Activation of Alkynols by [Cp*RuCl(PEt3)2]: New Intermediates and Alternative Dehydration Products. X-ray Crystal Structures of [Cp*Ru{=C=CHC(=CH2)Ph}(PEt3)2][BPh 4], [Cp*Ru(=C=C=CPh2<

Article abstract of DOI:10.1021/om990484b

The full sequence of species involved in the activation of alkynols by the fragment [Cp*Ru-(PEt₃)₂]⁺ was determined. The complex [Cp*RuCl(PEt₃)₂] (Cp* = C₅Me₅) reacts with 2-prop

Full text of DOI:10.1021/om990484b

Organometallics 1999, 18, 4563-4573
4563
Activa tion of Alk yn ols by [Cp *Ru Cl(P Et3)2]: New
In ter m ed ia tes a n d Alter n a tive Deh yd r a tion P r od u cts.
X-r a y Cr ysta l Str u ctu r es of
[Cp *Ru {dCdCHC(dCH2)P h }(P Et3)2][BP h 4],
[Cp *Ru (dCdCdCP h 2)(P Et3)2][BP h 4], a n d
[Cp *Ru {CtCC(P Et3)Me2}(P Et3)2][BP h 4]
Emilio Bustelo, Manuel J ime´nez Tenorio, M. Carmen Puerta,* and
Pedro Valerga
Departamento de Ciencia de Materiales e Ingenier´ıa Metalu´rgica y Quı´mica Inorga´nica,
Facultad de Ciencias, Universidad de Ca´diz, Apartado 40, 11510 Puerto Real, Ca´diz, Spain
Received J une 24, 1999
The full sequence of species involved in the activation of alkynols by the fragment [Cp*Ru-
(PEt3)2]+ was determined. The complex [Cp*RuCl(PEt3)2] (Cp* ) C5Me5) reacts with 2-propyn-
1-ol derivatives in the presence of NaBPh4, yielding the metastable 3-hydroxyalkynyl hydrido
complexes [Cp*Ru(H){CtCC(OH)RR′}(PEt3)2][BPh4], intermediates in the formation of the
corresponding 3-hydroxyvinylidene complexes [Cp*Ru{dCdCHC(OH)RR′}(PEt3)2][BPh4], to
which these compounds rearrange both in solution and in the solid state. η2-Alkynol
derivatives have been detected by 31P{1H} NMR at -40 °C as the first species involved in
the reaction of alkynols with [Cp*Ru(N2)(PEt3)2][BPh4]. Dehydration of 3-hydroxyalkynyl
hydrido and 3-hydroxyvinylidene complexes may be spontaneous or forced, leading to
vinylvinylidene, allenylidene, or the novel enynyl hydrido species. The unstable allenylidene
led to the formation of an alkynylphosphonio compound without an external source of
phosphine.
In tr od u ction
group. At the moment, the reactivity and catalytic
activity are centers of current scientific interest.4
Since the beginning, the dehydration of a hydroxyvi-
nylidene intermediate has been proposed as the reason-
able previous step to allenylidene.1,5 These species have
been isolated, both as complexes that cannot be dehy-
drated into allenylidene derivatives,6 or as intermedi-
ates sufficiently stable toward dehydration.7 The fact
that the dehydration may take two different reaction
pathways when deprotonatable groups are adjacent to
the carbon bearing the hydroxy group has become in
some cases a synthetic limitation in the preparation of
allenylidenes, yielding mixtures with the alkenylvi-
nylidene complex as side product.6c,8 However, there has
been increasing interest in a clean synthesis of alk-
enylvinylidene derivatives; these have not been fre-
quently isolated and characterized8,9 and have a less
It is reasonably well-established now that the reaction
of propargyl alcohols HCtCC(OH)R2 with ruthenium
complexes, which was reported for the first time by
Selegue,1 represents a simple and convenient route for
the preparation of allenylidene complexes. These spe-
cies, due to the unsaturated character of the carbon
chain, exhibit unusual behavior, giving rise to a variety
of C-C coupling reactions and yielding in many cases
unexpected products.2 So far, allenylidenes have been
obtained and studied with several substrate complexes,
and their synthesis has been extended to metals such
as the Cr triad, Mn, Fe, Os, Ir, and Rh,3 in addition to
ruthenium allenylidenes, which constitute the largest
* To whom correspondence should be addressed. E-mail: carmen-
.puerta@uca.es.
(1) Selegue, J . P. Organometallics 1982, 1, 217.
(2) (a) Esteruelas, M. A.; Go´mez, A.; Lo´pez, A. M.; Modrego, J .;
On˜ate, E. Organometallics 1997, 16, 5826. Bohanna, C.; Callejas, B.;
Edwards, A. J .; Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.;
Valero, C. Organometallics 1998, 17, 373. Esteruelas, M. A.; Go´mez,
A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz, N. Organometallics 1998, 17, 2297.
Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E. Organome-
tallics 1998, 17, 3567. (b) Wiedemann, R.; Steinert, P.; Gevert, O.;
Werner, H. J . Am. Chem. Soc. 1996, 118, 2495. Braun, T.; Meuer, P.;
Werner, H. Organometallics 1996, 15, 4075. (c) Fischer, H.; Leroux,
F.; Stumpt, R.; Roth, G. Chem. Ber. 1996, 129, 1475. (d) Cadierno, V.;
Gamasa, M. P.; Gimeno, J .; Lo´pez-Gonza´lez, M. C.; Borge, J .; Garc´ıa-
Granda, S. Organometallics 1997, 16, 4453. (e) Kalinin, V. N.; Deunov,
V. V.; Lusenkova, M. A.; Petrovsky, P. V.; Kolobova, N. E. J .
Organomet. Chem. 1989, 379, 303. (f) Touchard, D.; Dixneuf, P. H.
Coord. Chem. Rev. 1998, 178-180, 409.
(4) Trost, B. M.; Flygare, J . A. J . Am. Chem. Soc. 1992, 114, 5476.
Fu¨rstner, A.; Picquet, M.; Bruneau, C.; Dixneuf, P. H. J . Chem. Soc.,
Chem. Commun. 1998, 1315. Harlow, K. J .; Hill, A. F.; Wilton-Ely, J .
D. E. T. J . Chem. Soc., Dalton Trans. 1999, 285.
(5) Le Bozec, H.; Ouzzine, K.; Dixneuf, P. H. J . Chem. Soc., Chem.
Commun. 1989, 219.
(6) (a) Touchard, D.; Haquette, P.; Pirio, N.; Toupet, L.; Dixneuf, P.
H. Organometallics 1993, 12, 3132. (b) Le Lagadec, R.; Roman, E.;
Toupet, L.; Mu¨ller, U.; Dixneuf, P. H. Organometallics 1994, 13, 5030.
(c) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva, M.;
Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Organo-
metallics 1996, 15, 2137.
(7) (a) Braun, T.; Steinert, P.; Werner, H. J . Organomet. Chem. 1995,
488, 169. (b) de los R´ıos, J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga,
P. J . Organomet. Chem. 1997, 549, 221.
(3) Werner, H. J . Chem. Soc., Chem. Commun. 1997, 903. Bruce,
M. I. Chem. Rev. 1998, 98, 2797 and references therein.
(8) Touchard, D.; Pirio, N.; Dixneuf, P. H. Organometallics 1995,
14, 4920.
10.1021/om990484b CCC: $18.00 © 1999 American Chemical Society
Publication on Web 10/06/1999

4564 Organometallics, Vol. 18, No. 22, 1999
Bustelo et al.
Sch em e 1. Syn th esis of 3-Hyd r oxya lk yn yl
developed chemistry, despite the fact that they seem to
be active species involved in some C-C coupling
processes.7b,10
Hyd r id e Com p lexes
(dippe)]+ and [CpRu(PMe3)2]+ systems the η2 coordination
of monosubstituted alkynes13b,18 is well-known, but such
is not the case for [Cp*Ru(dippe)]+: although the use
of a Cp*Ru system containing this large, strong electron-
releasing phosphine seems to be the key for the isolation
of these Ru(IV) species, due to its electronic and steric
properties, it is also true that steric hindrance should
make more difficult the detection of the η2-alkynol
precursor which would be the first step in the overall
activation of alkynols. Despite this, we now show the
results of the activation of alkynols by the fragment
[Cp*Ru(PEt3)2]+, which has allowed us to complete the
full sequence of the aforementioned intermediates: η2-
alkynol, 3-hydroxyalkynyl hydrido, and 3-hydroxyvi-
nylidene.19 Alkenylvinylidene and allenylidene have
been obtained separately as dehydration products, but
this system makes also possible the novel synthesis of
hydrido enynyl complexes by carrying out the dehydra-
tion before isomerization of the 3-hydroxyalkynyl hy-
drido derivative. An unexpected nucleophilic phosphine
addition on an allenylidene moiety without an external
source of phosphine is reported as well.
The way to hydroxyvinylidene species implicates Ct
C bond coordination as the initial step in the activation
of propargyl alcohols, followed by a subsequent tautomer-
ization.7a Although an isomerization via a 1,2-H shift
from η2-alkyne into vinylidene seems to be the most
feasible explanation for the tautomerization process,11
there is another way that has been proven to be
accessible by the [Cp*Ru(dippe)]+ system. On the basis
of the ability of Cp* to stabilize Ru(IV) complexes,12 it
goes via oxidative addition of the alkyne, yielding
metastable alkynyl hydrido compounds, the tautomer-
ization process of which to vinylidene was studied in
depth.13 In the case of alkynols, the interaction with
i
[OsCl(NO)(PiPr2R)2] (R ) Ph, Pr) afforded stable (3-
hydroxyalkynyl)hydridoosmium(II) complexes.14 Like-
wise, the reactions of [RhCl(PiPr3)2] and [IrH2Cl(PiPr3)2]
with alkynols led to the formation of either (η2-alkynol)-
or (3-hydroxyalkynyl)hydridorhodium and (3-hydroxy-
alkynyl)hydridoiridium complexes, respectively, as the
first isolable products,15 but until now, there has not
been evidence for analogous ruthenium species.
Resu lts a n d Discu ssion
As we reported in a recent communication,19 when
[Cp*RuCl(PEt3)2]12b is added to a MeOH solution con-
taining NaBPh4 and an alkynol HCtCC(OH)RR′ at 0
°C, the 3-hydroxyalkynyl hydrido complexes [Cp*RuH-
{CtCC(OH)RR′}(PEt3)2][BPh4] (R,R′ ) H, H (1a ); H, Me
(1b); H, Ph (1c); Me, Ph (1d ); Ph, Ph (1e); Me, Me (1f);
C5H10 (1g)) precipitate immediately as white-yellow
solids. (Scheme 1) If the order in which the reagents
are mixed is reversed, the reaction is not so clean, and
mixtures of products of different natures are obtained
depending upon the alkynol used. Complexes 1a -g are
derived from the formal insertion of the metal atom into
the C-H bond of the alkynol, and hence, they must be
regarded as RuIV species. These compounds rearrange
irreversibly both in solution and in the solid state to
the corresponding 3-hydroxyvinylidene isomers; there-
fore, they must be handled and stored at temperatures
close to 0 °C in order to prevent isomerization. This
behavior is analogous to that previously observed in the
course of the reaction of [Cp*RuCl(dippe)] with 1-al-
kynes,13b which also led to the isolation of metastable
RuIV hydrido-alkynyl derivatives which rearrange to
their vinylidene tautomers. In this case, so far, a similar
behavior toward alkynols has not been observed.7b The
η2 coordination of alkynols has been observed in some
osmium complexes such as [CpOsCl{η2-HCtCC(OH)-
RR′}(PiPr3)] (R, R′) Me, C5H10, Ph) previous to the
formation of the alkenylvinylidene or allenylidene de-
rivative,16 as well as in the complex [CpOs{κ1-OC(O)-
CH3}{η2-HCtCC(OH)Ph2}(PiPr3)].17 In the [CpRu-
(9) (a) Selegue, J . P.; Young, B. A.; Logan, S. L. Organometallics
1991, 10, 1972. (b) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge,
J .; Garc´ıa-Granda, S. Organometallics 1997, 16, 3178. (c) Bianchini,
C.; Peruzzini, M.; Zanobini, F.; Lopez, C.; de los R´ıos, I.; Romerosa, A.
J . Chem. Soc., Chem. Commun. 1999, 443. (d) J ime´nez-Tenorio, M.
A.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Manuscript in
preparation.
(10) (a) Selegue, J . P. J . Am. Chem. Soc. 1983, 105, 5921. (b)
Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E.; Borge, J .; Garc´ıa-
Granda, S. Organometallics 1994, 13, 745. (c) J ime´nez-Tenorio, M. A.;
J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 1997,
16, 5528.
(11) Silvestre, J .; Hoffmann, R. Helv. Chim. Acta 1985, 68, 1461.
(12) (a) Suzuki, H.; Lee, D. H.; Oshima, N.; Moro-Oka, Y. Organo-
metallics 1987, 6, 1569. Arliguie, T.; Border, C.; Chaudret, B.; Devillers,
J .; Poilblanc, R. Organometallics 1989, 8, 1308. Masuda, K.; Ohkita,
H.; Kurumatani, S., Itoh, K. Organometallics 1993, 12, 2221. (b) Coto,
A.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics
1998, 20, 4392.
(13) (a) de los R´ıos, I.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga,
P. J . Chem. Soc., Chem. Commun. 1995, 1757. (b) de los R´ıos, I.;
J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. J . Am. Chem. Soc.
1997, 119, 6529.
(14) Werner, H.; Flu¨gel, R.; Windmu¨ller, B.; Michenfelder, A.; Wolf,
J . Organometallics 1995, 14, 612.
(15) Werner, H.; Rappert, T.; Wiedemann, R.; Wolf, J .; Mahr, N.
Organometallics 1994, 13, 2721. Werner, H.; Lass, R. W.; Gevert, O.;
Wolf, J . Organometallics 1997, 16, 4077.
(16) Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J . I. Orga-
nometallics 1997, 16, 4657. Crochet, P.; Esteruelas, M. A.; Lo´pez, A.
M.; Ruiz, N.; Tolosa, J . I. Organometallics 1998, 17, 3479.
(17) Crochet, P.; Esteruelas, M. A.; Gutie´rrez-Puebla, E. Organo-
metallics 1998, 17, 3141.
(18) Bullock, R. M. J . Chem. Soc., Chem. Commun. 1989, 165.
(19) A preliminary account of this work has appeared at: Bustelo,
E.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics
1999, 18, 950.

Activation of Alkynols by [Cp*RuCl(PEt3)2]
Organometallics, Vol. 18, No. 22, 1999 4565
Ta ble 1. Selected IR a n d 1H a n d 31P {1H} NMR Da ta for [Cp *Ru H{CtCC(OH)RR′}(P Et3)2][BP h 4]
31P{1H} NMRb
1H NMRc
4J HP
a
IR (Nujol, cm-1
)
R, R′
H, H
H, Me
H, Ph
Me, Ph
Ph, Ph
Me, Me
C5H10
OH, CtC, Ru-H
2J PP′
Ru-H
2J HP
C5Me5
R
R′
1a
1b
1c
1d
1e
1f
n.o., 2117, 2024
3528, 2109, 2074
n.o., 2108, 2018
3312, 2104, 2020
3450, 2103, 2026
3353, 2120, 2028
3331, 2105, 2029
36.8 s
36.6 s
37.1, 37.2, d
37.4, 37.2, d
38.0 s
-9.25 t
-9.37 t
-9.36 t
-9.35 t
-9.39 t
-9.28 t
-9.31 t
30.5
29.8
29.9
29.9
29.8
30.6
30.2
1.67 t
1.67 t
1.63 t
1.65 t
1.67 t
1.66 t
1.67 t
1.2
1.1
1.4
1.2
1.0
1.2
1.1
4.29 t
4.53 sa
5.46 sa
1.82 s
1.38 d (6.4 Hz)
7.30, 7.36, 7.37
7.29, 7.37, 7.55
7.29, 7.33, 7.50
20.1
21.3
36.8 s
37.2 s
1.46 s
1.45 m
1g
1.58 m
a
b
n.o. ) not observed. Conditions: 161.89 MHz, CDCl3, 273 K. Resonances are given in ppm, and coupling constants are given in Hz.
c Conditions: 400 MHz, CDCl3, 273 K. Resonances are given in ppm, and coupling constants are given in Hz.
Ta ble 2. Selected 13C{1H} NMR Da ta for [Cp *Ru H{CtCC(OH)RR′}(P Et3)2][BP h 4]
13C{1H} NMRa
R, R′
C5Me5
C5Me5
CR
2J CP
Câ
Cγ
R
R′
1a
1b
1c
1d
1e
1f
H, H
H, Me
H, Ph
Me, Ph
Ph, Ph
Me, Me
C5H10
10.11
10.14
10.04
10.08
10.15
10.09
10.15
101.4
101.4
101.4
101.3
101.5
101.3
101.3
91.4 t
89.6 t
94.6 t
91.2 t
97.1 t
87.1 t
88.0 t
30.1
30.1
31.2
30.2
29.5
30.2
31.0
112.9
116.9
114.7
118.2
115.9
119.3
119.0
53.1
59.9
66.1
58.3
50.7
66.2
68.9
25.8
127.7, 128.4, 128.7, 142.8
124.3, 127.1, 128.1, 146.4
126.1, 127.4, 128.0, 145.9
32.3
32.3
1g
22.3, 25.1, 40.4
a
Conditions: 201.12 MHz, CDCl3, 273 K. Resonances are given in ppm, and coupling constants are given in Hz.
Ta ble 3. Selected IR a n d 1H a n d 31P {1H} NMR Da ta for [Cp *Ru {dCdCHa CHb(OHc)R}-(P Et3)2][BP h 4]
31P{1H} NMRb
2J PP′ C5Me5 4J HP
1H NMRc
4J HP 3J H
IRa
OH, CdC
aHb
R, R′
H, H
H, Me
H, Ph
Me, Ph
Ph, Ph
Ha
R
R′
3
2a
2b
2c
2d
2e
2f
3459, 1679 30.6 s
1.74 t
1.73 t
1.71 t
1.71 t
1.72 t
1.75 t
1.76 t
1.8
1.0
1.1
1.1
1.0
1.3
1.1
4.21 tt
4.12 dt
4.39 dt
4.38 sa
4.73 sa
4.05 sa
4.08 sa
1.6
1.6
1.4
8.4
8.4
8.4
4.05 dd, J HbOH ) 5.4
3
3444, 1643 30.6, 31.0, d
3592, 1631 30.5, 30.8, d
3598, 1633 28.9, 29.1, d
3576, 1634 29.3 s
35.9
34.5
35.5
4.56 dc, J HbMe ) 6.2
1.27 d
3
5.45 dd, J HbOH ) 3.6 7.29, 7.31, 7.34
1.63 s
7.28, 7.34, 7.36
7.30, 7.35, 7.62
1.37 s
1.44-1.57 m
Me, Me 3543, 1643 28.9 s
2g
C5H10
3573, 1651 29.1 s
1.84-1.95 m
a
b
As Nujol mulls, in cm-1
.
Conditions: 161.89 MHz, CDCl3, 273 K. Resonances are given in ppm, and coupling constants are given in
Hz. c Conditions: 400 MHz, CDCl3, 273 K. Resonances are given in ppm, and coupling constants are given in Hz.
spectral properties of compounds 1a -g resemble those
of the [Cp*RuH(CtCR)(dippe)][BPh4] to a great extent.
IR and NMR spectral data are displayed in Tables 1
and 2. Thus, they exhibit in their IR spectra one strong
ν(CtC) band at 2100-2120 cm-1 and a weak ν(RuH)
absorption at 2020-2030 cm-1, besides a ν(OH) band
about 3350 cm-1. The hydride resonance appears as one
high-field triplet in all cases, whereas the 31P{1H} NMR
spectra consist of one sharp singlet, except for the
complexes 1b-d , for which two partially overlapped
doublet signals (2J PP′ = 20 Hz) corresponding to an AB
spin system are observed. This is attributed to the
presence of the chiral γ-carbon atom in the alkynyl
group, which induces the magnetic nonequivalence of
the phosphorus atoms, as has been previously noted.2d
It was possible to register the 13C{1H} NMR spectra of
compounds 1a -g at 0 °C (Table 2). The most relevant
feature of these spectra is the resonance of the metal-
bound carbon atom, which is observed as a triplet (2J CP
= 30 Hz) in the range δ 85-100 ppm, while the â-carbon
appears as a singlet at δ 110-120 ppm.20 The spectral
data are consistent with a transoid four-legged piano-
stool structure for these compounds, similar to that
found by X-ray crystallography for [Cp*RuH(CtCC-
OOMe)(dippe)][BPh4].21
Me, Ph (2d ); Ph, Ph (2e); Me, Me (2f); C5H10 (2g)). This
process takes place both in solution and in the solid
state. However, since the subsequent process of dehy-
dration of the 3-hydroxyvinylidene ligand takes place
in solution in most cases, the best synthetic procedure
for the isolation of these derivatives in pure form has
proven to be the solid-state isomerization at 30-35 °C.22
This process can be monitored by IR spectroscopy
following the decrease of the ν(CtC) band and the
increase in a new band in the range 1630-1680 cm-1
attributable to ν(CdC) of the orange complexes 2a -g,
besides the nearby ν(OH) band at 3500 cm-1. IR and
NMR data for them are listed in Tables 3 and 4. The
vinylidene proton appears either as one multiplet due
to coupling to phosphorus nuclei and to protons present
at the γ-carbon (2a -c) or just as a broad resonance (2d -
g). The 13C{1H} NMR spectra (Table 4) show the typical
low-field resonance for the R-carbon as a triplet at δ 345
ppm (2J CP = 15 Hz) and the â-carbon at δ 110-120 ppm.
(20) It is not unusual that the signal of the R-carbon appears at
higher field than the signal of the â-carbon. Although there are not
analogous Ru(II) compounds to compare, this sequence agrees with
the data for neutral 3-methoxy or 3-hydroxyalkynyl compounds of Ru-
(II),6 Os(II),14 Rh(III),15 and Ir(I): Esteruelas, M. A.; Oro, L. A.;
Schrickel, J . Organometallics 1997, 16, 796.
(21) In this case, inhibition of isomerization by acid made recrys-
tallization possible, but with the [Cp*Ru(PEt3)2]+ system this method
does not work, leading to extensive decomposition products. For the
structure, see ref 13b.
As has been already mentioned, the 3-hydroxyalkynyl
hydrides 1a -g rearrange spontaneously to their 3-hy-
droxyvinylidene isomers [Cp*Ru{dCdCHC(OH)RR′}-
(PEt3)2][BPh4] (R,R′ ) H, H (2a ); H, Me (2b); H, Ph (2c);
(22) Except complex 2e, in which dehydration also occurs in the solid
state.

4566 Organometallics, Vol. 18, No. 22, 1999
Ta ble 4. Selected 13C{1H} NMR Da ta for [Cp *Ru {dCdCHC(OH)RR′}(P Et3)2][BP h 4]
Bustelo et al.
13C{1H} NMRa
R, R′
H, H
H, Me
H, Ph
Me, Ph
Me, Me
Cy
C5Me5
C5Me5
CR
2J CP
Câ
Cγ
R
R′
2a
2b
2c
2d
2f
10.77
10.79
10.74
10.93
10.88
10.92
102.4
102.7
102.8
102.6
102.3
102.2
345.4 t
344.5 t
343.7 t
344.8 t
345.9 t
345.5 t
15.5
15.0
15.2
14.3
15.6
17.0
110.1
115.5
114.5
120.3
120.0
118.9
54.4
62.1
67.9
106.3
68.6
70.1
26.5
128.2, 128.8, 135.5, 143.8
123.8, 127.2, 128.4, 148.9
34.4
33.0
2g
22.3, 24.8, 41.0
a
Conditions: 201.12 MHz, CDCl3, 273 K. Resonances are given in ppm, and coupling constants are given in Hz. For 2e see ref 22.
As was the case for their precursors, the 31P{1H} NMR
consists of one singlet except for compounds 2b-d , for
which the presence of a chiral group makes the phos-
phorus nuclei nonequivalent, and therefore two com-
pletely separated doublet signals (2J PP′ = 35 Hz) are
observed. This has been also reported for the analogous
chiral methoxyvinylidene complexes [Cp*Ru{dCdCHCH-
(OMe)Me}(PMe2Ph)2][PF6]6b and [(η5-C9H7)Ru{dCd
CHCH(OMe)Ph}(PPh3)2][PF6].6c Formation of such meth-
oxy compounds is avoided for 2a -g, since the formation
of those derivatives should implicate a nucleophilic
addition of methanol to allenylidene.6b Instead of this,
F igu r e 1. 31P{1H} NMR spectrum of [Cp*Ru{η2-HCt
the 3-hydroxyvinylidene compounds are quite stable, as
CCH(OH)Me}(PEt3)2][BPh4] (3b) in (CD3)2CO at -40 °C,
expected for a very electron-rich ruthenium moiety,2f but
showing the two sets of two doublets, corresponding each
not as stable as [Cp*RuCl{dCdCHC(OH)Ph2}{κ2(P,O)-
of the two possible stereoisomers for the cation complex.
iPr2PCH2CO2Me}],7a and they spontaneously dehydrate
Sch em e 2. Sp ecies In volved in th e In ter a ction of
[Cp *Ru (N2)(P Et3)2][BP h 4] w ith HCtCCH(OH)R
(R ) H, Me, P h ) in (CD3)2CO
in solution just as [Cp*Ru{dCdCHC(OH)Me2}(dippe)]-
[BPh4],7b except for those derived from primary or
secondary alcohols (2a -c). These two aforementioned
complexes are the only precedents of 3-hydroxyvi-
nylidene isolation as intermediates prior to allenylidene
formation. So far, attempts to carry out a kinetic study
of the isomerization of 3-hydroxyalkynyl into 3-hydroxy-
vinylidene complexes in solution did not show a good
fit with a first-order process. In contrast, although η2
coordination of an alkynol seemed to be quite hindered
due to the steric requirement of the Cp* ring along with
the two phosphines, it was possible to detect the
formation of [Cp*Ru{η2-HCtCCH(OH)R}(PEt3)2][BPh4]
(R ) H (3a ), Me (3b), Ph (3c)) complexes by addition of
alkynol into a precooled (CD3)2CO solution of the
complex [Cp*Ru(N2)(PEt3)2][BPh4]23 at -40 °C. When
HCtCCH2OH is added, the resonance for the dinitrogen
complex (a singlet at δ 21.7 ppm) is replaced by two
The dynamic process responsible for the observed
fluxional behavior is possibly the spinning of the alkynol
ligand around the π metal-carbon bond, as has been
suggested elsewhere.13b The π-alkynol adducts 3b and
3c exhibit at -40 °C two sets of two doublets in their
31P{1H} NMR spectra (Figure 1). This has been at-
tributed to the occurrence in solution of two possible
isomers for both 3b and 3c, due to the chirality of the
γ-carbon of the alkynol ligand. The doublet signals for
both isomers dissappear before coalescence when the
temperature is raised over -15 °C, yielding mixtures
of 3-hydroxyalkynyl hydrides 1b,c and 3-hydroxyvi-
nylidenes 2b,c. When tertiary propargyl alcohols are
added under the same conditions, the resonance of the
dinitrogen complex disappears, being directly replaced
2
doublets (at δ 22.1 and 22.5 ppm, J PP′ ) 44.5 Hz)
corresponding to an AB spin system. If temperature is
raised, the two doublets coalesce and eventually become
a singlet at -20 °C. Above -10 °C, this resonance
dissappears, and signals corresponding to the 3-hy-
droxyalkynyl hydride 1a and to the 3-hydroxyvinylidene
2a arise. Since only above 0 °C does the 3-hydroxyalky-
nyl hydrido complex 1a isomerize perceptibly24 into the
3-hydroxyvinylidene complex 2a , the simultaneous for-
mation of 1a and 2a at -10 °C must occur by two
independent reaction pathways, namely C-H oxidative
addition and a 1,2-hydrogen shift from the η2 derivative
3a , as shown in Scheme 2. These processes have been
the subject of theoretical studies,25 and the detection of
this η2-alkyne as an intermediate may add an interest-
ing supplementary experimental support.
(25) Pe´rez-Carren˜o, E.; Paoli, P.; Ienco, A.; Mealli, C. Eur. J . Inorg.
Chem., in press. Chen, W. C.; Yu, C. H. Chem. Phys. Lett. 1997, 277,
245 and references therein. Wakatsuki, Y.; Koga, N.; Yamazaki, H.;
Morokuma, K. J . Am. Chem. Soc. 1994, 116, 8105. Wakatsuki, Y.;
Koga, N.; Werner, H.; Morokuma, K. J . Am. Chem. Soc. 1997, 119,
360. Stegmann, R.; Frenking, G. Organometallics 1998, 17, 2089.
(23) J ime´nez-Tenorio, M.; Padilla, J .; Puerta, M. C.; Valerga, P.
Manuscript in preparation.
(24) Attempts to carry out a 31P{1H} NMR kinetic study were made
in the range 25-50 °C.

Activation of Alkynols by [Cp*RuCl(PEt3)2]
Organometallics, Vol. 18, No. 22, 1999 4567
Sch em e 3. Su m m a r y of Deh yd r a tion P r od u cts of
3-Hyd r oxyvin ylid en e Com p lexes
spectra of both compounds consist of one singlet at δ
30.9 and 32.1 ppm, respectively. The most relevant
features in the 1H NMR spectrum of the vinylvinylidene
are the signal for the vinylidene proton and two
resonances corresponding to each of the protons of the
dCH2 group. The 13C{1H} NMR spectra show the typical
low-field resonances for the metal-bound carbon atoms
at δ 351.4 ppm (2J CP ) 15.1 Hz) for 4b and 301.6 ppm
(2J CP ) 17.5 Hz) for 5c, consistent with those expected
for these sorts of species.6c,8 There are no significant
differences between these data for 4b and 5c with the
rest of the alkenylvinylidene and allenylidene species
obtained with different alkynols.
The formation of the allenylidene complex 5c by
activation of a secondary propargyl alcohol results
particularly remarkable, since this sort of compound
still remains very scarce and exhibits a higher reactivity
than the disubstituted species. The proton attached at
the γ-carbon appears as one broad resonance at δ 9.13
by the signals corresponding to 3-hydroxyalkynyl hy-
drido and 3-hydroxyvinylidene species, in a ratio similar
to that observed after the 3a -c signals decreased (about
3:1), but without η2-alkynol detection. 1H NMR spectra
of the complexes 3a -c were obscured by the excess of
free alkynol added into the NMR tube, and the signals
were not assigned. All attempts to isolate these π-alkyne
complexes as solids were unsuccessful, due to that the
fast isomerization operates even in the solid state. The
fact that all of the 1a -g complexes could be isolated as
solids from [Cp*RuCl(PEt3)2] by precipitation in MeOH
without contamination of the 2a -g isomers can be
attributed to their higher insolubility, along with the
fact that in this system the C-H oxidative addition
seems to occur faster than the 1,2-H shift.
1
ppm in the H NMR spectrum. Such resonances have
been observed for the previously reported monosubsti-
tutedallenylidenes[(η5-C9H7)Ru(dCdCdCHPh)(PPh3)2]-
[PF6]6c and [RuCl(dCdCdCHR)(dppm)2][PF6] (R ) Ph,
p-PhCl, p-PhF, p-PhOMe)8 at δ 9.09 and in the range δ
8.0-8.5 ppm, respectively.
In contrast with 5c, [Cp*Ru(dCdCdCPhR)(PEt3)2]-
[BPh4] (R ) Me (5d ), Ph (5e)) could be obtained easily
by method A. The X-ray crystal structure of 5e was
determined. It seems that the presence and number of
aromatic groups as substituents at the γ-carbon con-
tribute to the stabilization of allenylidene complexes in
an additive form, as can be inferred from the increasing
stability of the allenylidenes (5e > 5d > 5c). In this
connection, the complex 5d exhibits behavior halfway
between the quite reactive 5c and the nearly inert 5e
allenylidene.
The next step in the activation of alkynols, dehydra-
tion of the 3-hydroxyvinylidene moiety, although better
established, is still an open question with regard to the
control of the allenylidene vs alkenylvinylidene forma-
tion (Scheme 3). The nature and stability of the dehy-
dration products mainly depend on the substituents of
the alkynol, which is also manifested in the [Cp*Ru-
(PEt3)2]+ system. We show the possibility of a selective
synthetic route to give either alkenylvinylidene or
allenylidene, by using the appropriate method: (A)
spontaneous dehydration in solution,26 by starting from
[Cp*RuCl(PEt3)2] in MeOH and the alkynol and stirring
for 6-8 h, leading to the most stable compound (ther-
modynamic control) and (B) forced dehydration by
passing a CH2Cl2 solution of the 3-hydroxyvinylidene
complex through acidic alumina,27 yielding a rapid
dehydration which sometimes leads to metastable prod-
ucts (kinetic control). The hydroxyvinylidene 2a , as
expected for a primary alcohol, does not undergo dehy-
dration by any method. Likewise, neither 2b nor 2c
dehydrates spontaneously, but they do dehydrate by
method B and the complexes [Cp*Ru(dCdCHCHd
CH2)(PEt3)2][BPh4] (4b) and [Cp*Ru(dCdCdCHPh)-
(PEt3)2][BPh4] (5c) were obtained. The IR spectra of
these dehydration products show one ν(CdC) band at
1620 cm-1 for 4b, or one strong ν(CdCdC) absorption
at 1907 cm-1 in the case of 5c. The 31P{1H} NMR
In the case of alkynols bearing deprotonatable alkyl
groups at the γ-carbon, method B may be applied to
3-hydroxyvinylidene as well as to 3-hydroxyalkynyl
hydrido species to force dehydration. Scheme 4 sum-
marizes all observed intermediates and final products
for the reaction of HCtCC(OH)MePh with [Cp*RuCl-
(PEt3)2]. Whereas the activation of the alkynol HCtCC-
(OH)MePh by method A yielded cleanly the allenylidene
5d , the dehydration of the 3-hydroxyvinylidene 2d by
method B gave rise to a mixture of the allenylidene/
vinylvinylidene isomers. Similar mixtures were obtained
in the activation of the same alkynol by the fragment
[(η5-C9H7)RuL2]+ (L2 ) 2 PPh3, dppe, dppm)6c and
represent a synthetic limitation of this method, because
these isomers can be hardly separated. However, if
method B is applied to the 3-hydroxyalkynyl hydrido
complex 1d , the dehydration occurs prior to isomeriza-
tion, leading to the RuIV hydrido η1-enynyl derivative
[Cp*RuH{CtCC(Ph)dCH2}(PEt3)2][BPh4] (6d ), a novel
compound which is obtained for the first time. The
spectral properties of 6d resemble those of the 3-hy-
droxyalkynyl hydride 1d . Both types of compounds
exhibit one strong ν(CtC) band in their IR spectra at
2090 and 2104 cm-1, respectively. However, the former
lack the ν(OH) band, as expected. One high-field triplet
is observed for the hydride ligand at δ -9.23 ppm (δ
-9.35 ppm for 1d ) and two resonances for the protons
of the methylidene group at δ 5.27 and 5.61 ppm as
(26) This is the most useful way to allenylidene, employed for the
first time by Selegue,1 although it may lead to a mixture with
alkenylvinylidene6c,8 or even to a selective synthesis of alkenylvinyli-
denes.9b
(27) Werner et al. used this method to dehydrate some stable
3-hydroxyvinylidene compounds: Martin, M.; Werner, H. J . Chem.
Soc., Dalton Trans. 1996, 2275. See also ref 7a and 15. We had to avoid
the use of catalytic amounts of a strong acid such as HBF4 because it
usually caused an extensive decomposition of the complexes.

4568 Organometallics, Vol. 18, No. 22, 1999
Bustelo et al.
Sch em e 4. Rea ction s a n d Sp ecies In volved in th e Activa tion of HCtCC(OH)MeP h by th e Com p lex
[Cp *Ru Cl(P Et3)2]
broad singlets. In contrast to 1d , the phosphorus atoms
are equivalent, as inferred from the presence of one
singlet in the 31P{1H} NMR spectra, due to the disap-
pearance of the chirality of the γ-carbon. These spectral
data also suggest a transoid four-legged piano-stool
structure for these species. Although it was possible to
detect appreciable formation of hydrido enynyl com-
plexes from those 3-hydroxyalkynyl hydrido compounds
with deprotonatable groups at the δ-carbon, it was
unable to obtain them with enough purity due to the
intrinsic limitations of the method B, namely that the
longer the acidic alumina column, the more the isomer-
ization takes place, a mixture being obtained with at
least four species.
views of the cationic complexes are shown in Figures 2
and 3. Both complexes adopt three-legged piano-stool
geometries. The vinylvinylidene ligand in 4d is char-
acterized by a Ru(1)-C(11) distance of 1.81(2) Å, a
C(11)-C(12) separation of 1.37(2) Å, and a Ru(1)-
C(11)-C(12) angle of 172(1)°. The angle C(11)-C(12)-
C(13) of 129(1)° indicates sp2 hybridization for C(12),
as expected for the â-carbon of a vinylidene ligand. The
separations C(12)-C(13) ) 1.44(2) Å and C(13)-C(14)
) 1.27(3) Å correspond respectively to a single and to a
double bond. These dimensions compare well in general
with those reported for the few other ruthenium vi-
nylvinylidene complexes structurally characterized, i.e.,
[CpRu{dCdCHCdCH(CH2)4}(PMe3)2][PF6],9a [(η5-C9H7)-
The compound 6d rearranges both in solution and in
the solid state to the vinylvinylidene isomer [Cp*Ru{d
CdCHC(dCH2)Ph}(PEt3)2][BPh4] (4d ). This solid-state
isomerization is the best synthetic method to obtain 4d
in pure form and allowed us to obtain not only the NMR
spectral data but also single crystals suitable for X-ray
diffraction analysis. As mentioned earlier, the alle-
nylidene 5d is the most stable product; therefore, it is
not surprising that in solution the vinylvinylidene 4d
spontaneously isomerizes into 5d . This observation
makes clear that the formation of 3-hydroxyvinylidene
intermediates is not always necessary for the formation
of alkenylvinylidene or allenylidene derivatives, which
explains the possibility of synthesizing allenylidene
complexes by activation of HCtCC(dCH2)CH3 with [(η6-
arene)Ru(L)Cl2] (L ) PR3, CNR)28 as well as with cis-
[RuCl2(dppm)2],8,29 through an overall reaction of 1,4-
migration of the alkyne proton likely via a vinylvinylidene
intermediate.
Ru{dCdC(Me)CdCH(CH2)4}(PPh3)2][CF3SO3],9b and
[TpRu {dCdC(COOMe)CH dCH COOMe}(dippe)]-
[BPh4].9d In the case of 5e, the diphenylallenylidene
ligand appears almost linearly assembled to ruthenium.
The observed sequence of C-C bond distances across
the carbon chain is quite representative of what is
expected for an allenylidene ligand having substantial
contribution of two different mesomeric forms. Thus, the
bond distances Ru(1)-C(11) ) 1.876(5) Å, C(11)-(12)
) 1.245(7) Å, and C(12)-C(13) ) 1.352(8) Å compare
well with the values found in other allenylidene com-
plexes such as [Cp*Ru(dCdCdCMePh)(dippe)][BPh4]
(1.884(5), 1.257(6), and 1.338(7) Å),7b [(η5-C9H7)Ru{d
CdCdC(C13H20)}(PPh3)2][PF6] (1.889(5), 1.256(7), and
1.339(7) Å),10b or [CpRu(dCdCdCPh2)(PMe3)2][PF6]
(1.884(5), 1.255(8), and 1.329(9) Å).1 The atoms C(12),
C(13), C(14), and C(20) define a plane which forms a
dihedral angle of 8.59° with the plane defined by C(11),
Ru(1), and the centroid of the Cp* ring. This disposition
has been commonly observed in other half-sandwich Ru
allenylidene derivatives, since it appears to maximize
the effectiveness of the metal-ligand π-overlap.30
The X-ray crystal structures of [Cp*Ru{dCdCHC(d
CH2)Ph}(PEt3)2][BPh4] (4d ) and of [Cp*Ru(dCdCd
CPh2)(PEt3)2][BPh4] (5e) were determined. General
crystallographic data for these compounds are shown
in Table 5. Selected bond lengths and angles for 4d and
5e are listed in Tables 6 and 7, respectively. ORTEP
Finally, the activation of the dialkyl-substituted
alkynols 2-methyl-3-butyn-2-ol and 1-ethynylcyclohex-
anol by method A led as final products to the zwitteri-
onic compounds [Cp*Ru{CtCC(PEt3)Me2}(PEt3)2][BPh4]
(28) Devanne, D.; Dixneuf, P. H. J . Chem. Soc., Chem. Commun.
1990, 641. Dussel, R.; Pilette, D.; Dixneuf, P. H.; Fehlhammer, W. P.
Organometallics 1991, 16, 3287.
(29) Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. J . Chem. Soc.,
Chem. Commun. 1991, 980.
(30) Schelling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L. J . Am.
Chem. Soc. 1977, 101, 585.

Activation of Alkynols by [Cp*RuCl(PEt3)2]
Organometallics, Vol. 18, No. 22, 1999 4569
Ta ble 5. Su m m a r y of Da ta for th e Cr ysta l Str u ctu r e An a lysis of 4d , 5e, a n d 7f
4d
5e
7f
formula
fw
C
56H73BP2Ru
C61H75BP2Ru
982.09
C57H86BP3Ru
976.11
920.02
cryst size (mm)
cryst syst
space group
cell params
a, Å
0.30 × 0.15 × 0.12
orthorhombic
P212121 (No. 19)
0.27 × 0.25 × 0.08
0.32 × 0.25 × 0.15
triclinic
triclinic
P1h (No. 2)
P1h (No. 2)
16.160(6)
19.838(5)
15.309(4)
13.573(5)
18.174(5)
11.020(4)
91.47(3)
101.53(3)
84.80(3)
2652(1)
2
1.230
0.710 69
3.84
1040.00
-3.60
0.887-1.000
4
14.538(7)
18.503(9)
10.755(4)
92.04(3)
99.95(3)
107.40(4)
2707(2)
2
1.197
0.710 69
4.03
1044.00
-0.65
0.751-1.000
4
b, Å
c, Å
R, deg
â, deg
γ, deg
V (Å3)
4907(4)
4
1.245
0.710 69
4.11
1952.00
-0.80
0.802-1.000
4
Z
Fcalcd (g cm-3
)
λ(Mo KR) (Å)
µ(Mo KR) (cm-1
F(000)
)
decay (%)
transmissn factors
scan speed (ω) (deg min-1
no.of measd rflns
no. of obsd rflns (I > 3σI)
no.of params
)
4177
2351
306
8576
5377
586
8672
5000
461
rfln/param ratio
7.68
9.18
10.85
Ra
0.0697
0.0812
0.9823
2.113
0.0491
0.0565
0.2314
1.625
0.0717
0.0871
8.953
-2
b
Rw (w ) σF
)
max ∆/σ in final cycle
GOF
2.545
a
b
2
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) (∑w(|Fo| - |Fc|)2/∑w|Fo| )1/2
.
Ta ble 6. Selected Bon d Dista n ces (Å) for 4d , 5e, a n d 7f
5e
4d
7f
Ru(1)-P(1)
Ru(1)-P(2)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Ru(1)-C(4)
Ru(1)-C(5)
Ru(1)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
C(13)-C(15)
2.351(4)
2.321(5)
2.25(2)
2.27(2)
2.27(2)
2.35(2)
2.30(2)
1.81(2)
1.37(2)
1.44(3)
1.27(3)
1.45(3)
Ru(1)-P(1)
Ru(1)-P(2)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Ru(1)-C(4)
Ru(1)-C(5)
Ru(1)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
C(13)-(20)
2.336(2)
2.344(2)
2.246(6)
2.276(6)
2.311(6)
2.315(6)
2.282(6)
1.876(5)
1.245(7)
1.352(8)
1.463(7)
1.493(8)
Ru(1)-P(1)
Ru(1)-P(2)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Ru(1)-C(4)
Ru(1)-C(5)
Ru(1)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
C(13)-(15)
P(3)-C(13)
2.293(3)
2.283(3)
2.22(1)
2.234(10)
2.23(1)
2.28(1)
2.29(1)
1.984(9)
1.22(1)
1.45(1)
1.54(1)
1.49(2)
1.83(1)
Ta ble 7. Selected An gles (d eg) for 4d , 5e a n d 7f
5e
4d
7f
P(1)-Ru(1)-P(2)
93.3(2)
P(1)-Ru(1)-P(2)
96.67(7)
89.5(2)
91.0(2)
172.1(5)
170.8(6)
122.3(6)
118.4(5)
119.2(5)
P(1)-Ru(1)-P(2)
97.8(1)
88.5(3)
87.7(3)
169.7(8)
173(1)
110.9(9)
113(1)
106(1)
P(1)-Ru(1)-C(11)
P(2)-Ru(1)-C(11)
Ru(1)-C(11)-C(12)
C(11)-C(12)-C(13)
C(12)-C(13)-C(14)
C(12)C(13)-C(15)
C(14)-C(13)-C(15)
90.5(6)
90.3(5)
172(1)
129(1)
123(2)
116(1)
120(2)
P(1)-Ru(1)-C(11)
P(2)-Ru(1)-C(11)
Ru(1)-C(11)-C(12)
C(11)-C(12)-C(13)
C(12)-C(13)-C(14)
C(12)-C(13)-C(20)
C(14)-C(13)-C(20)
P(1)-Ru(1)-C(11)
P(2)-Ru(1)-C(11)
Ru(1)-C(11)-C(12)
C(11)-C(12)-C(13)
C(12)-C(13)-C(14)
C(12)-C(13)-C(15)
C(14)-C(13)-C(15)
P(3)-C(13)-C(12)
P(3)-C(13)-C(14)
P(3)-C(13)-C(15)
108.8(8)
105.9(8)
111.2(8)
Hz, respectively. These spectral data, along with the
13C{1H} shifts and coupling constant values, are in
accord with those previously reported for alkynylphos-
phonio derivatives, generated by external addition of
free phosphine and regioselective attack at the γ-carbon
of allenylidene complexes.2d,9b The X-ray crystal struc-
ture of 7f was determined. Selected bond lengths and
angles are listed in Tables 6 and 7. An ORTEP view of
the complex cation is shown in Figure 4. This compound
(7f) and [Cp*Ru{CtCC(PEt3)(CH2)5}(PEt3)2][BPh4] (7g),
which result from the nucleophilic attack of PEt3 at the
γ-carbon of intermediate allenylidene complexes, [Cp*Ru-
(dCdCdCR2)(PEt3)2][BPh4] (Scheme 5). Compounds
7f,g exhibit one strong ν(CtC) band in their IR spectra
at significantly higher wavenumber than the observed
ν(CdCdC) band in allenylidene complexes. The 31P{1H}
NMR spectra display a pattern corresponding to a A2M
5
spin system, with J PP coupling constants of 3.5 and 4.7

4570 Organometallics, Vol. 18, No. 22, 1999
Bustelo et al.
Sch em e 5. F or m a tion of Alk yn ylp h osp h on io
Com p lexes [Cp *Ru {CtCC(P Et3)RR′}(P Et3)][BP h 4]
(R ) R′ ) Me (7f); R ) R′ ) C5H10 (7g))
F igu r e 2. ORTEP view (50% probability) of the cation
[Cp*Ru{dCdCHC(Ph)dCH2}(PEt3)2]+ in complex 4d, show-
ing the atom-labeling scheme. Hydrogen atoms have been
omitted.
F igu r e 4. ORTEP view (50% probability) of the cation
[Cp*Ru{CtCC(PEt3)Me2}(PEt3)2]+ in complex 7f, showing
the atom-labeling scheme. Hydrogen atoms have been
omitted.
F igu r e 3. ORTEP view (50% probability) of the cation
[Cp*Ru(dCdCdCPh2)(PEt3)2]+ in complex 5e, showing the
atom-labeling scheme. Hydrogen atoms have been omitted.
distance of 1.83(1) Å is on the same order of all the other
P-C separations observed within this complex cation,
being in the expected range. We have found no other
structural report for alkynylphosphonio complexes re-
sulting from the attack of the phosphine at the γ-carbon
of an allenylidene moiety, although the crystal structure
of the alkenylphosphonio species [(η7-C9H7)Ru{CHd
also displays a three legged piano-stool structure. The
C(11)-C(12)-C(13) chain shows only slight deviation
from linearity, as inferred from the angles Ru(1)-
C(11)-C(12) ) 169.7(8)°, and C(11)-C(12)-C(13) )
173(1)°. The Ru-C(11) separation of 1.984(9) Å is longer
than in the vinylvinylidene 4d or in the allenylidene
derivative 5e but is similar to Ru-C distances observed
in σ-alkynyl complexes of ruthenium such as [Cp*Ru-
{CtCC(dCH2)Ph}(dippe)] (1.994(7) Å)7b and [(η5-C9H7)-
Ru{CtCC(CtCH)Ph2}(PPh3)2] (1.993(2) Å),2d corre-
sponding to a single Ru-C bond. The C(11)-C(12) bond
distance of 1.22(1) Å is short and characteristic of a
carbon-carbon triple bond, whereas the C(12)-C(15)
separation of 1.45(1) Å suggests a single bond. All angles
around C(13) are consistent with a tetrahedral sp3
hybridization for this carbon atom. The C(13)-P(3)
C(PPh3)CdCH(CH2)4}(PPh3)2][PF6] has been recently
described,9b which results from the attack of PPh3 at
the â-carbon of a vinylvinylidene complex. Despite this,
the arrangement observed for the complex cation in 7f
has also been found in related half-sandwich derivatives
resulting from the regioselective addition of other kinds
of nucleophiles to the γ-carbon of an allenylidene ligand,
e.g. in [(η7-C9H7)Ru{CtC-C(CtCH)Ph2}(PPh3)2].2d
The products resulting from the phosphine loss re-
main uncharacterized. Apparently, phosphine dissocia-

Activation of Alkynols by [Cp*RuCl(PEt3)2]
Organometallics, Vol. 18, No. 22, 1999 4571
Triethylphosphine and tetraphenylborate protons and carbons
appeared for all the compounds in the appropriate shift ranges
and are not listed. The H NMR resonance for the OH proton,
when observed, appeared most times overlapping with the
phosphine signals and it was not possible to assign them
accurately. Microanalysis was performed by the Serveis Ci-
ent´ıfico-Te`cnics, Universitat of Barcelona.
tion occurs to some extent in solution, reacting with
allenylidene complexes. However, it is also possible that
the high electrophilicity of the γ-carbon, in the absence
of aromatic substituents, is responsible for the abstrac-
tion of PEt3 from other species present in solution.
When a solution of the 3-hydroxyvinylidene com-
pounds 2f,g was passed through an acidic alumina
column (method B), a brown band was first collected,
corresponding to the alkenylvinylidenes [Cp*Ru{dCd
CHC(dCH2)CH3}(PEt3)2][BPh4] (4f) and [Cp*Ru{dCd
1
P r ep a r a tion of 3-Hyd r oxya lk yn yl Hyd r id o Com p lexes
[Cp *Ru H{CtCC(OH)RR′}(P Et3)2][BP h 4] (R, R′ ) H, H
(1a ), H, Me (1b), H, P h (1c), Me, P h (1d ), P h , P h (1e), Me,
Me (1f), C5H10 (1g)). [Cp*RuCl(PEt3)2] (127 mg, 0.25 mmol)
was added to a solution of the corresponding alkynol (0.30
mmol) and NaBPh4 (81 mg, 0.50 mmol) in 10 mL of MeOH at
0 °C (ice bath). The mixture was warmed until a white/yellow
microcrystalline solid precipitated, which was filtered, washed
with cold EtOH and petroleum ether, and stored at -20 °C.
Yield: 80-90% in all cases. Microanalysis was not carried out
because these compounds rearrange to their vinylidene iso-
mers in the solid state. Selected IR and NMR spectral data
for these compounds are given in Tables 1 and 2.
CHCdCH(CH2)4}(PEt3)2][BPh4] (4g) (Scheme 3). Mini-
mal amounts of allenylidene were detected both by IR
and 31P{1H} NMR, but they could not be isolated. After
this, a second blue-violet band appeared, but attempts
at characterization were unsuccessful. This band, which
exhibits a continuous color change from blue to violet
and vice versa, seems to be related to the processes
leading to the formation of the mentioned alkynylphos-
phonio compounds and resembles the case reported by
Dixneuf et al. for the reaction of [Cp*RuCl(PMe2Ph)2]
with HCtCCMe2OH,6b where the presence of a bimetal-
lic structure is suggested on the basis of the character-
ized product obtained by Selegue et al.10a Our detection
in solution of both allenylidene and alkenylvinylidene
species supports this idea, and the in situ phosphine
release represents a new insight into this hypothetical
C-C coupling reaction involving a Cp* system.
P r epar ation of3-Hydr oxyvin yliden e Com plexes [Cp*Ru -
{dCdCHC(OH)RR′}(P Et3)2][BP h 4] (R, R′ ) H, H (2a ), H,
Me (2b), H, P h (2c), Me, P h (2d ), P h , P h (2e), Me, Me (2f),
C5H10 (2g)). Complexes 1a -g were heated as solids at 35 °C
for 3 h under an inert atmosphere, resulting in a gradual color
change from white-yellow to orange. A quantitative and clean
isomerization process into 2a -g takes place, except for
complex 2e, whose dehydration also occurs in the solid state.
Complexes 2a ,b can also be obtained cleanly by starting from
a solution of [Cp*RuCl(PEt3)2] (127 mg, 0.25 mmol) in 15 mL
of MeOH to which the alkynol (0.30 mmol) was added. After
this mixture was stirred for 4 h at room temperature, addition
of NaBPh4 (81 mg, 0.50 mmol) produced an orange solid
precipitate, which was filtered, washed with EtOH and
petroleum ether, and dried in vacuo. Selected IR and NMR
data for these compounds are given in Tables 3 and 4.
Con clu sion s
The isolation of (3-hydroxyalkynyl)hydridoruthenium
(IV) compounds (1) contributes to expand the number
and nature of ruthenium complexes known to be able
to follow this pathway in the alkynyl to vinylidene
isomerization.13b In this case we have shown a system
containing monodentate phosphines, which is used in
the activation of alkynols, connecting with the increas-
ing field of allenylidene chemistry. Methodologically,
these species are also the key for a clean synthesis and
characterization of 3-hydroxyvinylidene complexes (2),
making possible in some cases the control of the direc-
tion of the dehydration into alkenylvinylidene (4) or
allenylidene (5) and a change in the order of the
isomerization/dehydration processes, yielding a novel
hydrido enynyl species (6). We have detected the exist-
ence of η2-alkynol species (3) as the step after which
1,2-H shift and C-H oxidative addition take place
competitively. New attempts to acquire kinetic data
from which we can extract any mechanistic conclusions
about these isomerization processes are in progress with
related Cp* systems.
2a : Anal. Calcd for
C49H69BP2RuO: C, 69.4; H, 8.20.
Found: C, 69.5; H, 8.16. 2b: Anal. Calcd for C50H71BP2RuO:
C, 69.7; H, 8.30. Found: C, 69.7; H, 8.30. 2c: Anal. Calcd for
C
55H73BP2RuO: C, 71.5; H, 7.96. Found: C, 71.5; H, 7.90. 2d :
Anal. Calcd for C56H75BP2RuO: C, 71.7; H, 8.06. Found: C,
71.7; H, 8.07. 2e: unstable toward dehydration even in the
solid state. 2f: Anal. Calcd for C51H73BP2RuO: C, 69.9; H, 8.40.
Found: C, 69.9; H, 8.47. 2g: Anal. Calcd for C54H77BP2RuO:
C, 70.8; H, 8.47. Found: C, 70.9; H, 8.51.
Detection of [Cp*Ru {(η2-HCtCCH(OH)R}(P Et3)2][BP h 4]
(R ) H (3a ), Me (3b), P h (3c)) by NMR Sp ectr oscop y.
[Cp*Ru(N2)(PEt3)2][BPh4] was dissolved in (CD3)2CO in a NMR
tube. The solution was cooled at -40 °C with a liquid N2-
ethanol bath, and then an excess of alkynol was added. The
samples were inserted into the precooled NMR probe, and 31P-
{1H} NMR spectra were recorded. 1H NMR data are not
available due to the overlapping with the free alkynol signals.
Attempts to isolate any of these species as solids failed because
of the fast isomerization into 1a -c even in the solid state.
3a : 31P{1H} NMR (161.89 MHz, (CD3)2CO, 233 K): δ 22.11
and 22.53 (d, 2J PP′ ) 44.5 Hz). 3b: 31P{1H} NMR (161.89 MHz,
(CD3)2CO, 233 K): δ 21.43 and 23.72 (d, 2J PP′ ) 44.0 Hz, isomer
Exp er im en ta l Section
2
a), 21.84 and 22.88 (d, J PP′ ) 46.4 Hz, isomer b). 3c: 31P{1H}
All synthetic operations were performed under a dry dini-
trogen or argon atmosphere by following conventional Schlenk
techniques. Tetrahydrofuran, diethyl ether, and petroleum
ether (boiling point range 40-60 °C) were distilled from the
appropriate drying agents. All solvents were deoxygenated
immediately before use. [Cp*RuCl(PEt3)2]12b and [Cp*Ru(N2)-
(PEt3)2][BPh4]23 were prepared according to reported proce-
dures. IR spectra were recorded in Nujol mulls on Perkin-
Elmer FTIR Spectrum 1000 spectrophotometers. NMR spectra
were taken on a Varian Unity 400 MHz or Varian Gemini 200
MHz spectrometer. Chemical shifts are given in parts per
million from SiMe4 (1H and 13C{1H}) or 85% H3PO4 (31P{1H}).
NMR (161.89 MHz, (CD3)2CO, 233 K): δ 21.30 and 23.44 (d,
2J PP′ ) 44.0 Hz, isomer a), 21.76 and 22.60 (d, 2J PP′ ) 45.2 Hz,
isomer b).
P r ep a r a tion of Alk en ylvin ylid en e Com p lexes [Cp *Ru -
{dCdCHC(dCH2)R}(P Et3)2][BP h 4] (R ) H (4b), P h (4d ),
Me (4f)) a n d [Cp *Ru {dCdCHCdCH(CH2)4}(P Et3)2][BP h 4]
(4g). A solution of the corresponding hydroxyvinylidene com-
plex (0.25 mmol) in 1 mL of CH2Cl2 was passed through a
column with Al2O3 (acidic, activity grade I, height of column
5 cm). During the elution with CH2Cl2 and acetone (5:1) a color

4572 Organometallics, Vol. 18, No. 22, 1999
Bustelo et al.
1
change was observed from orange to orange-brown. This
fraction was collected and taken to dryness in vacuo, and the
residue was suspended in Et2O and the suspension treated
for 5 min in a ultrasonic bath. The solvent was removed and
the solid dried in vacuo and recrystallized in a acetone/ethanol
(1:2) mixture. Yield: 70-80%. The complex 4d could not be
cleanly obtained in this way but was obtained quantitatively
by solid-state isomerization at 35 °C of the hydrido enynyl
complex 6d , and its recrystallization had to be accomplished
at -20 °C, preventing the isomerization into the allenylidene
5d , yielding brown crystals. Selected spectral data are as
follows.
C, 72.9; H, 7.93. IR (Nujol): ν(CdCdC) 1907 cm-1. H NMR
4
(400 MHz, CDCl3, 298 K): δ 1.92 (t, J HP ) 1.0 Hz, C5(CH3)5),
7.47, 7.74 and 7.86 (m, RudCdCdCH(C6H5)), 9.13 (s, Rud
CdCdCHPh). 31P{1H} NMR (161.89 MHz, CDCl3, 298 K): δ
32.1 (s). 13C{1H} NMR (50.28 MHz, CD2Cl2, 298 K): 11.17 (s,
2
C5(CH3)5), 103.3 (s, C5(CH3)5), 301.6 (t, J CP ) 17.5 Hz, CR),
222.2 (s, Câ), 143.2 (s, Cγ), 129.8, 130.4, 131.6, and 140.3 (s,
C6H5).
5d : Anal. Calcd for C56H73BP2Ru: C, 73.1; H, 8.00 Found:
1
C, 73.2; H, 7.97. IR (Nujol): ν(CdCdC) 1908 cm-1. H NMR
4
(400 MHz, CDCl3, 298 K): δ 1.82 (t, J HP ) 1.2 Hz, C5(CH3)5),
7.38, 7.67, and 7.96 (m, RudCdCdCMe(C6H5)), 1.94 (s, Rud
CdCdCMePh). 31P{1H} NMR (161.89 MHz, CDCl3, 298 K): δ
32.8 (s). 13C{1H} NMR (50.28 MHz, CDCl3, 298 K): 10.95 (s,
4b: Anal. Calcd for C50H69BP2Ru: C, 71.2; H, 8.24. Found:
1
C, 71.1; H, 8.22. IR (Nujol): ν(CdC) 1620 cm-1. H NMR (400
4
2
MHz, CDCl3, 298 K): δ 1.73 (t, J HP ) 1.0 Hz, C5(CH3)5), 4.86
C5(CH3)5), 102.1 (s, C5(CH3)5), 293.9 (t, J CP ) 18.2 Hz, CR),
210.3 (s, Câ), 149.8 (s, Cγ), 127.0, 129.3, 131.5, and 142.3 (s,
C6H5), 30.77 (s, CH3).
a
b
(dt, 4J H ) 1.5 Hz, 3J H ) 16.9 Hz, RudCdCH CH (dCH2)),
a
a
b
P
H
4.43 and 5.01 (d, 1H each, J H H ) 10.1 Hz, RudCdCHCHb-
3
c
b
(dCHc2)), 6.15 (dt, 3J H ) 16.9 Hz, J H ) 10.1 Hz, RudCd
3
a
b
b
c
H
H
5e: Anal. Calcd for C61H75BP2Ru: C, 74.6; H, 7.70. Found:
CHaCHb(dCHc2)). 31P{1H} NMR (161.89 MHz, CDCl3, 298 K):
1
C, 74.6; H, 7.76. IR (Nujol): ν(CdCdC) 1907 cm-1. H NMR
δ 30.9 (s). 13C{1H} NMR (50.28 MHz, CDCl3, 298 K): 10.71 (s,
4
(400 MHz, CDCl3, 298 K): δ 1.86 (t, J HP ) 1.1 Hz, C5(CH3)5),
2
7.45, 7.67 and 7.72 (m, RudCdCdC(C6H5)2). 31P{1H} NMR
(161.89 MHz, CDCl3, 298 K): δ 33.1 (s). 13C{1H} NMR (50.28
MHz, CDCl3, 298 K): 10.89 (s, C5(CH3)5), 102.4 (s, C5(CH3)5),
293.1 (t, 2J CP ) 18.3 Hz, CR), 217.0 (t, 3J CP ) 2.2 Hz, Câ), 150.8
(s, Cγ), 128.6, 128.8, 130.4, and 144.2 (s, C6H5).
C5(CH3)5), 103.0 (s, C5(CH3)5), 351.4 (t, J CP ) 15.1 Hz, CR),
110.6 (s, Câ), 121.9 (s, Cγ), 114.5 (s, dCH2).
4d : Anal. Calcd for C56H73BP2Ru: C, 73.1; H, 8.00. Found:
1
C, 73.2; H, 8.02. IR (Nujol): ν(CdC) 1622 cm-1. H NMR (400
4
MHz, CDCl3, 298 K): δ 1.78 (t, J HP ) 1.0 Hz, C5(CH3)5), 4.90
(t, 4J HP ) 1.9 Hz, RudCdCHC(dCH2)Ph), 5.02 and 5.29 (br s,
1H each, RudCdCHC(dCH2)Ph), 7.34, 7.35, and 7.36 (m,
C6H5). 31P{1H} NMR (161.89 MHz, CDCl3, 298 K): δ 28.9 (s).
13C{1H} NMR (50.28 MHz, CDCl3, 298 K): 10.97 (s, C5(CH3)5),
P r ep a r a tion of Hyd r id o En yn yl Com p lexes [Cp *Ru H-
{CtCC(dCH2)P h }(P Et3)2][BP h 4] (6d ). A solution of the
hydroxyalkynyl hydride 1d was passed through a column with
Al2O3 (acidic, activity grade I, height of column 5 cm) as
previously described, but with cold solvents (0 °C) as eluents
being used as a precaution. A yellow band was obtained, giving
rise to a pale yellow solid after the solvent was removed.
Yield: 70-80%. Microanalysis was not carried out because this
compound rearranges to the vinylvinylidene isomer 4d in the
solid state. Selected spectral data for 6d are as follows. IR
4
103.7 (s, C5(CH3)5), 350.5 (t, J CP ) 14.8 Hz, CR), 112.0 (s, Câ),
126.2 (s, Cγ), 113.6 (s, dCH2), 128.2, 128.5, 138.1 and 140.5
(s, C6H5).
4f: Anal. Calcd for C51H71BP2Ru: C, 71.4; H, 8.34. Found:
1
C, 71.4; H, 8.32. IR (Nujol): ν(CdC) 1607 cm-1. H NMR (400
4
MHz, CDCl3, 298 K): δ 1.74 (t, J HP ) 1.1 Hz, C5(CH3)5), 4.74
4
(br s, RudCdCHC(dCH2)CH3), 4.42 (dc, 2J H ) 2.0 Hz, J H
a
b
a
c
(Nujol): ν(CtC) 2090, ν(Ru-H) 2020, ν(CdC) 1560 cm-1. H
NMR (400 MHz, CDCl3, 273 K): δ -9.23 (t, J HP ) 29.7 Hz,
Ru-H), 1.71 (t, J HP ) 1.1 Hz, C5(CH3)5), 5.27 and 5.61 (br s,
1H each, RuCtCC(dCH2)Ph)), 7.32, 7.34, and 7.55 (m, RuCt
CC(dCH2)(C6H5)). 31P{1H} NMR (161.89 MHz, CDCl3, 273
K): δ 37.6 (s). 13C{1H} NMR (201.12 MHz, CDCl3, 273 K):
10.21 (s, C5(CH3)5), 101.7 (s, C5(CH3)5), 100.0 (t, J CP ) 30.9
Hz, CR), 115.0 (s, Câ), 133.2 (s, Cγ), 116.9 (s, RuCtCC(dCH2)-
Ph)), 125.9, 127.9, 128.1, and 139.0 (s, C6H5).
P r epar ation of Alkyn ylph osph on io Com plexes [Cp*Ru -
{CtCC(P Et3)RR′}(P Et3)2][BP h 4] (R, R′ ) Me, Me (7f),
C5H10 (7g)). Complexes 7f,g were obtained by starting from a
solution of [Cp*RuCl(PEt3)2] (127 mg, 0.25 mmol) in 15 mL of
MeOH to which the alkynol (0.30 mmol) was added. After the
mixture was stirred for 8 h at room temperature, addition of
NaBPh4 (81 mg, 0.50 mmol) caused the precipitation of a
brown solid, which was filtered, washed with EtOH and
petroleum ether, and dried in vacuo. Slow crystallization from
a acetone/ethanol (1:2) mixture gave dark red crystals. Yield:
40-45%. Selected spectral data are as follows.
H
H
1
) 1.5 Hz, RudCdCHC(dCHaHb)CHc3), 4.58 (br s, RudCd
CHC(dCHaHb)CH3), 1.70 (br s, RudCdCHC(dCH2)CH3). 31P-
{1H} NMR (161.89 MHz, CDCl3, 298 K): δ 27.8 (s). 13C{1H}
NMR (50.28 MHz, CDCl3, 298 K): 10.82 (s, C5(CH3)5), 103.0
2
4
2
(s, C5(CH3)5), 352.9 (t, J CP ) 15.3 Hz, CR), 109.8 (s, Câ), 132.2
(s, Cγ), 116.3 (s, dCH2), overlapping with phosphine methyl
groups (s, CH3).
2
4g: Anal. Calcd for C54H75BP2Ru: C, 72.2; H, 8.42. Found:
1
C, 72.3; H, 8.50. IR (Nujol): ν(CdC) 1633 cm-1. H NMR (400
4
MHz, CDCl3, 298 K): δ 1.75 (t, J HP ) 1.0 Hz, C5(CH3)5), 4.60
(br s, RudCdCH(C6H9)), 5.33 (t, 3J H ) 3.9 Hz, RudCdCHC-
a
b
H
(dCHaCHb2CH2CH2CH2)), 1.60, 1.85 and 2.18 (m, RudCd
CHC(dCH(CH2)4). 31P{1H} NMR (161.89 MHz, CDCl3, 298
K): δ 28.3 (s). 13C{1H} NMR (50.28 MHz, CDCl3, 298 K): 10.82
(s, C5(CH3)5), 102.7 (s, C5(CH3)5), 354.5 (t, 2J CP ) 15.5 Hz, CR),
116.6 (s, Câ), 125.0 (s, Cγ), 121.7 (s, dCH2), 21.9, 22.7, 25.4,
and 29.7 (s, RudCdCHC(dCH(CH2)4)).
P r ep a r a tion of Allen ylid en e Com p lexes [Cp *Ru (dCd
CdCRR′)(P Et3)2][BP h 4] (R, R′ ) H, P h (5c), Me, P h (5d ),
P h , P h (5e)). Complex 5c was obtained from the hydroxyvi-
nylidene 3c by passing through a Al2O3 column (acidic, activity
grade I, height of column 10 cm) as previously described,
collecting a dark brown band. Yield: 70-80%. Complexes 5d ,e
were obtained starting from a solution of [Cp*RuCl(PEt3)2]
(127 mg, 0.25 mmol) in 15 mL of MeOH to which the alkynol
(0.30 mmol) was added. After the mixture was stirred for 8 h
at room temperature, addition of NaBPh4 (81 mg, 0.50 mmol)
caused the precipitation of a dark brown solid, which was
filtered, washed with EtOH and petroleum ether, and dried
in vacuo. The solids were recrystallized in a acetone/ethanol
(1:2) mixture, yielding dark brown crystals. Yield: 85-90%.
Selected spectral data are as follows.
7f: Anal. Calcd for C57H86BP3Ru: C, 70.1; H, 8.88. Found:
1
C, 70.1; H, 8.86. IR (Nujol): ν(CtC) 2050 cm-1. H NMR (400
4
MHz, CDCl3, 298 K): δ 1.68 (t, J HP ) 1.2 Hz, C5(CH3)5), 1.27
3
(d, J HP′ ) 15.5 Hz, RuCtCC(PEt3)(CH3)2). 31P{1H} NMR
(161.89 MHz, CDCl3, 298 K): δ 31.9 (d, 5J PP′ ) 3.6 Hz, Cp*Ru-
5
(PEt3)2), 40.3 (t, J PP′ ) 3.6 Hz, RuCtCC(PEt3)Me2). 13C{1H}
NMR (50.28 MHz, CDCl3, 298 K): 11.03 (s, C5(CH3)5), 91.43
2
2
(t, J CP ) 1.8 Hz, C5(CH3)5), 103.4 (t, J CP ) 2.9 Hz, CR), 99.03
2
1
(d, J CP′ ) 5.2 Hz, Câ), 33.55 (d, J CP′ ) 47.2 Hz, Cγ), 6.88 (d,
2J CP′ ) 5.7 Hz, Ru-CtCC(PEt3)(CH3)2).
7g: Anal. Calcd for C60H90BP3Ru: C, 70.8; H, 8.92. Found:
1
C, 70.7; H, 8.88. IR (Nujol): ν(CtC) 2037 cm-1. H NMR (400
MHz, CDCl3, 298 K): δ 1.69 (t, 4J HP ) 1.6 Hz, C5(CH3)5), 1.16,
1.27, and 1.58 (m, RuCtCC(PEt3)(CH2)5). 31P{1H} NMR (161.89
MHz, CDCl3, 298 K): δ 32.8 (d, 5J PP′ ) 4.7 Hz, Cp*Ru(PEt3)2),
5c: Anal. Calcd for C55H71BP2Ru: C, 72.9; H, 7.90. Found:

Activation of Alkynols by [Cp*RuCl(PEt3)2]
Organometallics, Vol. 18, No. 22, 1999 4573
5
38.8 (t, J PP′ ) 4.7 Hz, RuCtCC(PEt3)Me2). 13C{1H} NMR
vinylvinylidene ligand were anisotropically refined; the re-
maining non-hydrogen atoms were isotropically refined. For
compound 5e all non-hydrogen atoms were anisotropically
refined. Disorder was found for an ethyl group in compound
7f, and it was modeled using two positions for C(32) and C(33)
with aproximately two-thirds and one-third occupation. All
non-hydrogen atoms for 7f except C atoms in ethyl groups were
anisotropically refined. In every case the hydrogen atoms were
included at idealized positions and not refined. All calculations
for data reduction, structure solution, and refinement were
carried out on a VAX 3520 computer at the Servicio Central
de Ciencia y Tecnolog´ıa de la Universidad de Ca´diz, using the
TEXSAN32 software system and ORTEP33 for plotting.
2
(50.28 MHz, CDCl3, 298 K): 11.20 (s, C5(CH3)5), 91.52 (t, J CP
) 2.1 Hz, C5(CH3)5), 116.7 (t, 2J CP ) 1.8 Hz, CR), 96.12 (d, 2J CP′
1
2
) 7.3 Hz, Câ), 40.47 (d, J CP′ ) 47.0 Hz, Cγ), 10.42 (d, J CP′
)
10.4 Hz, RuCtCC(PEt3)(CH2(CH2)3CH2)), 24.93 and 33.26 (s,
RuCtCC(PEt3)(CH2(CH2)3CH2)).
X-r a y Str u ctu r e Deter m in a tion of th e Com p ou n d s 4d ,
5e, a n d 7f. X-ray diffraction measurements were made on
crystals of the appropriate size, which were mounted onto a
glass fiber and transferred to an AFC6S-Rigaku automatic
diffractometer (T ) 290 K, Mo KR radiation, graphite mono-
chromator, λ ) 0.710 73 Å). Accurate unit cell parameters and
an orientation matrix were determined in each case by least-
squares fitting from the settings of 25 high-angle reflections.
Crystal data and details of the data collection and refinement
are given in Table 5. Data were collected by the ω/2θ scan
method. Lorentz and polarization corrections were applied.
Decay was monitored by measuring 3 standard reflections
every 100 measurements. Decay and semiempirical absorption
corrections (ψ method) were also applied.
Ack n ow led gm en t. We wish to thank the Ministerio
de Educacio´n y Cultura of Spain (DGICYT, Project
PB97-1357) and J unta de Andaluc´ıa (PAI-FQM 0188)
for financial support. We also thank to J ohnson Matthey
plc for including us in their precious metal loan scheme.
Su p p or tin g In for m a tion Ava ila ble: Tables giving crys-
tallographic data for 4d , 5e, and 7f. This material is available
free of charge via the Internet at http://pubs.acs.org.
The structure was solved in each case by Patterson methods
and subsequent expansion of the model using DIRDIF.31
Reflections having I > 3σ(I) were used for structure refine-
ment. For compound 4d Ru, P, and the C atoms in the
OM990484B
(32) TEXSAN: Single-Crystal Structure Analysis Software, version
5.0; Molecular Structure Corp., Houston, TX, 1989.
(31) Beurskens, P. T. DIRDIF; Technical Report 1984/1; Crystal-
lography Laboratory, Toernooiveld, The Netherlands, 1984.
(33) J ohnson, C. K. ORTEP, A Thermal Ellipsoid Plotting Program;
Oak Ridge National Laboratory, Oak Ridge, TN, 1965.