Reactions of RuCp and RuCp* allyl carbene complexes: Products derived from activation of phenyl, cyclohexyl, and methyl C-H bonds in PPh3, PCy3, and Cp* ligands

Article abstract of DOI:10.1021/om020094g

Ruthenium allyl carbene complexes of the type [RuCp(=C(R)-(η³-CHC(R)CHPR′₃))]PF₆ (R, R′ = aryl, alkyl substituents) are characterized by two reaction modes, (i) They behave as masked coordinatively unsaturated complexes and react readily with the donor ligands PR₃ and P(OR)₃ to give η³-butadienyl complexes. This is not a simple nucleophilic addition at the metal center but involves changes in both the bonding mode and the stereochemistry of the allyl carbene C₄-chain. The incoming nucleophile induces C-H bond activation effecting formally a 1,4 hydrogen shift, (ii) They are capable of activating C-H bonds of aryl and alkyl groups in the bulky tertiary phosphine ligands PPh₃ and PCy₃ to give novel η⁴-butadiene complexes. In these, one R of PR₃ is σ-bonded to the metal center. A divergent rearrangement results if the allyl carbene complex derives from parent acetylene (instead of a terminal alkyne). In this case the C₄-unit features a η₃-allyl moiety and the metal center is η₂-coordinated to an arene ring of the PPh₃ substituent. Finally, RuCp* allyl carbene complexes have been prepared for the first time. They are reactive entities and react slowly with cleavage of one of the ring methyl C-H bonds of the Cp* ligand to give tetramethyl-fulvene-type complexes.

Full text of DOI:10.1021/om020094g

2912
Organometallics 2002, 21, 2912-2920
Rea ction s of Ru Cp a n d Ru Cp * Allyl Ca r ben e Com p lexes:
P r od u cts Der ived fr om Activa tion of P h en yl, Cycloh exyl,
a n d Meth yl C-H Bon d s in P P h 3, P Cy3, a n d Cp * Liga n d s
Eva Ru¨ba,† Kurt Mereiter,‡ Roland Schmid,† and Karl Kirchner*,†,§
Institute of Applied Synthetic Chemistry and Institute of Chemical Technologies and Analytics,
Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria
Emilio Bustelo, M. Carmen Puerta, and Pedro Valerga
Departamento de Ciencias de los Materiales e Ingenier´ıa Metalu´rgica y Quı´mica Inorga´nica,
Facultad de Ciencias, Universidad de Ca´diz, Apartado 40, Puerto Real 11510, Spain
Received February 8, 2002
Ruthenium allyl carbene complexes of the type [RuCp(dC(R)-(η3-CHC(R)CHPR′3))]PF6 (R,
R′ ) aryl, alkyl substituents) are characterized by two reaction modes. (i) They behave as
masked coordinatively unsaturated complexes and react readily with the donor ligands PR3
and P(OR)3 to give η3-butadienyl complexes. This is not a simple nucleophilic addition at
the metal center but involves changes in both the bonding mode and the stereochemistry of
the allyl carbene C4-chain. The incoming nucleophile induces C-H bond activation effecting
formally a 1,4 hydrogen shift. (ii) They are capable of activating C-H bonds of aryl and
alkyl groups in the bulky tertiary phosphine ligands PPh3 and PCy3 to give novel η4-butadiene
complexes. In these, one R of PR3 is σ-bonded to the metal center. A divergent rearrangement
results if the allyl carbene complex derives from parent acetylene (instead of a terminal
alkyne). In this case the C4-unit features a η3-allyl moiety and the metal center is
η2-coordinated to an arene ring of the PPh3 substituent. Finally, RuCp* allyl carbene
complexes have been prepared for the first time. They are reactive entities and react slowly
with cleavage of one of the ring methyl C-H bonds of the Cp* ligand to give tetramethyl-
fulvene-type complexes.
In tr od u ction
This feature is worthy of consideration since quite
recently5 a large variety of ruthenium allyl carbene
complexes became readily available by the reaction of
labile [RuCp(PR3)(CH3CN)2]PF6 (R ) tertiary phos-
phines)6 with alkynes. In a preliminary communication5a
we have reported that allyl carbenes are reactive species
that are able not only to add nucleophiles to the metal
center but also to dehydrogenate a cyclohexyl group of
the bulky PCy3 ligand initiated by C-H bond activation.
In the present paper we shall investigate the reactiv-
ity of ruthenium allyl carbenes in more detail. It will
be seen that nucleophiles are accommodated with
formation of η3-butadienyl complexes. In addition, C-H
bonds of bulky tertiary substituents are activated under
mild conditions. This leads to the formation of novel η4-
diene complexes with σ-bonded arene and cyclohexyl
ligands. We will also examine in what ways the reactiv-
ity is changed if the Cp* ligand is substituted for Cp.
Included are also the X-ray structures of representative
reaction products.
Coordinatively unsaturated complexes and complexes
with labile ligands are the most promising candidates
for catalytic activity. Clearly, the availability of a vacant
coordination site is prerequisite to both stoichiometric
and catalytic molecular transformations of organic
molecules at a transition metal center. A particularly
notable situation is encountered with ligands that are
capable of reversibly changing their bonding mode.
Examples include η5 T η3 ring slippage of Cp and
indenyl ligands1 as well as η1-vinyl T η2-vinyl or η1-
vinylcarbene T η3-vinylcarbene rearrangements.2 Simi-
larly, a few years ago Green et al. reported3,4 that
ruthenium η3-allyl carbene (structure A in Scheme 1)
can convert into the η3-butadienyl species (structure B).
Accordingly, allyl carbenes may be considered as masked
coordinatively unsaturated complexes that can accom-
modate an attacking nucleophile at the metal center
(Scheme 1).
† Institute of Applied Synthetic Chemistry.
‡ Institute of Chemical Technologies and Analytics.
§ E-mail: kkirch@mail.zserv.tuwien.ac.at.
(5) (a) Mauthner, K.; Soldouzi, K. M.; Mereiter, K.; Schmid, R.;
Kirchner, K. Organometallics 1999, 18, 4681. (b) Ru¨ba, E.; Mereiter,
K.; Schmid, R.; Kirchner, K.; Schottenberger, H. J . Organomet. Chem.
2001, 637-639, 70. (c) Ru¨ba, E.; Mereiter, K.; Schmid, R.; Kirchner,
K. Chem. Commun. 2001, 1996. (d) Ru¨ba, E.; Mereiter, K.; Sapunov,
V. N.; Schmid, R.; Kirchner, K.; Schottenberger, H.; Calhorda, M. J .
Veiros, L. F. Eur. J . Chem., in press.
(6) Ru¨ba, E.; Simanko, W.; Mauthner, K.; Soldouzi, K. M.; Slugovc,
C.; Mereiter, K.; Schmid, R.; Kirchner, K. Organometallics 1999, 18,
3843.
(1) For a review on Cp ring slippage reactions see: O’Connor, J .
M.; Casey, C. P. Chem. Rev. 1987, 87, 307.
(2) For a review on η1/η3-vinyl carbene complexes see: Mitsudo, T.
Bull. Chem. Soc. J pn. 1998, 71, 1525.
(3) Crocker, M.; Green, M.; Nagle, K. R.; Orpen, A. G.; Neumann,
H. P.; Morton, C. E.; Schaverin, C. J . Organometallics 1990, 9, 1422.
(4) Crocker, M.; Dunne, B. J .; Green, M.; Orpen, A. G. J . Chem. Soc.,
Dalton Trans. 1991, 1589.
10.1021/om020094g CCC: $22.00 © 2002 American Chemical Society
Publication on Web 06/06/2002

RuCp and RuCp* Allyl Carbene Complexes
Organometallics, Vol. 21, No. 14, 2002 2913
Sch em e 1
Sch em e 2
Resu lts a n d Discu ssion
The reaction sequence presented in Scheme 1 applies
to using tertiary phosphines and phosphites as the
nucleophile. This type of reaction is intriguing since not
only a change in the bonding mode of the allyl carbene
fragment is involved but also a change in stereochem-
istry of substituents on the terminal carbon of the allyl
moiety. In precursor A the hydrogen occupies a pseudo
syn position, whereas in the butadienyl complex C the
stereochemistry is reversed with the hydrogen in the
pseudo anti position and the phenyl substituent in the
pseudo syn site. Such a stereomutation has been pro-
posed to occur via a ring-opening/ring-flip mechanism.3
In the present work we have treated complex 2a with
1 equiv of PPh3. According to Scheme 2, the η3-
butadienyl complex [RuCp(CPMe3dCPh-η2-CHdCHPh)-
(PPh3)]PF6 (3) is formed, whose molecular structure
from X-ray crystallography is depicted in Figure 1. In
contrast to allyl carbenes the butadienyl ligand in
complex 3 binds with σ-vinyl and η2-alkene functions.
The σ-bonding of the butadienyl ligand is reflected in
the Ru-C(9) bond distance of 2.139(4) Å, while the C(6)
and C(7) comprise an olefinic unit bound to the metal
with Ru-C(6) and Ru-C(7) distances of 2.292(4) and
2.197(4) Å, respectively. The butadienyl C-C bond
distances adopt a typical short-long-short pattern (the
C(6)-C(7), C(7)-C(8), and C(8)-C(9) bond distances are
1.399(5), 1.489(5), and 1.334(5) Å, respectively). The
asymmetric manner in which the butadienyl unit is
coordinated to the ruthenium center is demonstrated
by the respective Ru-C(9)-C(8) and Ru-C(6)-C(7)
angles of 99.9(2)° and 68.2(2)°. The atoms Ru, C(7), C(8),
and C(9) are approximately coplanar, showing an rms
deviation from planarity of 0.031 Å. Ru and C(8) deviate
from this plane by 0.019(1) and 0.042(2) Å bent toward
P(2).
F igu r e 1. Structural view of [RuCp(CPMe3dCPh-η2-CHd
-
CHPh)(PPh3)]PF6 (3) showing 20% thermal ellipsoids (PF6
omitted for clarity). Selected bond lengths (Å) and angles
(deg): Ru-C(1-5)av 2.220(4), Ru-C(6) 2.292(4), Ru-C(7)
2.197(4), Ru-C(9) 2.139(4), Ru-P(2) 2.326(2), P(1)-C(9)
1.786(4), C(6)-C(7) 1.399(5), C(7)-C(8) 1.489(5), C(8)-C(9)
1.334(5), C(6)-C(7)-C(8) 123.0(3), C(9)-C(8)-C(7) 104.9-
(3).
syn site. It may be speculated that such a formal 1,4
hydrogen shift reaction proceeds most likely via an
initial C-H activation step induced by the incoming
nucleophile PPh3. The hydrogen is then delivered
through the metal center to the carbene carbon atom
via the inside face of the molecule to give 3. According
to this finding, the mechanism of the reaction shown in
Scheme 1 has to be reconsidered. We believe that this
reaction also involves a C-H activation step, and
consequently complex D should be obtained rather than
the isomeric C.
Apart from their reactions with simple donor ligands,
ruthenium allyl carbene complexes are capable of
activating nearby C-H bonds of aryl and alkyl groups
in tertiary phosphine ligands. This occurs if the latter
are sufficiently bulky such as PPh3 and PCy3, whereas
no such reaction is observed with PMe3. A pertinent
reaction is given in Scheme 3 for the reaction of 1a with
terminal alkynes HCtCR (R ) C6H5, n-Bu, Ph-p-NO2,
[Cc]+ (cobaltocenium), H). The initially formed allyl
carbene complexes 2b-e are not stable and transform
slowly at room temperature into the novel η4-butadiene
complexes [RuCp(η4-CHRCHCCH-PPh2(η1-C6H4)]PF6
(4a -d ) featuring an orthometalated arene ligand de-
rived from PPh3 (an exception is the reaction involving
the parent acetylene, see below). The complexes 4 are
air-stable in the solid state and were characterized by
a combination of elemental analysis and 1H, 13C{1H},
and 31P{1H} NMR spectroscopy.
Unfortunately, no intermediate formation could be
detected by NMR monitoring, although, as remarked
above, the reaction is not a simple nucleophilic addition
of PPh3 at the metal center.
Note that the hydrogen of the terminal allyl carbon
atom of 2a which occupies a pseudo syn position
migrates to the carbene carbon atom, then adopting an
anti position, while the PMe3 substituent ends up in a

2914 Organometallics, Vol. 21, No. 14, 2002
Ru¨ba et al.
Sch em e 3
legs. The Ru-C(23) bond distance is 2.112(5) Å. The
Ru-C(6), Ru-C(7), Ru-C(8), and Ru-C(9) bond dis-
tances are 2.141(5), 2.181(4), 2.176(6), and 2.297(6) Å,
respectively. The C-C distances within the diene frag-
ment are very similar, ranging from 1.439 to 1.392 Å.
A somewhat different reaction takes place when 1a
is treated with parent acetylene in that the allyl carbene
intermediate 2f eventually rearranges into [RuCp(η3-
CHCHCH-CH2PPh2-η2-C6H4)]PF6 (5), shown in Scheme
3, in 89% isolated yield. The structure and bonding
features of 5 are rather unusual. First, an ortho C-H
bond of the PPh3 substituent has been activated, result-
ing in C-C bond formation between the carbene carbon
atom of the allyl carbene moiety and the ortho arene
carbon atom. In the course of this process the ortho
hydrogen atom has been transferred to the terminal
carbon of the allyl carbene unit involving carbon sp2 f
sp3 rehybridization. Furthermore, besides coordination
to an η3-allyl moiety, the metal center is η2-coordinated
to a double bond of a phenyl ring adjacent to the P-donor
of the PPh3 substituent. This bonding mode is very rare,
and thus only a few examples have been reported
recently.7 Complex 5 was fully characterized by elemen-
F igu r e 2. Structural view of [RuCp(η4-CH(C6H9)CHC-
(C6H9)CH-PPh2(η1-C6H4))]PF6 (4a ) showing 20% thermal
ellipsoids (PF6- omitted for clarity). Selected bond lengths
(Å) and angles (deg): Ru-C(1-5)av 2.217 (7), Ru-C(6)
2.141(5), Ru-C(7) 2.181(4), Ru-C(8) 2.176(6), Ru-C(9)
2.297(6), Ru-C(23) 2.112(5), P(1)-C(6) 1.778(5), C(6)-C(7)
1.439(6), C(7)-C(8) 1.432(7), C(8)-C(9) 1.392(7), C(6)-
C(7)-C(8) 120.5(4), C(7)-C(8)-C(9) 124.1(6).
Thus, in the 1H NMR spectrum of 4a the Cp ring gives
rise to a singlet at 5.33 ppm. The diene moiety exhibits
three characteristic doublets centered at 5.99, 4.75, and
1.97 ppm assignable to H3, H1, and H,4 respectively. In
the 13C{1H} NMR spectrum the orthometalated carbon
atom displays a characteristic singlet at 181.9 ppm,
while the carbon atoms of the diene unit are observed
at 99.9, 85.9, 76.3, and 36.5 (d, J CP ) 78.1 Hz),
assignable to C2, C4, C3, and C1, respectively. The Cp
ligand shows a singlet at 89.2 ppm. The NMR spectra
of 4b-d are analogous and are not described here. In
addition to spectroscopic and analytical characteriza-
tions of 4a -d , the solid state structure of 4a was
determined by single-crystal X-ray diffraction. An ORTEP
diagram is shown in Figure 2, with selected bond
distances and angles reported in the caption. Accord-
ingly, the complex adopts a three-legged piano stool
conformation with the orthometalated phenyl substitu-
ent and the two CdC bonds of the diene moiety as the
1
tal analysis and H, 13C{1H}, and 31P{1H} NMR spec-
1
troscopy. Characteristic are the H NMR resonances of
the CH2 moiety giving rise to resonances at 3.59 and
2
1.84 ppm with a geminal coupling constant J HH of 16.3
Hz. In the 13C{1H} NMR spectrum the sp3 carbon atom
C1 shows a doublet resonance centered at 28.8 ppm (J CP
) 67.3 Hz).
The structure of 5 as determined from a single-crystal
X-ray study is shown in Figure 3, with selected bond
distances and angles reported in the caption. Clearly,
one phenyl substituent of PPh3 forms a C-C bond with
the original carbene carbon atom and is bound in η2-
fashion to the metal center. The allyl functionality is
asymmetrically bonded to the metal with the Ru-C
bond distance to the central allyl carbon atom C(7)
(2.133(4) Å) slightly shorter than the Ru-C bonds to
(7) For related PAr2(η2-arene) complexes see: (a) Feiken, N.;
Pregosin, P. S.; Trabesinger, G.; Scalone, M. Organometallics 1997,
16, 537. (b) Feiken, N.; Pregosin, P. S.; Trabesinger, G.; Albinati, A.;
Evoli, G. L. Organometallics 1997, 16, 5756. (c) Cheng, T.-Y.; Szalda,
D. J .; Bullock, R. M. J . Chem. Soc., Chem. Commun. 1999, 1629. (d)
Aneetha, H.; J imenez-Tenorio, M.; Puerta, M. C.; Valerga, P.; Mereiter,
K. Organometallics 2002, in press.

RuCp and RuCp* Allyl Carbene Complexes
Organometallics, Vol. 21, No. 14, 2002 2915
(2), and 2.250(2) Å, respectively. Further, the C-C
distances within the diene fragment are rather uniform,
ranging between 1.437 and 1.391 Å.
In the present work we include also experiments with
the first Cp* analogue [RuCp*(PEt3)(CH3CN)2]+ (1c).
This complex is obtained in essentially quantitative
1
yields (as monitored by H NMR spectroscopy) by the
9
treatment of [RuCp*(CH3CN)3]PF6 with 1 equiv of the
PEt3 at room temperature. The complex is stable to air
in the solid state but decomposes slowly in solutions
exposed to air.
Scheme 6 summarizes the reactions of 1c with the
alkynes HCtCR (R ) COOMe, n-Bu) and 1,6-hep-
tadiyne. The η3-allyl carbene complexes 8a -c, respec-
tively, were obtained in high isolated yields. The identity
F igu r e 3. Structural view of [RuCp(η3-CHCHCH-CH2-
PPh2-η2-C6H4)]PF6 (5) showing 20% thermal ellipsoids
1
of these compounds follows from H, 13C{1H}, and 31P-
-
{1H} NMR spectroscopy and elemental analysis. Char-
acteristic is the low-field signal of the carbene hydrogen
atom giving rise to a signal at 11.71 ppm in the 1H NMR
spectrum of 8c and doublet resonances at 256.3 and
227.1 ppm (J CP ) 7-6 Hz) and a doublet in the range
32.2-28.6 ppm (J CP ) 66-55 Hz) in the 13C{1H} NMR
spectra of 8a -c, which are assigned to the carbene
carbon atoms and the terminal allyl carbon atom
bearing the phosphine substituent, respectively. It may
be mentioned that no isomers were obtained, meaning
that C-C coupling is highly selective in a head-to-tail
fashion (for terminal alkynes) with the substituents
ending up in the 1 and 3 position. Noteworthy, RuCp*
allyl carbene complexes have been also prepared re-
cently by the reaction of RuCp* metallacyclopentatriene
complexes with tertiary phosphines and phosphites,
respectively.10
(PF6 omitted for clarity). Selected bond lengths (Å) and
angles (deg): Ru-C(1-5)av 2.188(4), Ru-C(6) 2.192(4),
Ru-C(7) 2.133(4), Ru-C(8) 2.222(4), Ru-C(10) 2.198(3),
Ru-C(11) 2.207(3), P(1)-C(9) 1.778(3), P(1)-C(10) 1.787-
(3), C(6)-C(7) 1.393(7), C(6)-C(11) 1.441(6), C(7)-C(8)
1.412(5), C(8)-C(9) 1.525(5), C(10)-C(11) 1.476(4), C(6)-
C(7)-C(8) 121.7(4).
the outer carbon atoms C(6) and C(8) (2.192(4) and
2.222(4) Å, respectively). The phenyl moiety of the PPh3
ligand is bonded to the metal center with the Ru-C
bonds to the carbon atoms C(10) and C(11) being 2.198-
(3) and 2.207(3) Å, respectively. The C(10)-C(11) bond
distance is 1.474(4) Å and thus slightly longer than the
other C-C bond distances within the phenyl substitu-
ent. For comparison,7b in [RuCp(MeO-Bihep)]+ (MeO-
Bihep ) 6,6′-dimethoxybiphenyl-2,2′-diyl)bis(bis(3,5-di-
tert-butylphenyl)phosphine)), where a biaryl double
bond adjacent to the P-donor atom coordinates to the
ruthenium atom in η2-fashion, the respective Ru-
C(aryl) bond distances are longer, being 2.38(1) and
In contrast to 8b, both complexes 8a and 8c are
unstable in solution and react slowly at room temper-
ature to [Ru(η6-C5Me4CH2)(η4-CH(COOMe)dCH-
C(COOMe)dCHPEt3)]PF6 (9a ) and [Ru(η6-C5Me4CH2)-
(η4-CH2dC(CH2)3CdCH-PEt3)]PF6 (9b), respectively.
In both, one of the ring methyl C-H bonds of the Cp*
ligand has been cleaved (Scheme 6). In these transfor-
mations, the hydrogen atom is transferred to the car-
bene carbon atom at the inside face of the molecule,
forming an η4-diene unit. The methylene protons of 9a
exhibit two characteristic singlets at 5.05 and 4.75 ppm
2.31(1) Å. Similarly, also in [RuCp(PPri Me)(PPh2-η2-
2
C6H5)]+, where one phenyl double bond of the PPh3
ligand is η2-coordinated, the Ru-C(aryl) bond lengths
are considerably longer, being 2.371(3) and 2.459(3) Å.7d
We then repeated the reaction of Scheme 3, but used
PCy3 instead of PPh3. Our motive was to see whether
the presence of â-hydrogen atoms imposes any mecha-
nistic changes. However, it is noteworthy that no
â-elimination occurred. Instead, the reaction taking
place is identical to that using PPh3; that is, one Cy
group of the PCy3 ligand becomes σ-bonded to the metal
center (Scheme 4). The only difference from Scheme 3
is that no allyl carbene intermediate could be detected.
The lack of â-elimination contrasts with our recent
observation that the analogous reaction of 1b with 1,6-
heptadiyne did not stop after the oxidative addition step,
but â-elimination took place to give complex 7, where
eventually one cyclohexyl substituent of the phosphine
ligand features an η2-coordinated cyclohexenyl ligand
(Scheme 5).8
1
in the H NMR spectrum. The small coupling constant
(0-3 Hz) is typical of geminal hydrogens attached to
sp2-hybridized carbons (whereas those attached to sp3-
hybridized carbon exhibit typical coupling constants in
the range 12-15 Hz). In the 13C{1H} NMR spectrum
the methylene carbon atom gives rise to a doublet
centered at 51.8 ppm (J CP ) 3.1 Hz). Of course, the NMR
spectra of 9b are very similar. On the basis of the NMR
spectroscopic data the newly formed η6-C5Me4CH2 ligand
may be envisioned as tetramethylfulvene rather than
a tetramethylcyclopentadienyl-σ-alkyl ligand. X-ray data
are also consistent with a tetramethylfulvene rather
than an η1:η5-CH2C5Me4 (σ:η5-CH2C5Me4) description
The identity of 6a was proven by NMR spectroscopic
and analytical characterization as well as by single-
crystal X-ray diffraction. A structural view is depicted
in Figure 3, with selected bond distances and angles
reported in the caption. It is seen that the structures of
6a and 4a are very similar, both adopting a three-legged
piano stool conformation. The Ru-C(23) bond distance
is 2.214(2) Å. The Ru-C(6), Ru-C(7), Ru-C(8), and
Ru-C(9) bond distances are 2.258(2), 2.154(2), 2.182-
(8) Dehydrogenation of cyclohexyl groups in monodendate PCy3 to
give η2- and η3-cyclohexyl units: (a) Christ, M. L.; Sabo-Etienne, S.;
Chaudret, B. Organometallics 1995, 14, 1082. (b) Borowski, A. F.; Sabo-
Etienne, S.; Christ, M. L.; Donnadieu, B.; Chaudret, B. Organometallics
1996, 15, 1427. (c) Chaudret, B.; Dagnac, P.; Labroue, D.; Sabo-Etienne,
S. New J . Chem. 1996, 20, 1137. (d) Six, C.; Gabor, B.; Go¨rls, H.;
Mynott, R.; Philipps, P.; Leitner, W. Organometallics 1999, 18, 3316.
(9) Steinmetz, B.; Schenk, W. A. Organometallics 1999, 18, 943.
(10) Ernst, C.; Walter, O.; Dinjus, E. J . Organomet. Chem. 2001,
627, 249.

2916 Organometallics, Vol. 21, No. 14, 2002
Ru¨ba et al.
Sch em e 4
Sch em e 5
Sch em e 6
(vide infra). Related methyl C-H activation processes
of transition metal coordinated C5Me5 and C6Me6 ligands
have been reported previously.11,12
To gain further insight into the bonding of the C5-
Me4CH2 ligand, for 9a also a single-crystal diffraction
study has been performed. A structural view is shown
in Figure 5, with selected bond distances and angles
reported in the caption. Most notably, the CH2 group of
the η6-bonded C5Me4CH2 ligand is bent toward the
metal by about 0.92(1) Å from the C5 plane, correspond-
ing to an angle of about 38.4°. The Ru-C(6) bond
distance is comparable (2.298(7) Å) to those of other
ruthenium complexes containing the η6-C5Me4CH2 ligand
(cf. 2.301(2), 2.268(4) (2.271(4)), and 2.430(11) Å in Ru-

RuCp and RuCp* Allyl Carbene Complexes
Organometallics, Vol. 21, No. 14, 2002 2917
F igu r e 5. Structural view of[Ru(η6-C5Me4CH2)(η4-CH2d
C(CH2)3CdCHPEt3)]PF6 (9b) showing 20% thermal el-
lipsoids (PF6 omitted for clarity). Selected bond lengths
F igu r e 4. Structural view of [RuCp(η4-CH(C6H9)CHC-
(C6H9)CH-PCy2(η1-C6H10))]PF6 (6a ) showing 20% thermal
ellipsoids (PF6- omitted for clarity). Selected bond lengths
(Å) and angles (deg): Ru-C(1-5)av 2.233(3), Ru-C(6)
2.158(2), Ru-C(7) 2.182(2), Ru-C(8) 2.154(2), Ru-C(9)
2.250(2), Ru-C(23) 2.214(2), P(1)-C(6) 1.784(2), C(6)-C(7)
1.451(3), C(7)-C(8) 1.437(3), C(8)-C(9) 1.391(3), C(6)-
C(7)-C(8) 120.4(1), C(7)-C(8)-C(9) 123.5(2).
-
(Å) and angles (deg): Ru-C(1) 2.070 (7), Ru-C(2) 2.197-
(7), Ru-C(3) 2.267(7), Ru-C(4) 2.280(7), Ru-C(5) 2.183-
(6), Ru-C(6) 2.297(7), Ru-C(11) 2.147(7), Ru-C(12) 2.156-
(8), Ru-C(13) 2.143(7), Ru-C(14) 2.147(7), C(1)-C(2)
1.420(11), C(1)-C(6) 1.426(11), C(1)-C(5) 1.436(10), C(2)-
C(3) 1.408(11), C(3)-C(4) 1.444(11), C(4)-C(5) 1.412(11),
C(11)-C(12) 1.423(10), C(12)-C(13) 1.437(19), C(13)-C(14)
1.448(10), P(1)-C(14) 1.778(7), C(11)-C(12)-C(13) 121.2-
(7), C(12)-C(13)-C(14) 119.3(6).
(η6-C5Me4CH2)(COD),12a [Ru(η6-C5Me4CH2)Cl2]2,12b,c and
[Ru(η6-C5Me4CH2)(Me2NCH2CH2NMe2)(OH)]PF6,12e re-
spectively).
[RuCp(PCy3)(CH3CN)2]PF6 (1b) were prepared according to the
literature.6 Synthetic and spectroscopic details of complexes
[RuCp(dC(Ph)(η3-CHC(Ph)CHPMe3)]PF6 (2a), [RuCp(dC(C6H9)-
(η3-CHC(C6H9)CHPPh3)]PF6 (2b), [RuCp(dC(n-Bu)(η3-CHC(n-
Bu)CHPPh3)]PF6 (2c), [RuCp(dCH-η3-CHCHCHPPh3)]PF6 (2f),
and [RuCp(dCH-(η3-CC(CH2)3CHPCy3)]PF6 (2g), which are
intermediates of the reactions presented in this paper, as well
as of complexes [RuCp(-CPMe3dCPh-η2-CHdCHPh)(PPh3)]-
PF6 (3) and [RuCp(η3-CH2C(CH2)3CCH2PCy2(η2-C6H9)]PF6 (7)
have been reported previously.5a IR spectra were recorded in
Nujol mulls on a Perkin-Elmer FTIR Spectrum 1000 spectro-
photometer. 1H, 13C{1H}, and 31P{1H} NMR spectra were
recorded on Bruker AVANCE-250, Varian Unity 400 MHz, or
Varian Gemini 200 MHz spectrometers and were referenced
to SiMe4 and H3PO4 (85%), respectively. 1H and 13C{1H} NMR
In summary, we have shown that allyl carbene
complexes indeed behave as reactive masked 16e species
which are able to accommodate nucleophiles at the
metal center to give η3-butadienyl complexes. In the
course of this process a C-H bond activation takes place
resulting in an overall 1,4 hydrogen shift. Moreover, we
have demonstrated that intramolecular C-H activation
reactions are a very prominent feature of allyl carbenes,
and C-H bonds of both aryl and alkyl substituents of
tertiary phosphine ligands as well as methyl C-H bonds
of the Cp* ligand are readily activated and cleaved to
give novel η4-butadiene complexes featuring metal
carbon σ-bonds.
1
signal assignments were confirmed by H-COSY, 135-DEPT,
and HMQC(1H-13C) experiments. Microanalysis was per-
formed by the Serveis Cient´ıfico-Te`cnics, Universitat of Bar-
celona.
Exp er im en ta l Section
Gen er a l In for m a tion . All manipulations were performed
under an inert atmosphere of argon by using Schlenk tech-
niques. All chemicals were standard reagent grade and used
without further purification. The solvents were purified ac-
cording to standard procedures.13 The deuterated solvents were
purchased from Aldrich and dried over 4 Å molecular sieves.
[RuCp*(CH3CN)3]PF6,9 [RuCp(PPh3)(CH3CN)2]PF6 (1a ), and
[Ru Cp *(P Et3)(CH3CN)2]P F 6 (1c). A solution of [RuCp*-
(CH3CN)3]PF6 (504 mg, 1.00 mmol) in CH3CN (5 mL) was
treated with 1 equiv of PEt3 (148.4 µL, 1.00 mmol) and stirred
for 2 h at room temperature. The solvent was then removed
under vacuum, and the residue was washed with Et2O and
dried under vaccum. Yield: 512 mg (88%). Anal. Calcd for
C
20H36F6N2P2Ru: C, 41.9; H, 6.28. Found: C, 41.9; H, 6.29.
(11) (a) Riley, P. N.; Parker, J . R.; Fanwick, P. E.; Rothwell, I. P.
Organometallics 1999, 18, 3579, and references therein. (b) Klahn, A.
H.; Oelckers, B.; Godoy, F.; Garland, M. T.; Vega, A.; Perutz, R.;
Higgitt, C. L. J . Chem. Soc., Dalton Trans. 1998, 3079, and references
therein.
(12) For related ruthenium tetramethylfulvene complexes see: (a)
Li, C.; Luo, L.; Nolan, S. P.; Marshall, W.; Fagan, P. J . Organometallics
1996, 15, 3456. (b) Fan, L.; Turner, M. L.; Hursthouse, M. B.; Malik,
K. M. A.; Gusev, O. V.; Maitlis, P. M. J . Am. Chem. Soc. 1994, 116,
385. (c) Fan, L.; Wei, C.; Aigbirhio, F. I.; Turner, M. L.; Gusev, O. V.;
Morozova, L. N.; Knowles, D. R. T.; Maitlis, P. M. Organometallics
1996, 15, 98. (d) Hankin, D. M.; Danopoulos, A. A.; Wilkinson, G.;
Sweet, T. K. N.; Hursthouse, M. B. J . Chem. Soc., Dalton Trans. 1996,
4063. (e) Gemel, C.; Mereiter, K.; Schmid, R.; Kirchner, K. Organo-
metallics 1997, 16, 5601 (f) Ko¨lle, U.; Kang, B.-S.; J . Organomet. Chem.
1990, 386, 267.
1H NMR (δ, CDCl3, 20 °C): 2.41 (bs, 6H, CH3CN), 1.64 (m,
6H, P(CH2CH3)3), 1.57 (s, 15H, C5(CH3)5), 0.95 (dt, 9H, 3J HP
)
17.7 Hz, 3J HH ) 7.5 Hz, P(CH2CH3)3). 13C{1H} NMR (δ, CDCl3,
2
20 °C): 124.5 (s, CH3CN), 85.0 (d, J CP ) 2.1 Hz, C5(CH3)5),
1
18.0 (d, J CP ) 23.0 Hz, PCH2CH3), 9.33 (s, C5(CH3)5), 6.72 (s,
PCH2CH3), 4.08 (s, CH3CN). 31P{1H} NMR (δ, CDCl3, 20 °C):
32.1 (s). IR (Nujol, cm-1): 2269 (m, νCN).
[R u Cp (η4-CH (C6H 9)CH C(C6H 9)CH -P P h 2(η1-C6H 4))]-
P F 6 (4a ). A solution of 1a (200 mg, 0.319 mmol) and 1-ethi-
nylcyclohexene (83 µL, 0.701 mmol) in CH3NO2 (5 mL) was
stirred for 20 h at room temperature. The color of the solution
changed from yellow via violet to brown. After removal of the
solvent under reduced pressure, the residue was dissolved in
CH2Cl2 (2 mL) and Et2O (10 mL) was added. A yellow
(13) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 3rd ed.; Pergamon: New York, 1988.

2918 Organometallics, Vol. 21, No. 14, 2002
Ru¨ba et al.
precipitate was formed, which was collected on a glass frit,
washed with Et2O, and dried under vacuum. Yield: 120.3 mg
(48%). Anal. Calcd for C39H40P2F6Ru: C, 59.62; H, 5.13.
Found: C, 59.43; H, 5.09. 1H NMR (δ, acetone-d6, 20 °C):
8.53-8.33 (m, 1H, Ph), 8.06-6.89 (m,13H, Ph), 6.61 (m, 1H,
(70 mg, 0.100 mmol), was added. The reaction mixture was
stirred at room temperature for 20 h, whereupon the color of
the solution changed from yellow to green and finally to dark
orange. After that the solvent was removed under vacuum,
the residue was redissolved in CH2Cl2 (0.5 mL), and Et2O (10
mL) was added. An orange precipitate was formed, which was
collected on a glass frit, washed with Et2O, and dried under
vacuum. Yield: 103 mg (85%). Anal. Calcd for C47H40F18P4-
3
C6H9), 5.99 (d, J HH ) 9.3 Hz, 1H, H3), 5.33 (s, 5H, Cp), 4.75
2
(d, J PH ) 5.1 Hz, 1H, H1), 4.56 (m, 1H, C6H9), 2.67-2.11 (m,
4H, CH2), 1.97 (d, 3J HH ) 9.3 Hz, 1H, H4), 1.91-1.33 (m, 12H,
CH2). 13C{1H} NMR (δ, acetone-d6, 20 °C): 181.9 (d, J CP ) 32.3
Hz, 1C, Phm2), 144.9, 144.6, 142.4, 137.2, 137.1, 135.4, 134.9,
134.8, 134.7, 133.6, 133.5, 133.3, 133.0, 132.8, 132.7, 132.6,
131.9, 131.1, 131.0, 130.9, 130.8, 130.7, 130.5, 128.3, 127.8,
126.3, 125.2, 124.6, 124.4 (21C, Ph, C6H9), 99.9 (1C, C2), 89.2
1
Co2Ru: C, 43.77; H, 3.13. Found: C, 43.62; H, 3.15. H NMR
(δ, acetone-d6, 20 °C): 8.26-7.27 (m, 14H, Ph), 7.19 (d, J HH
)
8.7 Hz, H3), 6.72 (m, 1H, Cc), 6.56 (m, 1H, Cc), 6.16 (m, 2H,
Cc), 6.06 (m, 1H, Cc), 5.99 (s, 5H, CpCo), 5.86 (m, 1H, Cc), 5.78
(m, 2H, Cc), 5.56 (d, J HP ) 4.0 Hz, H1), 5.45 (s, 5H, CpCo), 5.35
(s, 5H, CpRu), 5.04 (m, 1H, Cc), 2.37 (d, J HH ) 8.7 Hz, H4). 13C-
{1H} NMR (δ, CD3NO2, 20 °C): 170.9 (d, J CP ) 28.7 Hz, 1C,
Phm2), 144.2, 143.9, 142.5, 140.6, 135.5, 134.5, 134.3, 134.0,
133.9, 133.8, 133.2, 133.1, 132.8, 132.7, 131.9, 131.7, 131.1,
130.9, 126.5, 126.4 (17C, PPh3), 106.5 (d, J CP ) 5.3 Hz, 1C,
C2), 104.1 (1C, Cc), 92.8 (5C, CpRu), 90.3 (1C, C4), 86.4 (5C,
CpCo), 85.9 (2C, Cc), 85.8 (2C, Cc), 85.4 (5C, CpCo), 84.9 (2C,
Cc), 84.6 (1C, Cc), 82.8 (1C, Cc), 80.0 (1C, Cc), 77.8 (1C, C3),
44.9 (d, J CP ) 77.0 Hz, 1C, C1). 31P{1H} NMR (δ, acetone-d6,
20 °C): 47.5 (PPh2), -142.6 (J PF ) 711.2 Hz, PF6-).
1
(5C, Cp), 85.9 (1C, C4), 76.3 (1C, C3), 36.5 (d, J CP ) 78.1 Hz,
1C, C1), 26.9, 26.5, 24.2, 23.2, 23.0, 22.9, 22.7, 22.6 (16C, CH2).
31P{1H} NMR (δ, acetone-d6, 20 °C): 48.7 (PPh2), -142.7 (J PF
) 707.8 Hz, PF6-).
[Ru Cp (η3-CHCHCH-CH2P P h 2-η2-C6H4)]P F 6 (5). A solu-
tion of 1a (100 mg, 0.159 mmol) in CH3NO2 (4 mL) was stirred
under an atmosphere of acetylene at room temperature for 30
min. The color changed from yellow to red. The solvent was
removed under reduced pressure. The remaining residue was
dissolved in CH2Cl2 (3 mL) and was stirred for 1 h at room
temperature, whereupon the color of the solution became
orange. After removal of the solvent under reduced pressure,
the remaining solid was washed with petroleum ether and
dried under vacuum. Yield: 88 mg (89%). Anal. Calcd for
C27H24F6P2Ru: C, 51.85; H, 3.87. Found: C, 51.81; H, 3.84.
1H NMR (δ, acetone-d6, 20 °C): 8.42-8.26 (m, 2H, PPh2(C6H4)),
8.09-7.79 (m, 4H, PPh2(C6H4)), 7.74-7.62 (m, 1H, PPh2-
(C6H4)), 7.57-7.44 (m, 2H, PPh2(C6H4)), 7.16-6.88 (m, 5H,
[R u Cp (η4-CH (n -Bu )CH C(n -Bu )CH -P P h 2(η1-C6H 4))]-
P F 6 (4b). A solution of 2b (40 mg, 0.136 mmol) in acetone-d6
was kept at room temperature for 31 days. During that time
the color of the solution changed gradually from red to orange.
1H NMR (δ, acetone-d6, 20 °C): 8.58 (d, J HH ) 7.3 Hz, 1H,
C6H4), 8.53 (d, J HH ) 7.3 Hz, 1H, C6H4), 8.10-7.24 (m, 10H,
Ph), 7.11 (m, 1H, C6H4), 6.85 (m, 1H, C6H4), 4.34 (s, 5H, Cp),
4.25 (d, J HH ) 4.9 Hz, H3), 4.12 (d, J PH ) 13.4 Hz, H1), 2.46-
2.28 (m, 1H, CH2), 2.23-1.96 (m, 4H, CH2), 1.93-1.63 (m, 4H,
CH2, H4), 1.59-1.36 (m, 2H, CH2), 1.29-1.05 (m, 2H, CH2),
3
4
PPh2(C6H4)), 6.85 (dd, J HH ) 6.0 Hz, J HP ) 2.0 Hz, 1H, H4),
3
3
5.65 (ddd, J HH ) 7.4 Hz, J HH ) 6.0 Hz, J HH ) 2.8 Hz, 1H,
H3), 4.79-4.46 (m, 1H, H2), 4.54 (s, 5H, Cp), 3.59 (ddd, 2J HH
)
3
3
0.94 (t, J HH ) 7.3 Hz, CH3), 0.64 (t, J HH ) 7.3 Hz, CH3). 31P-
{1H} NMR (δ, acetone-d6, 20 °C): 30.3 (PPh2), -142.7 (PF6,
J PF ) 707.8 Hz).
3
2
16.3 Hz, J HH ) 16.1 Hz, J HP ) 9.5 Hz, 1H, H1), 1.84 (ddd,
2J HH ) 16.3 Hz, J HH ) 4.0 Hz, J HP ) 2.8 Hz, 1H, H1′). 13C-
{1H} NMR (δ, CDCl3, 20 °C): 135.4, 135.3, 135.2, 134.8, 134.7,
134.6, 134.3, 134.2, 134.1, 133.7, 133.6, 133.5, 132.4, 132.1,
132.0, 131.9, 131.7, 130.5, 130.1, 129.9, 128.8, 128.7, 128.6,
128.5, 127.5, 127.4, 123.8, 122.8, 121.9, 121.7, 121.4 (15C,
PPh2(C6H4)), 91.6 (1C, C4), 82.5 (d, J CP ) 1.8 Hz, 1C, C3), 81.1
(5C, Cp), 42.4 (1C, C2), 28.8 (d, J CP ) 67.3 Hz, 1C, C1). 31P-
{1H} NMR (δ, CDCl3, 20 °C): 63.7 (PPh2), -143.4 (J PF ) 712.1
Hz, PF6-).
3
2
[R u Cp (η4-CH (P h -p -NO2)CH C(P h -p -NO2)CH -P P h 2(η1-
C6H4))]P F 6 (4c). A solution of 1a (30 mg, 0.048 mmol) und
p-nitrophenylacetylene (15 mg, 0.100 mmol) in CD3NO2 (0.4
mL) was kept at room temperature for 4 days. The color of
the solution changed from yellow to dark green and eventually
to dark orange. The reaction was monitored by NMR spec-
troscopy, revealing the intermediacy of the allyl carbene
complex [RuCp(dC(Ph-p-NO2)-η3-CH-C(Ph-p-NO2)CHPPh3]-
PF6 (2d ). 1H NMR (δ, CD3NO2, 20 °C): 8.31-8.16 (m, 4H,
NO2-C6H4-), 7.81-7.68 (m, 4H, NO2-C6H4-), 7.65-7.35 (m,
2
15H, PPh3), 6.32 (d, J HP ) 8.5 Hz, 1H, H4), 5.89 (s, 1H, H2),
5.32 (s, 5H, Cp). 31P{1H} NMR (δ, CD3NO2, 20 °C): 31.8 (PPh3),
-143.4 (1J PF ) 706.9 Hz, PF6-). 1a was quantitatively con-
1
verted to 4c after about 4 days. H NMR (δ, CD3NO2, 20 °C):
8.74-8.55 (m, 1H, PPh2C6H4), 8.38-7.16 (m, 19H, PPh3,
3
3
p-NO2-C6H4), 7.08 (d, J HH ) 8.5 Hz, H3), 6.96 (d, J HH ) 8.6
Hz, 2H, p-NO2-C6H4), 5.26 (s, 5H, Cp), 5.17 (d, 2J HP ) 3.8 Hz,
H1), 2.46 (d, J HH ) 8.5 Hz, H4). 13C{1H} NMR (δ, acetone-d6,
3
20 °C): 175.6 (d, J CP ) 30.5 Hz, Phm2), 149.3, 148.11, 147.5,
147.0, 144.9, 144.6, 142.8, 141.0, 135.8, 135.4, 135.2, 134.9,
134.7, 133.6, 133.3, 133.2, 133.0, 131.4, 131.2, 131.0, 130.8,
130.6, 130.4, 129.6, 127.1, 125.6, 124.9, 124.8, 124.6, 124.3
(28C, PPh3, p-NO2-C6H4), 97.9 (1C, C2), 93.0 (5C, Cp), 87.7
[R u Cp (η4-CH (C6H 9)CH C(C6H 9)CH -P Cy2(η1-C6H 10))]-
P F 6 (6a ). A solution of 1b (100 mg, 0.148 mmol) and 1-ethi-
nylcyclohexene (40 µL, 0.341 mmol) in CH2Cl2 (4 mL) was
stirred at room temperature for 20 h. After removal of the
solvent under reduced pressure, the dark yellow solid was
obtained, which was washed with Et2O (5 mL) and dried under
vacuum. The crude product was purified by column chroma-
tography (neutral Al2O3/acetone). The yellow band was col-
lected. Yield: 105 mg (88%). Anal. Calcd for C39H58F6P2Ru:
C, 58.27; H, 7.27. Found: C, 58.31; H, 7.29. 1H NMR (δ, CDCl3,
(1C, C4), 72.8 (1C, C3), 44.4 (d, J CP ) 77.7 Hz, 1C, C1). 31P-
1
{1H} NMR (δ, acetone-d6, 20 °C): 49.0 (PPh2), -142.6 (1J PF
)
707.8 Hz, PF6-).
[R u Cp (η4-CH (Cc)CH C(Cc)CH -P P h 2(η1-C6H 4))](P F 6)3
(4d ). To a solution of 1a (58 mg, 0.094 mmol) in CH3NO2 (5
mL) 1-ethinyl cobaltocenium hexafluorophosphate, [Cc]PF6

RuCp and RuCp* Allyl Carbene Complexes
Organometallics, Vol. 21, No. 14, 2002 2919
Ta ble 1. Cr ysta llogr a p h ic Da ta for 3, 4a , 5, 6a , a n d 9b
3
4a
5
6a
9b
formula
fw
C
42H41F6P3Ru
C39H40F6P2Ru
785.72
C27H24F6P2Ru
625.47
C39H58F6P2Ru
803.86
C23H38F6P2Ru
591.54
853.73
cryst size, mm
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
0.40 × 0.20 × 0.04
P1h (no. 2)
10.007(5)
10.727(6)
20.578(9)
75.14(2)
82.54(2)
65.72(2)
1946(2)
2
1.457
296(2)
0.585
multiscan
872
0.40 × 0.24 × 0.06
P21 (no. 4)
10.007(4)
17.243(6)
10.643(4)
90
104.21(1)
90
1780.3(12)
2
1.466
297(2)
0.589
multiscan
804
0.50 × 0.40 × 0.35
P21 (no. 4)
8.138(3)
10.724(4)
14.922(6)
90
104.23(2)
90
1262.3(8)
2
1.646
297(2)
0.807
multiscan
628
0.65 × 0.24 × 0.12
Pca21 (no. 29)
20.101(4)
10.857(3)
17.249(4)
90
90
90
3764(2)
4
1.418
0.84 × 0.18 × 0.12
P1h (no. 2)
8.032(3)
8.888(3)
18.442(7)
85.38(2)
79.46(2)
86.59(2)
1288.8(8)
2
1.524
297(2)
0.785
multiscan
608
Z
F
T, K
calc, g cm-3
297(2)
0.558
multiscan
1680
µ, mm-1 (Mo KR)
abs corr
F(000)
transmn factor min./max.
0.75/0.96
25
-11 e h e 11
-12 e k e 12
-24 e l e 24
21 495
6807
4751
470
0.042
0.79/0.93
25
-11 e h e 11
-20 e k e 20
-12 e l e 12
18 502
6257
5273
442
0.038
0.79/1.00
30
-11 e h e 11
14 e k e 14
20 e l e 20
32 734
7088
6435
335
0.034
0.71/0.89
30
-26 e h e 28
-15 e k e 15
-24 e l e 24
52 744
10 825
9246
438
0.028
0.76/1.00
25
-9 e h e 9
-10 e k e 10
-21 e l e 21
9650
3467
3125
289
0.062
θ
max, deg
index ranges
no. of reflns measd
no. of unique reflns
no. of reflns I > 2σ(I)
no. of params
R1 (I > 2σ(I))a
R1 (all data)a
0.074
0.097
0.050
0.097
0.042
0.079
0.037
0.071
0.069
0.151
wR2 (all data)b
diff Fourier peaks
-0.70/0.58
-0.29/0.64
-0.84/0.92
-0.35/0.37
-0.90/1.11
min./max., e Å-3
R1 ) ∑||Fo| - |Fc||/∑|Fo|. wR2 ) [∑(w(Fo2-Fc2)2)/∑(w(Fo2)2)]1/2
.
a
b
20 °C): 6.20 (m, 1H, C6H9), 5.76 (m, 1H, C6H9), 5.50 (d, 3J HH,trans
26.0, 25.6, 25.4 (16C, Cy). 31P{1H} NMR (δ, CDCl3, 20 °C): 61.2
(PCy2), -143.4 (1J PF ) 713.4 Hz, PF6-).
3
) 8.2 Hz, 1H, H3), 4.76 (s, 5H, Cp), 4.55 (vt, J HH ) 10.6 Hz,
[Ru Cp*(dC(COOMe)-η3-CHC(COOMe)CHP Et3)]P F6 (8a).
A solution of 1c (200 mg, 0.344 mmol) in acetone (5 mL) was
treated with a slight excess of HCtCCOOCH3 (70.0 µL, 0.787
mmol). The color changed to dark green after stirring for 5
min. The solvent was then removed under vacuum and the
residue washed with petroleum ether and Et2O and dried,
obtaining a dark green solid. Yield: 196 mg (87%). Anal. Calcd
for C24H38F6O4P2Ru: C, 44.0; H, 5.80. Found: C, 43.9; H, 5.80.
1H NMR (δ, acetone-d6, 0 °C): 6.15 (s, 1H, H2), 4.98 (d, 1H,
2J HP ) 6.3 Hz, H4), 3.87 and 3.83 (both s, 3H each, COOCH3),
1.89 (m, 6H, P(CH2CH3)3), 1.76 (s, 15H, C5(CH3)5), 1.11 (dt,
2
1H, Cym2), 3.44 (d, J HP ) 3.5 Hz, 1H, H1), 2.73-2.50 (m, 1H,
Cym1), 2.40-0.90 (m, 48 H, Cy, Cym, C6H9), 1.50 (s, 1H, H4).
13C{1H} NMR (δ, CDCl3, 20 °C): 138. 5 (1C, C6H91), 137.1 (d,
J CP ) 4.8 Hz, 1C, C6H61′), 130.9 (1C, C6H92), 127.1 (1C, C6H92′),
97.0 (1C, C2), 88.0 (5C, Cp), 73.9 (1C, C3), 69.5 (1C, C4), 53.5
1
1
(d, J CP ) 56.5 Hz, 1C, PCym1), 35.4 (d, J CP ) 31.3 Hz, 1C,
PCy1), 33.7 (d, 1J CP ) 43.2 Hz, 1C, PCy1′), 32.2 (1C, CH2), 30.3
(1C, PCym2), 30.2 (1C, CH2), 29.2 (d, J CP ) 64.3 Hz, 1C, C1),
1
28.3, 28.2, 27.6, 27.5, 27.3, 26.7, 26.6, 26.6, 26.5, 26.4, 26.2,
25.7, 25.6, 23.0, 22.9, 22.8, 22.4 (20C, CH2). 31P{1H} NMR (δ,
CDCl3, 20 °C): 61.2 (PCy2), -143.1 (J PF ) 705.3 Hz, PF6-).
3
2
9H, J HP ) 18.0 Hz, J HH ) 7.6 Hz, P(CH2CH3)3). 13C{1H} (δ,
[Ru Cp (η4-CH(P h -p-OMe)CHC(P h -p-OMe)CH-P Cy2(η1-
C6H10))]P F 6 (6b). A solution of 1b (285 mg, 0.423 mmol) and
p-methoxyphenylacetylene (137 µL, 1.058 mmol) in CH2Cl2 (3
mL) was stirred for 20 h at room temperature. The solvent
was removed under vacuum, and the dark brown residue was
purified by column chromatography (neutral Al2O3/CH2Cl2).
The second brown fraction was collected. After removal of the
solvent, the dark brown solid was washed with Et2O and dried
acetone-d6, 0 °C): 227.1 (d, J CP ) 7.2 Hz, C1), 172.0 (s,
3
COOCH3), 168.5 (d, J CP ) 5.5 Hz, COOCH3), 100.3 (s, C2),
2
94.8 (s, C5(CH3)5), 90.5 (d, 2J CP ) 2.5 Hz, C3), 53.1 and 52.4 (s,
COOCH3), 32.2 (d, J CP ) 66.6 Hz, C4), 14.0 and 13.5 (s,
1
2
P(CH2CH3)3), 10.1 (s, C5(CH3)5), 5.0 (d, J CP ) 5.0 Hz,
P(CH2CH3)3). 31P{1H} NMR (δ, acetone-d6, 0 °C): 47.4 (PEt3).
IR (Nujol, cm-1): 1713 (s, νCOOMe), 1632 (m, νCdC).
under vacuum. Yield: 290 mg (80%). Anal. Calcd for C41H54
-
F6O2P2Ru: C, 57.54; H, 6.36. Found: C, 57.48; H, 6.24. 1H
3
NMR (δ, CDCl3, 20 °C): 7.57 (d, J HH ) 8.9 Hz, 2H, CH3-
3
3
OC6H4), 7.24 (d, J HH ) 8.9 Hz, 2H, CH3OC6H4), 7.05 (d, J HH
3
) 8.9 Hz, 2H, CH3OC6H4), 6.91 (d, J HH ) 8.9 Hz, 2H, CH3-
3
OC6H4), 6.31 (d, J HH ) 7.9 Hz, 1H, H3), 4.74 (s, 5H, Cp), 4.74
(vt, J HH ) 10.3 Hz, 1H, Cym2), 3.88 (s, 3H, CH3OC6H4), 3.85
3
(s, 3H, CH3OC6H4), 3.62 (d, J HP ) 3.6 Hz, H1), 2.95-2.71 (m,
2
1H, PCym1), 2.48-1.23 (m, 32H, Cy, H4). 13C{1H} NMR (δ,
CDCl3, 20 °C): 160.9 (1C, CH3OC6H44), 158.6 (1C, CH3OC6H44′),
135.4 (1C, CH3OC6H41), 132.6 (d, J CP ) 5.4 Hz, 1C, CH3-
3
OC6H41′), 129.2 (2C, CH3OC6H42,6), 127.8 (2C, CH3OC6H42′,6′),
115.0 (2C, CH3OC6H43,5), 114.6 (2C, CH3OC6H43′,5′), 96.0 (1C,
C2), 90.4 (5C, Cp), 81.6 (1C, C3), 63.4 (1C, C4), 55.8, 55.6 (2C,
OCH3), 53.2 (d, 1J CP ) 55.7 Hz, 1C, PCym1), 41.8 (d, J CP ) 12.6
1
[Ru Cp *(dC(n -Bu )-η3-CHC(n -Bu )CHP Et3)]P F 6 (8b). This
complex has been prepared analogously to 8a with 1c (200
Hz, 1C, CH2), 35.3, 34.8, 33.7, 32.9, 32.7, 31.1, 30.7 (d, J CP
)
62.8 Hz, 1C, C1), 28.2, 28.0, 27.2, 26.6, 26.5, 26.4, 26.3, 26.1,

2920 Organometallics, Vol. 21, No. 14, 2002
Ru¨ba et al.
mg, 0.344 mmol) and 2 equiv of 1-hexyne (81.2 µL, 0.688 mmol)
as the starting materials. Yield: 212 mg (94%). Anal. Calcd
for C28H50F6P2Ru: C, 51.3; H, 7.63. Found: C, 51.3; H, 7.64.
2
1H NMR (δ, acetone-d6, 25 °C): 4.87 (s, 1H, H2), 3.89 (d, J HP
3
) 10.0 Hz, 1H, H4), 3.17 (m, 1H, H5b), 2.35 (t, J HH ) 8.1 Hz,
2H, H9), 2.12 (m, 1H, H5a), 1.85 (s, 15H, C5(CH3)5), 1.91, 1.72,
and 1.51 (m, 14H, H6, H7, H10, H11 + P(CH2CH3)3), 1.14 (dt,
3J HP ) 17.2 Hz, 3J HH ) 7.5 Hz, 9H, P(CH2CH3)3), 0.98 and 0.97
3
(both t, J HH ) 7.4 Hz, 6H, -CH3). 13C{1H} (δ, acetone-d6, 25
3
2
°C): 256.3 (d, J CP ) 6.0 Hz, C1), 106.7 (d, J CP ) 5.1 Hz, C3),
94.7 (s, C5(CH3)5), 84.4 (s, C2), 42.8 (s, C5), 38.6 (d, J CP ) 4.5
3
Hz, C9), 34.7 (s, C6), 31.4 (d, J CP ) 67.1 Hz, C4), 29.9 (s, C10),
1
23.5 and 23.6 (s, C7 and C11), 15.2 and 15.7 (s, P(CH2CH3)3),
14.1 and 14.2 (s, C8 and C12), 11.0 (s, C5(CH3)5), 6.4 (d, J CP
)
2
[Ru (η6-C5Me4CH2)(η4-CH2dC(CH2)3CdCHP Et3)]P F6 (9b).
A solution of 8b (150 mg, 0.254 mmol) in acetone (5 mL) was
stirred at room temperature for 18 h. The solvent was removed
under vacuum and the residue washed with petroleum ether
(2 × 5 mL) and dried. Slow recrystallization from a acetone/
petroleum ether (1:3) mixture gave orange crystals. Yield: 143
mg (95%). Anal. Calcd for C23H38F6P2Ru: C, 46.7; H, 6.47.
5.1 Hz, P(CH2CH3)3). 31P{1H} NMR (δ, acetone-d6, 25 °C): 43.8
(s). IR (Nujol, cm-1): 1605 (m, νCdC).
[Ru Cp *(dCH-η3-C(CH2)3CCHP Et3)]P F 6 (8c). A solution
of 1c (200 mg, 0.344 mmol) in acetone (5 mL) was treated with
1,6-heptadiyne (39.4 µL, 0.344 mmol). An immediate color
change from pale yellow to dark violet was observed. The
solvent was removed under vacuum and the residue washed
with petroleum ether (3 × 5 mL) and dried, obtaining a violet
solid. Yield: 191 mg (94%). Anal. Calcd for C23H38F6P2Ru: C,
46.70; H, 6.47. Found: C, 46.50; H, 6.47. 1H NMR (δ, acetone-
1
Found: C, 46.7; H, 6.47. H NMR (δ, acetone-d6, 25 °C): 4.83
and 4.67 (both s, 1H each, H2C), 3.12 (m, 1H, H7b), 2.92 (m, 1
H, H5b), 2.19-1.92 (m, 9H, H6b, H7a, H1 + P(CH2CH3)3), 1.86
(d, 1H, 2J HH ) 3.6 Hz, H4b), 1.82 (m, 1H, H5a), 1.75, 1.66, 1.61,
and 1.56 (all s, 3H each, C5(CH3)4), 1.47 (d, 1H, 2J HH ) 3.6 Hz,
2
d6, 0 °C): 11.71 (bs, 1H, H1), 4.29 (d, 1H, J HP ) 7.4 Hz, H4),
2.84 (m, 2H, CH2), 2.03 (m, 4H, CH2), 1.84 (s, 15H, C5(CH3)5),
3
3
H4a), 1.34 (m, 1H, H6a), 1.20 (dt, 9H, J HP ) 17.7 Hz, J HH
)
3
2
1.59 (m, 6H, P(CH2CH3)3), 1.07 (dt, 9H, J HP ) 17.3 Hz, J HH
) 7.9 Hz, P(CH2CH3)3). 13C{1H} NMR (δ, acetone-d6, 0 °C):
227.1 (d, 3J CP ) 6.9 Hz, C1), 114.7 (d, 2J CP ) 5.5 Hz, C3), 110.3
7.9 Hz, P(CH2CH3)3). 13C{1H} NMR (δ, acetone-d6, 25 °C):
102.0 (d, J CP ) 5.2 Hz, C2), 106.3, 104.0, 99.9, 99.7, and 98.1
2
(s, C5(CH3)4), 95.5 (s, C3), 51.8 (d, J CP ) 3.1 Hz, CH2), 34.4
3
3
(s, C2), 95.7 (s, C5(CH3)5), 33.8 (d, J CP ) 4.1 Hz, C7), 28.6 (d,
and 33.9 (both s, C5 and C7), 32.3 (s, C4), 22.3 (s, C6), 20.5 (d,
1J CP ) 68.6 Hz, C4), 28.1 and 25.0 (s, C5 and C6), 14.3 and 13.7
1J CP ) 64.1 Hz, C1), 17.3 and 17.8 (s, P(CH2CH3)3), 10.0, 9.7,
2
(s, P(CH2CH3)3), 10.9 (s, C5(CH3)5), 5.9 (d, J CP ) 5.5 Hz,
3
8.4, and 8.2 (s, C5(CH3)4), 6.5 (d, J HP ) 5.2 Hz, P(CH2CH3)3).
P(CH2CH3)3). 31P{1H} NMR (δ, acetone-d6, 0 °C): 43.1 (PEt3).
IR (Nujol, cm-1): 1642 (m, νCdC).
31P{1H} NMR (δ, acetone-d6, 25 °C): 43.6 (PEt3). IR (Nujol,
cm-1): 1709 and 1579 (m, νCdC).
X-r a y Str u ctu r e Deter m in a tion for 3, 4a , 5, 6a , a n d 9b.
Crystals of 3, 4a , 5, 6a , and 9b were obtained by diffusion of
Et2O into CH2Cl2 solutions. Crystal data and experimental
details are given in Table 1. X-ray data were collected on a
Siemens Smart CCD area detector diffractometer (graphite
monochromated Mo KR radiation, R ) 0.71073 Å, 0.3° ω scan
frames covering complete spheres of the reciprocal space.
Corrections for Lorentz and polarization effects, for crystal
decay, and for absorption were applied. The structures of 3,
4a , 5, and 6a were solved by direct methods, while the
structure of 9a was solved with the Patterson method using
in all cases the program SHELXS97.14 Structure refinement
on F2 was carried out with the program SHELXL97.15 All non-
hydrogen atoms were refined anisotropically. Most hydrogen
atoms were inserted in idealized positions and were refined
riding with the atoms to which they were bonded; allyl or diene
bound hydrogen atoms were freely refined in x, y, and z.
[R u (η6-C5Me4CH 2)(η4-CH (COOMe)dCH -C(COOMe)d
CHP Et3)]P F 6 (9a ). A solution of 8a (150 mg, 0.258 mmol) in
acetone (5 mL) was stirred at room temperature for 18 h. The
solvent was removed under vacuum and the residue washed
with petroleum ether (2 × 5 mL) and dried. Slow recrystalli-
zation from a acetone/petroleum ether (1:3) mixture gave
orange crystals. Yield: 144 mg (96%). Anal. Calcd for
Ack n ow led gm en t. Financial support by the “O¨ s-
terreichischer Akademischer Austauschdienst” (Ac-
ciones Integradas Project 8/2002) and the Ministerio de
Ciencia y Tecnolog´ıa (Acciones Integradas HU 2001-020)
is gratefully acknowledged.
C
24H38F6O4P2Ru: C, 44.00; H, 5.80. Found: C, 44.10; H, 5.80.
2
1H NMR (δ, acetone-d6, 25 °C): 5.98 (d, 1H, J HH ) 6.7 Hz,
H4), 5.05 and 4.75 (both s, 1H each, H2Cd), 3.88 and 3.61 (both
s, 3H each, COOCH3), 2.46 (d, 1H, J HP ) 3.1 Hz, H1), 2.25-
2
Su p p or tin g In for m a tion Ava ila ble: Listings of atomic
coordinates, anisotropic temperature factors, bond lengths and
angles, and least-squares planes for 3, 4a , 5, 6a , and 9b. This
material is available free of charge via the Internet at
http://pubs.acs.org.
2.10 (m, 7 H, H3 + P(CH2CH3)3), 1.68, 1.64, 1.48, and 1.41 (all
s, 3H each, C5(CH3)4), 1.25 (dt, 9H, 3J HP ) 17.6 Hz, 2J HH ) 7.7
Hz, P(CH2CH3)3). 13C{1H} NMR (δ, acetone-d6, 25 °C): 172.5
(s, COOCH3), 169.7 (d, 3J CP ) 3.4 Hz, COOCH3), 106.3, 104.0,
103.3, 100.8, and 80.9 (s, C5(CH3)4), 95.6 (s, C2), 90.4 (s, C4),
57.9 (s, CH2), 53.0 and 51.4 (s, COOCH3), 45.8 (s, C3), 25.9 (d,
1J CP ) 63.1 Hz, C1), 17.5 and 17.0 (s, P(CH2CH3)3), 9.1, 9.0,
OM020094G
(14) Sheldrick, G. M. SHELXS97: Program for the Solution of
Crystal Structures; University of Go¨ttingen: Germany, 1997.
(15) Sheldrick, G. M. SHELXL97: Program for Crystal Structure
Refinement; University of Go¨ttingen: Germany, 1997.
2
7.1, and 6.2 (s, C4(CH3)4), 6.3 (d, J CP ) 5.5 Hz, P(CH2CH3)3).
31P{1H} NMR (δ, acetone-d6, 25 °C): 42.6 (PEt3). IR (Nujol,
cm-1): 1715 (s, νCOOMe), 1587 (s, νCdC).