%=PPh3 (4a), L=L%=PMe2Ph (4b), L=PPh3, L%=
PMe3 (4d). The first ruthenium oxacycloheptylidene
complexes (5a–d) are reported. In addition, the first
DA
29.7(5)
CA
Torsion angles
C1ꢁO1ꢁC6ꢁC5
C6ꢁO1ꢁC1ꢁC2
O1ꢁC1ꢁC2ꢁC3
C1ꢁC2ꢁC3ꢁC4
74(2)
−13(2)
−58(2)
84(2)
C2ꢁC3ꢁC4ꢁC5
C3ꢁC4ꢁC5ꢁC6
C4ꢁC5ꢁC6ꢁO1
−64(2)
58(2)
−76(2)
crystallographic characterization of an 2-oxacyclo-
heptylidene complex, [Ru{ꢀCOCH2(CH2)3CH2}(h5-
C9H7)(PPh3)2][PF6] 5a, is also reported.
a D=d(RuꢁC9,C10)−d(RuꢁC8,C11).
¸¹¹¹¹¹¹¹¹º
b FA (fold angle)=angle between the planes defined by [C8, C7,
C11] and [C10, C15, C14, C13, C12, C9].
c HA (hinge angle)=angle between the planes defined by [C8, C7,
C11] and [C8, C11, C10, C9].
d DA (dihedral angle)=angle between the planes defined by [C*,
Ru, C1] and [Ru, C1, O1, C2].
4. Experimental
e CA (conformational angle)=angle between the planes defined by
[C**, C*, Ru] and [C*, Ru, C1]. C*=centroid of C8, C7, C11, C10,
C9. C**=centroid of C9, C10, C15, C14, C13, C12.
The reactions were carried out under dry nitrogen
using Schlenk techniques. All solvents were dried by

M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
31
standard methods and distilled under nitrogen before
use. The complexes [RuCl(h5-C9H7)LL%] (L=L%=
PPh3, PMe2Ph; LL%=dppm; L=PPh3, L%=PMe3)
were prepared by literature methods [11,12]. Alkynols
and NaPF6 were used as received from Aldrich Chemi-
cal Co.
Anal. Calc. for RuC34H37F6OP3; C, 52.99; H, 4.84.
Found: C, 53.14; H, 4.94; 139%. For 3d, 30 min; 70;
1247, 838; Anal. Calc. for C35H39F6OP3Ru; C, 53.64;
H, 5.01. Found: C, 52.73; H, 5.13; 155%.
4.2. Synthesis of the hydroxybutyl6inylidene complexes
[Ru{ꢀCꢀC(H)(CH2)3CH2OH}(p5-C9H7)LL%][PF6].
L=L%=PPh3 (4a), L=L%=PMe2Ph (4b); L=PPh3,
L%=PMe3 (4d)
Infrared spectra were recorded on a Perkin–Elmer
1720-XFT spectrometer. The conductivities were mea-
sured at room temperature (r.t.), in ca. 10−3 mol dm−3
acetone solutions, with a Jenway PCM3 conductimeter.
The C, H and N analyses were carried out with a
Perkin–Elmer 240-B microanalyzer (uncompleted com-
bustions were observed for 3a, 2c and 3d). NMR
spectra were recorded on a Bruker AC300 or AC200
instruments at 300 MHz (1H), 121.5 MHz (31P) or 75.4
MHz (13C) or 200 MHz (1H), 50.32 (13C) or 81.01 (31P),
5-Hexyn-1-ol (0.54 ml, 5 mmol) was added to a
refluxing solution of the complex [RuCl(h5-C9H7)LL%]
(1 mmol) and NaPF6 (0.330 g, 2 mmol) in 40 ml of
ethanol. The resulting solution was refluxed (ca. 15
min) to give an orange solution. The solvent was then
evaporated to dryness, and the solid residue was dis-
solved in CH2Cl2 (ca. 4 ml) and filtered into stirred
Et2O (ca. 100 ml) to give a precipitate. The resulting
solid was washed with Et2O (3×20 ml) and vacuum-
dried. Yield (%), IR (KBr, w(PF−6 ), cm−1) and analyti-
cal data are as follows: For 4a, 75; 839; Anal. Calc. for
C51H47F6OP3Ru; C, 62.26; H, 4.81. Found: C, 61.50; H,
4.93%. For 4b, 75, 840; Anal. Calc. for C31H39F6-
OP3Ru; C, 50.61; H, 5.34. Found: C, 50.79; H, 5.52%.
For 4d, 80; 839; Anal. Calc. for C36H41F6OP3Ru; C,
54.20; H, 5.18. Found: C, 54.61; H, 5.27%.
1
using SiMe4 or 85% H3PO4 as standards. H-, 13C{1H}-
and 31P{1H}-NMR spectroscopic data for the cyclic
carbene and the hydroxybutylvinylidene complexes are
collected in Tables 1–4.
4.1. Synthesis of 2-oxacyclopentylidene and
2-oxacyclohexylidene complexes
¸¹¹¹¹¹¹¹º
[Ru{ꢀCOCH2(CH2)nCH2}(p5-C9H7)LL%][PF6].
L=L%=PPh3, n=1 (2a), 2 (3a); L=L%=PMe2Ph,
n=1 (2b), 2 (3b); LL%=dppm, n=1 (2c), 2 (3c);
L=PPh3, L%=PMe3, n=1 (2d), 2 (3d)
4.3. Synthesis of the 2-oxacycloheptylidene complexes
¸¹¹¹¹¹¹¹º
[Ru{ꢀCOCH2(CH2)3CH2}(p5-C9H7)LL%][PF6].
L=L%=PPh3 (5a); L=L%=PMe2Ph (5b);
LL%=dppm (5c); L=PPh3, L%=PMe3 (5d)
4.1.1. General procedure
A suspension of the complex [RuCl(h5-C9H7)LL%]
1a–d (1 mmol), NaPF6 (0.252 g, 1.5 mmol) and the
corresponding alkynol (5 mmol) in 40 ml ethanol was
refluxed until the colour of the solution changed from
red to yellow. The resulting solution was then evapo-
rated to dryness, and the solid residue was dissolved
in CH2Cl2 (ca. 3 ml) and filtered into stirred Et2O (ca.
4.3.1. General procedure
A suspension of the complex [RuCl(h5-C9H7)LL%]
1a–d (1 mmol), NaPF6 (0.252 g, 1.5 mmol) and the
corresponding alkynol (5 mmol) in 40 ml ethanol was
refluxed until the colour of the solution changed from
red to yellow. The resulting solution was then evapo-
rated to dryness, and the solid residue was dissolved
in CH2Cl2 (ca. 3 ml) and filtered into stirred Et2O (ca.
100 ml) giving
a
light yellow precipitate of
¸¹¹¹¹¹¹¹¹º
[Ru{ꢀCOCH2(CH2)nCH2}(h5-C9H7)LL%][PF6]. Reaction
time, yield (%), IR (KBr, w(COC), w(PF−6 ), cm−1),
analytical and conductivity (acetone, 20 °C, V−1 cm2
mol−1) data are as follows: for 2a, 20 min; 80; 1181,
840; Anal. Calc. for C49H43F6OP3Ru; C, 61.57; H, 4.53.
Found: C, 61.06; H, 5.06; 143%. For 3a, 20 min; 85;
1253, 840; Anal. Calc. for C50H45F6OP3Ru; C, 61.92;
H, 4.68. Found: C, 61.03; H, 4.71; 152%. For 2b, 30
min; 70; 1168, 842; Anal. Calc. for C29H35F6OP3Ru; C,
49.23; H, 4.98. Found: C, 49.68; H, 4.97; 142%. For 3b,
30 min; 60; 1239, 836; Anal. Calc. for C30H37F6OP3Ru;
C, 49.93; H, 5.17. Found: C, 49.89; H, 5.16; 105%. For
2c, 20 min; 60; 1167, 838; Anal. Calc. for
C38H35F6OP3Ru; C, 55.96; H, 4.32. Found: C, 55.02; H,
4.38; 136%. For 3c, 20 min; 60; 1243, 838; Anal. Calc.
for C39H37F6OP3Ru; C, 56.46; H, 4.49. Found: C,
56.23; H, 4.69; 152%. For 2d, 30 min; 90; 1168, 837;
100 ml) giving
a
light yellow precipitate of
¸¹¹¹¹¹¹¹¹º
[Ru{ꢀCOCH2(CH2)3CH2}(h5-C9H7)LL%][PF6]. Reaction
time, yield (%), IR (KBr, w(COC), w(PF−6 ), cm−1),
analytical and conductivity (acetone, 20 °C, V−1 cm2
mol−1) data are as follows: For 5a, 3 h; 75; 1241, 840;
Anal. Calc. for C51H47F6OP3Ru; C, 62.26; H, 4.81.
Found: C, 61.34; H, 5.69; 127%. For 5b, 3 h; 65; 1240,
838; Anal. Calc. for C31H39F6OP3Ru; C, 50.61; H, 5.34.
Found: C, 50.21; H, 5.46; 161%. For 5c, 1 h; 60; 1230,
837; Anal. Calc. for C40H39F6OP3Ru; C, 56.94; H, 4.66.
Found: C, 57.45; H, 4.80; 111%. For 5d, 2h; 65; 1243,
837; Anal. Calc. for C36H41F6OP3Ru; C, 54.20; H, 5.18.
Found: C, 53.71; H, 5.21; 125%.

32
M.P. Gamasa et al. / Journal of Organometallic Chemistry 651 (2002) 22–33
Table 6
5.66 (s br, 1H, H-2), 6.33 (m, 1H, Ind), 6.76–7.50 (m,
18H, PPh3, Ind). For 8d, 55; 31P{1H}(C6D6) l: 6.20 (d,
Crystallographic data for C51H47F6OP3Ru·CH2Cl2
2
2JPP%=34.7 Hz, PMe3), 57.20 (d, JPP%=34.7 Hz, PPh3).
Formula C51H47F6OP3Ru·CH2Cl2
1H(C6D6) l: 0.98 (d, 9H, JHP=8.4 Hz, PMe3), 1.74 (m,
4H, 2CH2), 2.29 (m, 2H, ꢀCCH2), 3.84 (m, 2H, OCH2),
4.90 (m, 2H, ꢀCH and Ind), 5.03 (s br, 1H, Ind), 5.85 (s
br, 1H, H-2), 6.48 (m, 1H, Ind), 6.85–7.38 (m, 18H,
PPh3, Ind).
,
a (A)
12.087(2)
17.752(6)
24.413(8)
92.97(4)
1068.84
5232(3)
1.36
2184
0.7107
293
Mo–Ka
Graphite crystal
P21/n
Monoclinic
0.18, 0.28, 0,21
0.55
0.84–1.18
v–2u
2–22
,
b (A)
,
c (A)
i (°)
Molecular weight
3
,
V (A )
Dcalc (g cm−3
F (000)
)
4.5. X-ray structure determination
,
Wavelength (A)
Temperature (K)
Radiation
Monochromator
Space group
A summary of the fundamental crystal data is given
in Table 6. Data were collected from a single crystal on
a PW1100 diffractometer, using graphite-monochro-
mated Mo–Ka. A total of 6484 independent reflections
were measured, of which 4808 were considered ob-
served according to the criterion I\3|(I). Scattering
factors and dispersion corrections were taken from
International Tables for Crystallography [13]. The
structure was solved by Patterson methods and Fourier
synthesis and most of the calculations were performed
by using XRAY80 [14] and DIRDIF [15]. The structure
was refined by least-squares methods using unit weights
and anisotropic thermal parameters for all non-hydro-
gen atoms. The positions of the H atoms were calcu-
lated geometrically and were fixed during the
least-squares refinement. No extinction correction was
applied but three low angle reflections which were
observed much smaller than calculated were not used.
At the end of the isotropic refinement, an empirical
absorption correction was carried out using DIFABS
[16].
Crystal system
Crystal size (mm)
v (mm−1
)
Range of abs
Diffraction geom
qRange (°)
Index ranges for data collection −135h513, 05k520, 05l526
Number of contrib. reflections 4808
Number of variables
Final R factors R(I\3|(I))
586
R=0.080, Rw=0.084
4.4. Oxacycloalkenyl complexes
¸¹¹¹¹¹¹¹¹¹º
[Ru{CꢀCH(CH2)nCH2O}(p5-C9H7)LL%].
L=L%=PPh3, n=2 (7a); L=PPh3, L%=PMe3, n=1
(6d), 2 (7d), 3 (8d)
LitBu (60 ml of a 1.7 M solution, 0.1 mmol) was
¸¹¹¹¹¹¹¹º
added to a suspension of [Ru{ꢀCOCH2(CH2)nCH2}(h5-
C9H7)LL%][PF6] (0.1 mmol) in THF at −20 °C to give
an orange solution. After stirring at r.t. for 15 min, the
solvent was evaporated under vacuum and the solid
residue was extracted with Et2O. The evaporation of
Acknowledgements
the Et2O gave an orange, air- and moisture-sensitive
This work was supported by the Direccio´n General
de Investigacio´n Cient´ıfica y Te´cnica of Spain (DGI-
CYT, Project PB96-0558) and the Ministerio de Ciencia
y Tecnolog´ıa (MCT, Project BQU 2000-0227). We
thank the Fundacio´n para la Investigacio´n Cient´ıfica y
Te´cnica de Asturias (FICYT) for fellowship to
B.M.M.-V.
¸¹¹¹¹¹¹¹¹¹º
solid of [Ru{CꢀCH(CH2)nCH2O}(h5-C9H7)LL%]. Yield
(%), and NMR spectroscopic data are as follows: For
1
7a, 60; 31P{1H}(C6D6) l: 50.77; H(C6D6) l: 2.30 (m,
2H, CH2), 2.98 (m, 2H, ꢀCCH2), 3.68 (m, 2H, OCH2),
4.96 (d, 2H, JHH=2.2 Hz, H-1,3), 5.13 (s br, 1H, ꢀCH),
5.63 (m, 2H, Ind), 5.87 (s br, 1H, H-2), 6.86–7.15 (m,
32H, PPh3, Ind). For 6d, 55; 31P{1H}(C6D6) l: 7.75 (d,
2
2JPP%=33.4 Hz, PMe3), 56.45 (d, JPP%=33.4 Hz, PPh3).
1H(C6D6) l: 1.22 (d, 9H, JHP=8.7 Hz, PMe3), 2.94 (m,
2H, ꢀCCH2), 4.27 (t, 2H, JHH=9.0 Hz, OCH2), 4.89 (t,
1H, JHH=1.9 Hz, ꢀCH), 5.11 and 5.12 (s br, 1H each,
H-1 and H-3), 5.79 (s br, 1H, H-2), 6.52 (m, 1H, Ind),
7.00–7.62 (m, 18H, PPh3, Ind). For 7d, 60;
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The
first
oxacycloheptylidene
osmium
complex
¸¹¹¹¹º
[Os{ꢀCO(CH2)4CH2}(h5-C9H7)(PPh3)2][PF6] has been recently
prepared by activation of 5-hexyn-1-ol by [OsCl(h5-
C9H7)(PPh3)2]: J. Gimeno, M. Gonza´lez-Cueva, E. Lastra, un-
published work.
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