New acetylide migration and oxygen transfer reactions in ruthenium complexes containing an acetyl-substituted Cp ligand

Article abstract of DOI:10.1021/om010893j

Formation of [η⁵:η¹-C₅H₄C(CH₃) =C(Ph)C(O)](PPh₃)2Ru (3a) from the reaction of (η⁵-C₅H₄-COCH₃)(PPh₃) ₂RuCl (2a) with PhC≡CH proceeds via the vinylidene intermediate [(η⁵-C₅H₄-COCH₃)(PPh₃ )₂Ru=C=CHPh]Cl (4a). In this reaction the oxygen atom of the pendant acetyl group in the cyclopentadienyl ligand of 4a is transferred to C_α of the vinylidene ligand, and this transfer is accompanied by formation of a C=C bond, giving 3a. Treatment of 2a with LiC≡CPh affords (η⁵-C₅H₄C(CCPh)(OH)CH₃)(PPh ₃)₂RuCl (6a), and passing 6a through a column packed with alumina also gives 3a. The latter transformation involves a new migration of an acetylide group from exocyclic C_α of a substituted cyclopentadienyl ligand to the Ru center followed by the same oxygen transfer process. The metal acetylide (η⁵-C₅H₄COCH₃)(BINAP)RuC=CPh (5c), resulting from the same migration but with no oxygen transfer, is isolated when two PPh₃ ligands are replaced by BINAP. The structures of complexes 3a and 6b, a chirophos analogue of 6a, have been determined by X-ray diffraction analysis.

Full text of DOI:10.1021/om010893j

Organometallics 2002, 21, 1355-1361
1355
New Acetylid e Migr a tion a n d Oxygen Tr a n sfer Rea ction s
in Ru th en iu m Com p lexes Con ta in in g a n
Acetyl-Su bstitu ted Cp Liga n d
J en-Fuh Liu, Shou-Ling Huang, Ying-Chih Lin,* Yi-Hung Liu, and Yu Wang
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China
Received October 12, 2001
Formation of [η5:η1-C5H4C(CH3)dC(Ph)C(O)](PPh3)2Ru (3a ) from the reaction of (η5-C5H4-
COCH3)(PPh3)2RuCl (2a ) with PhCtCH proceeds via the vinylidene intermediate [(η5-C5H4-
COCH3)(PPh3)2RudCdCHPh]Cl (4a ). In this reaction the oxygen atom of the pendant acetyl
group in the cyclopentadienyl ligand of 4a is transferred to CR of the vinylidene ligand, and
this transfer is accompanied by formation of a CdC bond, giving 3a . Treatment of 2a with
LiCtCPh affords (η5-C5H4C(CCPh)(OH)CH3)(PPh3)2RuCl (6a ), and passing 6a through a
column packed with alumina also gives 3a . The latter transformation involves a new
migration of an acetylide group from exocyclic CR of a substituted cyclopentadienyl ligand
to the Ru center followed by the same oxygen transfer process. The metal acetylide (η5-
C5H4COCH3)(BINAP)RuCtCPh (5c), resulting from the same migration but with no oxygen
transfer, is isolated when two PPh3 ligands are replaced by BINAP. The structures of
complexes 3a and 6b, a chirophos analogue of 6a , have been determined by X-ray diffraction
analysis.
Sch em e 1
In tr od u ction
We have previously reported the deprotonation reac-
tion of (cyclopentadienyl)ruthenium vinylidene com-
plexes,1 generating a rare class of cyclopropenyl com-
plexes. The electrophilic CR of the vinylidene ligand facil-
itates cyclization via a facile nucleophilic addition of the
neighboring carbanion after deprotonation to afford the
product. It has been demonstrated that nucleophilic
addition of a hydroxyl group to CR of a vinylidene com-
plex provides access to an oxacarbene, and this has been
employed in the cycloisomerization transformation of
terminal alkynyl alcohol in efficient syntheses of anti-
viral nucleosides, polycyclic ethers, and oligosaccha-
rides.2 Since the chemistry of substituted π-bonded
cyclopentadienyl3 organometallic complexes continues
to be of great interest due to their potential importance
in the development of carbon-carbon bond formations4
and their uses in the syntheses of unsaturated organic
species and organometallic polymers,5 we prepared an
(acetylcyclopentadienyl)ruthenium chloride complex6
and carried out the reaction of this chloride with phen-
ylacetylene in order to get a similar cyclopropenyl com-
plex. Surprisingly, in this reaction a new type of oxygen
transfer process is observed. Herein we report this new
reaction where the oxygen atom transfers from the
pendant acetyl group of the acetylcyclopentadienyl lig-
and to the vinylidene ligand. Such a transfer is followed
by a carbon-carbon bond formation between the vi-
nylidene and the pendant unit of the acetylcyclopenta-
dienyl ligands to yield a new metal acyl complex. Also
reported is a novel acetylide migration reaction found
during our investigation into the mechanism of the
oxygen transfer reaction.
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10.1021/om010893j CCC: $22.00 © 2002 American Chemical Society
Publication on Web 02/26/2002

1356 Organometallics, Vol. 21, No. 7, 2002
Liu et al.
12.5 Hz, indicating the presence of a metal acyl carbon.9
This 13C resonance shifts significantly downfield from
that (δ 197.1) of the acetyl unit of 2a . The triplet pattern
resulting from coupling with two phosphine atoms is
consistent with the presence of a metal acyl group. Two
resonances at δ 168.1 and 142.3 are assigned to two
olefinic carbon atoms of the pendant chain. The 1H NMR
spectrum of 3a displays a singlet resonance at δ 2.12,
assignable to the methyl group. From an HMBC (het-
eronuclear multiple bond connectivity) 2D NMR spec-
trum,10 long-range C-H couplings of this methyl proton
Sch em e 2
1
are revealed by three cross-peaks of this H resonance,
showing correlation with the 13C resonances at δ 168.1,
142.3, and 247.7 assignable to two olefinic carbons and
the acyl carbon, respectively. These data reveal that the
methyl group remains attached in the substituted Cp
ligand and is also bonded to the added portion derived
from phenylacetylene. In the 31P NMR spectrum, the
singlet resonance at δ 49.13 is assigned to the PPh3
ligand. Two IR absorption peaks at 1772 and 1681 cm-1
are assigned to the CdO and CdC stretching, respec-
tively. We have carried out reactions of phenylacetylene
with the similar complexes 2b, 2c, and 2d , yielding 3b
(81%), 3c (72%), and 3d (65%), respectively. These
reactions all give complexes of the same type. Charac-
teristic 13C resonances at δ 250 ( 8 are all observed for
these complexes. All 31P NMR resonances of 3 shift
toward a downfield region relative to those of their
corresponding chloride complexes 2.
Resu lts a n d Discu ssion
Spectroscopic data for 3 mentioned above are not
sufficient for making a full assignment of the structure.
Attempts were thus made to search for reaction inter-
mediates. We noticed that, during the course of the
reaction of 2a with PhCtCH, the color of the mixture
changed from deep red to orange and then to yellow. A
reaction, carried out in an oil bath at 50 °C, was thus
stopped in 3 h, while the color of the mixture was
orange. From the mixture, the intermediate 4a , showing
a singlet 31P NMR resonance at δ 42.87, was observed
along with 3a in a 1:1 ratio. This intermediate trans-
formed to 3a quantitatively at the reflux temperature
of MeOH. Attempted column chromatographic separa-
tion of the mixture by using a silica gel packed column
caused decomposition of the intermediate and gave only
3a . The structure of the intermediate was thus deduced
spectroscopically. The 31P NMR resonance of this inter-
mediate at δ 42.87 is nearly that of a Ru vinylidene
complex.11 The 1H NMR resonance at δ 4.74 also
resembles that of a vinylidene terminal proton.12 It is
known that metal acetylide can be readily prepared
from deprotonation of a metal vinylidene containing a
terminal proton. We therefore carried out the reaction
of 2a with phenylacetylene in the presence of sodium
methoxide. This reaction gave 3a and the expected
acetylide complex (η5-C5H4COCH3)(PPh3)2RuCtCPh
(5a ) in a 1:2 ratio. Complex 5a is characterized by its
31P NMR spectrum, showing a singlet resonance at δ
51.85 for phosphine ligands. The FAB mass spectrum
displays the parent peak at m/z 692.3, corresponding
P r ep a r a tion of Acetylcyclop en ta d ien yl Com -
p lexes. The literature method7 for the preparation of a
ruthenium chloride complex with an acetylcyclopenta-
dienyl ligand is modified to give the desired product in
a higher yield. Hydrated ruthenium trichloride, RuCl3‚
xH2O, in ethanol is added to a heated solution of acetyl-
cyclopentadiene8 and PPh3 in ethanol/ether (4:1), and
the solution turns red in about 2 h. The deep red product
obtained from this solution is identified as (η5-C5H4-
COCH3)(PPh3)2RuCl (2a ). Complex 2a is soluble in
CHCl3, CH2Cl2, and acetone and insoluble in CH3OH,
ether, and hexane. 1H and 31P NMR data of 2a are
consistent with the literature values.7 In addition, in
the 13C NMR spectrum of 2a the resonance attributable
to the carbonyl carbon appears at δ 197.1. Similar
complexes (η5-C5H4COCH3)(L-L)RuCl (L-L ) (2S,3S)-
(-)-Ph2PCHMeCHMePPh2, 2b; L-L ) (R)-(+)-BINAP,
2c; L-L ) dppe, 2d ) are prepared from the reaction of
2a with the corresponding bidentate phosphines under
various reaction conditions. The 13C NMR resonances
of the acyl carbon in these complexes all appear at δ
197 ( 1. The chemical shifts of two 31P NMR resonances
of the bidentate chiral phosphine ligands in 2b (δ 81.11,
68.85) and 2c (δ 49.21, 39.55) are significantly different.
Rea ction of P h en yla cetylen e w ith 2. The reaction
of 2a with PhCtCH in MeOH at 64 °C for 4 h proceeds
via a somewhat complicated and unprecedented process
to afford [η5:η1-C5H4C(CH3)dC(Ph)C(O)](PPh3)2Ru (3a )
in 86% yield (see Scheme 2). The 13C NMR spectrum of
3a displays a triplet resonance at δ 247.7 with J C-P
)
(9) Lehmkuhl, H.; Schwickardi, R.; Mehler, G.; Krueger, C.; God-
dard, R. Z. Anorg. Allg. Chem. 1991, 606, 141.
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179.
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Soc. 1980, 102, 1196.
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(11) Lomprey, J . R.; Selegue, J . P. Organometallics 1993, 12, 616.
(12) (a) Trost, B. M.; Kulawiec, R. J . J . Am. Chem. Soc. 1992, 114,
5579. (b) Bruce, M. I.; Hinterding, P.; Tiekink, E. R. T. J . Organomet.
Chem. 1993, 450, 209.

Ru Complexes with an Acetyl-Substituted Cp Ligand
Organometallics, Vol. 21, No. 7, 2002 1357
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of [η5:η1-C5H4C(CH3)dC(P h )C(O)](P P h 3)2Ru
(3a )
Ru-P1
C1-O1
C2-C3
C3-C4
2.3111(9)
1.226(5)
1.339(6)
1.506(6)
Ru-C1
C1-C2
C2-C5
C3-C9
2.009(5)
1.556(6)
1.488(6)
1.495(6)
P1-Ru-P1A
Ru-C1-C2
C2-C1-O1
C1-C2-C5
C2-C3-C4
C4-C3-C9
104.02(4)
112.7(3)
115.5(4)
116.4(4)
126.6(4)
117.2(4)
P1-Ru-C1
Ru-C1-O1
C1-C2-C3
C3-C2-C5
C2-C3-C9
C3-C9-C10
92.59(8)
131.8(3)
118.0(4)
125.6(4)
116.2(4)
125.3(2)
about the ruthenium metal center consists of the
π-bound Cp ring with its pendant chain bound also to
the metal through the acyl unit and two triphenylphos-
phine ligands. The Ru-C1 distance of 2.009(5) Å is a
normal Ru-C single-bond distance for a metal acyl
group. The C2-C3 bond length of 1.339(6) Å is typical
of a CdC double bond.
F igu r e 1. ORTEP drawing of [η5:η1-C5H4C(CH3)dC(Ph)C-
(O)](PPh3)2Ru (3a ), with thermal ellipsoids shown at the
30% probability level.
Mech a n ism of Oxygen Tr a n sfer . Formation of 3a
can be accounted for by the mechanism depicted in
Scheme 3. The reaction of 2a with phenylacetylene first
yields the cationic vinylidene complex 4a with chloride
as its counteranion. It is well-known that CR of a
vinylidene ligand is susceptible to nucleophilic attack,13
particularly by a nitrogen or an oxygen donor, to give a
Fischer type carbene complex. This is exceptionally
facile when the nucleophilic attack is assisted by an
intramolecular chelation. In our system, the oxygen
atom of the pendant acetyl unit in the cyclopentadienyl
ligand nearby serves as a nucleophile, giving A (see
Scheme 3). This cation is stabilized not only by delo-
calizing the cationic charge in the Cp substituent but
also by a significant contribution of the electron-rich
ruthenium bisphosphine group via η6-complexation and
possibly by a neighboring group participation of the
vinyl group. Electron donation from the neighboring
vinyl group to the carbenium center causes carbon-
carbon bond formation. Thus, the nucleophilic attack
is followed by formation of a C-C bond and subsequent
deprotonation generates the product 3a . The presence
of NaOMe causes deprotonation of the vinylidene in-
termediate 4a to occur to give the acetylide complex 5a .
An oxygen atom transfer from niobium ketene to iso-
cyanide or nitrile, yielding a niobium vinylidene com-
plex, has been reported.14
Sch em e 3
to cleavage of the acetylide and the acetyl fragments.
On the basis of these data, it is reasonable to assume
that the initial step of the reaction of 2 with HCtCPh,
in the presence of MeONa, possibly proceeds via addi-
tion of phenylacetylene to the Ru metal center followed
by deprotonation to give 5a . We therefore believe that
the intermediate isolated in the absence of sodium
methoxide is [(η5-C5H4COCH3)(PPh3)2RudCdCHPh]Cl
(4a ), shown in Scheme 3. In the presence of acid, 5a
readily turned to 3a , possibly also via 4a .
Acetylid e Ad d ition to th e Acetyl Gr ou p of th e
Cp Liga n d . In an attempt to prepare the acetylide
complex 5a , we carried out the reaction of 2a with 3
equiv of LiCtCPh in CH2Cl2. Surprisingly, the reaction
did not give the expected product but instead generated
(η5-C5H4C(CCPh)(OH)CH3)(PPh3)2RuCl (6a ) in moder-
ate yield (see Scheme 2) and, interestingly, the reaction
in the presence of air gave a higher yield than that in
the absence of air. If the reaction in CH2Cl2 was carried
out under nitrogen, 6a and many unidentified products
To establish the solid-state structure of 3a , an X-ray
diffraction study was carried out on a single crystal of
3a recrystallized from n-hexane. This complex crystal-
lizes in the orthorhombic space group Pnma with four
molecules in a unit cell. The molecule possesses a mirror
plane. An ORTEP drawing is shown in Figure 1;
symmetry-generated atoms are indicated with the suffix
A, and selected bond distances and angles are listed in
Table 1. The molecule of 3a lies on a mirror plane with
a distorted-tetrahedral metal center. The environment
(13) (a) Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. Orga-
nometallics 1998, 17, 827. (b) Bianchini, C.; Casares, J . A.; Peruzzini,
M.; Romerosa, A.; Zanobini, F. J . Am. Chem. Soc. 1996, 118, 4585. (c)
Bianchini, C.; Peruzzini, M.; Romerosa, A.; Zanobini, F. Organome-
tallics 1995, 14, 3152. (d) Barrett, A. G. M.; Carpenter, N. E.
Organometallics 1987, 6, 2249. (e) Quzzine, K.; Le Bozec, H.; Dixneuf,
P. H. J . Organomet. Chem. 1986, 317, C25. (f) Nombel, P.; Lugan, N.;
Mathieu, R. J . Organomet. Chem. 1995, 503, C22.
(14) Fermin, M. C.; Bruno, J . W. J . Am. Chem. Soc. 1993, 115, 7511.

1358 Organometallics, Vol. 21, No. 7, 2002
Liu et al.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d
An gles (d eg) of
[(η5-C5H4C(CCP h )(OH)CH3)](Ch ir a p h os)Ru Cl (6b)
Ru-P1
Ru-P2
C1-C2
C1-O1
2.2899(12)
2.3392(13)
1.573(9)
Ru-C1
C1-C11
C1-C3
C3-C4
2.4680(11)
1.529(9)
1.508(9)
1.211(9)
1.445(7)
P1-Ru-P2
P1-Ru-Cl
P2-Ru-Cl
C11-C1-C2
O1-C1-C2
O1-C1-C3
82.86(4)
86.21(4)
95.12(4)
109.1(6)
105.4(5)
110.8(5)
C3-C1-C2
110.0(5)
175.4(7)
178.8(6)
125.8(5)
125.7(5)
108.3(5)
C1-C3-C4
C3-C4-C5
C1-C11-C15
C1-C11-C12
C15-C11-C12
activated alumina or when a solution of 6a was stirred
in the presence of MeONa or CF3COOH, the same
transformation occurred, but with much lower yield, and
several intractable products were also observed. A new
acetylide migration followed by the oxygen transfer
mentioned above accounts for the transformation of 6a
to 3a . The phenylacetylide group migrates from the
exocyclic CR of the substituted Cp ligand to the Ru metal
center. This is followed by formation of a vinylidene
complex via protonation, and then the oxygen transfer
mentioned above takes place to give the final product
3a . The acetylide migration process could be assisted
by dissociation of the chloride ligand in methanol. The
presence of the electron-rich CtC triple bond of the
propargylic group could provide yet another stabilization
effect via coordination to the metal center to give the
final product. Treatment of 6c with alumina resulted
in the formation of 5c. In this system, the vinylidene
complex 4c could be prepared by protonation of 5c with
CF3COOH. Complex 4c decomposed to several uniden-
tified products at room temperature. The oxygen trans-
fer product was observed only as a minor product.
Interestingly, when 6d was subjected to chromatog-
raphy on an alumina-packed column, dehydration was
observed, yielding [η5-C5H4C(dCH2)CCPh](dppe)RuCl
(7d ), which was identified by spectroscopic methods.
Two vinylic protons give two singlet resonances at δ 5.46
and 5.59 in the 1H NMR spectrum. Both correlate to
the 13C resonance at δ 118.3 in the 2D NMR HMQC
spectrum and to 13C resonances at δ 94.6 (quaternary
carbon on Cp) and δ 88.9 and 89.2 (two acetylene
carbons) in the 2D NMR HMBC spectrum. The 31P NMR
spectrum displays a singlet resonance at δ 79.66,
indicating the lack of a stereogenic center. For the
ferrocenyl carbocation, it is known that nucleophilic
addition reactions often proceed in competition with
deprotonation.16 The reaction of 7d with CF3COOH gave
a carbenium ion product (8d ) showing a two-doublet
pattern at δ 86.46 and 73.93 (J P-P ) 24.1 Hz) in the
31P NMR spectrum. Protonation presumably occurs at
the exocyclic Câ,17 and the restricted rotation of the
exocyclic group originating from the neighboring group
participation of the metal satisfactorily accounts for the
planar chirality. Deprotonation of this unstable carbe-
nium product, which does not undergo acetylide migra-
tion, in the presence of some weak nucleophiles readily
gives back 7d . Reversed migration of an acetylide group
F igu r e 2. ORTEP drawing of [η5-C5H4C(OH)(CCPh)CH3]-
(Chiraphos)RuCl (6b), with thermal ellipsoids shown at the
30% probability level.
were obtained. This reaction carried out in THF also
gave a mixture of products. Nucleophilic addition takes
place at the acetyl group, forming a propargylic alcohol
group at the Cp ligand. Triphenylphosphine oxide was
also observed as a byproduct in this reaction, and 6a
was purified by recrystallization from a mixture of
n-hexane and CH2Cl2. Complex 6a in solution is un-
stable and decomposes to give OPPh3 as the only
identifiable product at room temperature, but a solid
sample could be stored for 2 days at room temperature.
In the 31P NMR spectrum of 6a two doublet resonances
at δ 39.0 and 38.2 with J P-P ) 41.4 Hz indicates the
presence of a stereogenic center in the complex. The
hydroxy proton appears as a broad singlet resonance
at δ 6.27 in the 1H NMR spectrum, and this proton
readily exchanges with deuterium in the presence of
D2O. These spectroscopic data as well as a crystal
structure determination of a similar complex described
below firmly establish the structure of the nucleophilic
addition product. Complexes 6b, 6c, and 6d were
similarly prepared from the reaction of LiCtCPh with
2b, 2c, and 2d , respectively, in high yields. For the
formation of 6b and 6c from 2b and 2c, the diastereo-
selectivities are 32% and 24%, respectively. The lower
diastereoselectivity in this system relative to that
observed in the chromium tricarbonyl system15 is not
unexpected, since the chiral phosphine ligand is rela-
tively farther away from the reactive center.
Single crystals of 6b were obtained by recrystalliza-
tion from n-hexane/acetone, and the molecular structure
was determined by an X-ray diffraction analysis. An
ORTEP drawing is shown in Figure 2, and selected bond
distances and angles are listed in Table 2. The environ-
ment about the ruthenium metal center consists of a
π-bound Cp ring, a chlorine atom, and a chirophos
ligand. The acetylide group is bonded to the exocyclic
CR of the Cp ligand. The pendant chain is in line with
the less hindered Cl ligand. The Ru-Cl distance of
2.468(1) Å is a normal Ru-Cl single-bond distance. The
C3-C4 bond length of 1.211(9) Å is typical of a CtC
triple bond.
A New Acetylid e Migr a tion . Transformation of 6a
to 3a readily occurred in methanol (see Scheme 2).
When 6a was passed through a column packed with
(16) Bunton, C. A.; Crawford, W.; Watts, W. E. Tetrahedron Lett.
1977, 3755.
(17) (a) Pittman, C. U., J r.; Olah, G. A. J . Am. Chem. Soc. 1965, 87,
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Am. Chem. Soc. 1974, 96, 5855.
(15) Netz, A.; Polborn, K.; Mu¨ller, T. J . J . J . Am. Chem. Soc. 2001,
123, 3441.

Ru Complexes with an Acetyl-Substituted Cp Ligand
Organometallics, Vol. 21, No. 7, 2002 1359
ligands followed the procedure given in the literature. For
example, complex 2b was obtained from a thermal reaction of
2a with Chiraphos in benzene for 4 h and was purified by
recrystallization from n-hexane/CH2Cl2 (10:1) in 95% yield.
Spectroscopic data for 2b (Chiraphos) are as follows. 1H NMR
(CDCl3): δ 8.03-7.00 (m, 20H, Ph), 5.30 (br, 1H, Cp), 5.04 (br,
1H, Cp), 4.77 (br, 1H, Cp), 2.99 (br, 1H, Cp), 2.87-2.79 (m,
1H, PCH(CH3)), 2.05-1.94 (m, 1H, PCH(CH3)), 1.69 (s, 3H,
CH3), 1.06-1.00 (m, 3H, PCH(CH3)), 0.91-0.85 (m, 3H, PCH-
(CH3)). 13C NMR (CDCl3): δ 196.9 (s, CdO), 140.3-127.8 (m,
Ph), 97.6, 88.2, 83.1, 80.7, 75.8 (s, Cp), 38.2-37.6 (m, PCH-
(CH3)), 35.7-35.1 (m, PCH(CH3)), 28.5 (s, CH3), 16.3-15.9 (m,
PCH(CH3)), 15.2-14.9 (m, PCH(CH3)). 31P NMR (CDCl3): δ
81.11 (d, J P-P ) 42.5 Hz), 68.85 (d, J P-P ) 42.5 Hz). MS
from an Fe metal to a cyclopentadienyl ligand has been
reported recently.18 In our system the migration is from
the exocyclic CR of a substituted group on the Cp ligand
to the metal.
Con clu d in g Rem a r k s. A new oxygen transfer reac-
tion from an acetyl group on a substituted cyclopenta-
dienyl ligand to a coordinated vinylidene ligand was
observed in the reaction of 2 with phenylacetylene,
giving 3. The reaction proceeds via addition of phenyl-
acetylene to the ruthenium metal center to yield the
vinylidene ligand. The proximity of the acetyl group and
the vinylidene ligand and the electrophilicity of CR of
the vinylidene ligand promote such an oxygen transfer
process and facilitate CdC bond formation. In the
presence of MeOH, complex 6a undergoes a new acetyl-
ide migration from exocyclic CR of the substituted Cp
ligand to the Ru metal center to yield 3a . The migration
is possibly assisted by dissociation of the chloride ligand
in 6a and is followed by formation of a similar vi-
nylidene complex in which oxygen transfer takes place
to give the final product 3a . Possible applications of such
a reaction in synthesizing new organometallic complexes
are currently under investigation.
(FAB): m/z 670.1 (M+), 635.1 (M+ - Cl). Anal. Calcd for C35H35
-
OP2RuCl: C, 62.73; H, 5.26, Found: C, 62.49; H, 4.97.
Complex 2c was obtained similarly from a thermal reaction
of 2a with BINAP in toluene for 10 days in 90% yield.
1
Spectroscopic data for 2c are as follows. H NMR (CDCl3): δ
7.90-6.15 (m, 32H, Ph), 5.04 (br, 1H, Cp), 4.47 (br, 1H, Cp),
4.22 (br, 1H, Cp), 4.12 (br, 1H, Cp), 2.17 (s, 3H, CH3). 13C NMR
(CDCl3): δ 197.3 (s, CdO), 143.1-125.4 (m, Ph), 95.3, 89.8,
84.2, 81.6, 77.7 (s, Cp), 29.5 (s, CH3). 31P NMR (CDCl3): δ 49.21
(d, J P-P ) 54.5 Hz), 39.55 (d, J P-P ) 54.5 Hz). MS (FAB): m/z
866.2 (M+), 831.3 (M+ - Cl). Anal. Calcd for C51H39OP2RuCl:
C, 70.70; H, 4.54, Found: C, 70.54; H, 4.70.
P r ep a r a tion of (η5-CH3COC5H4)(d p p e)Ru Cl (2d ).20
A
Exp er im en ta l Section
solution of 0.1 g of Ru(η5-CH3COC5H4)Cl(PPh3)2 (2a ; 0.13
mmol) and 0.052 g (0.13 mmol) of dppe (1,2-bis(diphenylphos-
phino)ethane) in toluene (20 mL) was heated to reflux for 6 h.
The volume was reduced to 5 mL, and 20 mL of light petroleum
ether was added. The faint yellow precipitates were filtered
off, and the filtrate was stored at -5 °C overnight to give the
product as orange crystals. Spectroscopic data for 2d are as
follows. 1H NMR (CDCl3): δ 7.70-7.10 (m, 20H, Ph), 5.29 (br,
2H, Cp), 4.13 (br, 2H, Cp), 2.72-2.29 (m, 4H, PCH2CH2P), 1.94
(s, 3H, CH3). 13C NMR (CDCl3): δ 196.4 (s, CdO), 139.9-127.0
(m, Ph), 88.4, 88.0, 66.2 (s, Cp), 28.1 (s, CH3), 26.7 (t,
PCH2CH2P, J C-P ) 22.4 Hz). 31P NMR (CDCl3): δ 78.86 (s).
MS (FAB): m/z 642.1 (M+), 607.1 (M+ - Cl). Anal. Calcd for
Gen er a l P r oced u r es. Unless mentioned otherwise, all
manipulations were performed under nitrogen using vacuum-
line, drybox, and standard Schlenk techniques. CH2Cl2 was
distilled from CaH2, and diethyl ether and THF were distilled
from Na/benzophenone. All other solvents and reagents were
of reagent grade and were used as received. NMR spectra were
recorded on Bruker AM-300WB and DMX-500 spectrometers
at room temperature (unless stated otherwise). Chemical shifts
are given in δ and referenced to TMS. FAB mass spectra were
recorded on a J EOL SX-102A spectrometer. Αcetylcyclopen-
tadienide was prepared according to the methods reported in
the literature.19 RuCl3‚xH2O was purchased from Strem Chemi-
cals. Elemental analyses and X-ray diffraction studies were
carried out at the Regional Center of Analytical Instrument
located at the National Taiwan University.
C
33H31OP2RuCl: C, 61.72; H, 4.87. Found: C, 61.74; H, 4.89.
P r epar ation of [η5η1-C5H4C(CH3)dC(P h )C(O)](P P h 3)2Ru
(3a ). To a solution of 2a (0.25 g, 0.326 mmol) in MeOH (50
mL) was added HCtCPh (360 µL, 3.25 mmol). The deep red
solution was heated to reflux (64 °C) for 4 h. The solution first
turned to orange and finally to yellow and, after being cooled,
was concentrated to ca. 10 mL; it was then slowly added to 70
mL of a stirred solution of ether. The yellow precipitate thus
formed was filtered off and washed with ether. The yellow
product was recrystallized from CH2Cl2/ether (1:10) and
identified as complex 3a (0.23 g, 86%). Spectroscopic data for
P r ep a r a tion of (η5-C5H4COCH3)(P P h 3)2Ru Cl (2a ). A
solution of sodium acetylcyclopentadienide (18.0 g) in HCl
aqueous solution (1.0 N, 500 mL) was stirred for 30 min. The
acetylcyclopentadiene was extracted with 4 × 25 mL of diethyl
ether and dried over MgSO4, and the volume of the ethereal
solution was reduced to ca. 10 mL. PPh3 (8.0 g, 30.5 mmol)
and 40 mL of absolute ethanol were added to the ethereal
solution, and the mixture was refluxed for 10 min; subse-
quently RuCl3‚xH2O (2.4 g, ca. 11.6 mmol) in 20 mL of absolute
ethanol was added to the boiling solution by syringe. The
mixture was heated to reflux for another 2 h; the red
precipitates thus formed were filtered off and washed with
ethanol and n-hexane (5.1 g, 57.2%). The product can be
recrystallized from CH2Cl2/n-hexane. Spectroscopic data for 2a
3a are as follows. IR (cm-1, CH2Cl2): 1772 (s, νCdO), 1681 (w,
1
ν
CdC). H NMR (CDCl3): δ 7.36-7.02 (m, 35H, Ph), 4.67 (br,
2H, Cp), 3.92 (br, 2H, Cp), 2.12 (s, 3H, CH3). 13C NMR
(CDCl3): δ 247.7 (t, J C-P ) 12.5 Hz, CdO), 168.1 (s, COCPh),
142.3 (s, CCH3), 140.7-124.7 (m, Ph), 126.3, 94.4, 83.3 (s, Cp),
19.3 (s, CH3). 31P NMR (CDCl3): δ 49.13 (s). MS (FAB): m/z
834.4 (M+), 572.2 (M+ - PPh3), 543.2 (M+ - PPh3, CO), 467.1
(M+ - PPh3, CO, Ph). Anal. Calcd for C51H42OP2Ru: C, 73.45;
H, 5.08. Found: C, 73.67; H, 4.96.
are as follows. IR (CH2Cl2): ν(CdO) 1663 cm-1 1H NMR
.
(CDCl3): δ 7.44-7.07 (m, 30H, Ph), 5.09 (br, 2H, Cp), 3.60 (br,
2H, Cp), 2.19 (s, 3H, CH3). 13C NMR (CDCl3): δ 197.1 (s,
CdO), 137.5-127.4 (m, Ph), 88.3 (s, Cp), 86.4 (s, Cp), 79.0 (s,
Cp), 29.3 (s, CH3). 31P NMR (CDCl3): δ 37.96 (s). FAB mass:
m/z 768.2 (M+), 733.2 (M+ - Cl), 471.0 (M+ - PPh3,Cl). Anal.
Calcd for C43H37OP2RuCl: C, 67.23; H, 4.86, Found: C, 67.40;
H, 4.72.
P r ep a r a tion of [η5η1-C5H4C(CH3)dC(P h )C(O)](Ch ir a -
p h os)Ru (3b). To a solution of 2b (100 mg, 0.15 mmol) in
anhydrous MeOH (20 mL) was added phenylacetylene (50 µL,
0.45 mmol), and the mixture was heated to reflux for 3 h. Then
the yellow solution was evaporated to dryness, and the residue
was recrystallized from CH2Cl2/n-hexane to give a yellow
powder identified as 3b (89 mg, 81% yield). Spectroscopic data
are as follows. 1H NMR (CDCl3): δ 7.57-6.49 (m, 25H, Ph),
P r ep a r a tion of 2b, 2c, a n d 2d . Preparation of 2b, 2c, and
2d from the reactions of 2a with corresponding free phosphine
(18) Liu, L. K.; Chang, K. Y.; Wen, Y. S. J . Chem. Soc., Dalton Trans.
1998, 1, 741.
(19) Rogers, R. D.; Atwood, J . L.; Rausch, M. D.; Macomber, D. W.;
Hart, W. P. J . Organomet. Chem. 1982, 238, 79.
(20) Alonso, A. G.; Revento´s, L. B. J . Organomet. Chem. 1988, 338,
249.

1360 Organometallics, Vol. 21, No. 7, 2002
Liu et al.
5.61 (br, 1H, Cp), 5.46 (br, 1H, Cp), 4.76 (br, 1H, Cp), 4.64 (br,
1H, Cp), 3.62-3.40 (m, 1H, PCH(CH3)), 2.15-1.99 (m, 1H,
PCH(CH3)), 1.91 (s, 3H, CH3), 1.36-1.28 (m, 3H, PCH(CH3)),
0.93-0.88 (m, 3H, PCH(CH3)). 13C NMR (CDCl3): δ 257.6 (dd,
J C-P ) 16.1, 11.7 Hz, CdO), 153.0 (s, COCPh), 143.0 (s, CCH3),
138.2-124.7 (m, Ph), 95.2, 92.5, 91.6, 86.6, 67.8 (s, Cp), 41.5-
40.9 (m, PCH(CH3)), 34.1-33.5 (m, PCH(CH3)), 27.4 (s, CH3),
15.3-14.9 (m, PCH(CH3)). 31P NMR (CDCl3): δ 93.69 (d, J P-P
µL, 0.39 mmol in 1 M THF). The reaction mixture was stirred
at room temperature for 30 min. Then the solvent was removed
under vacuum. The residue was extracted with 1 mL of
CH2Cl2, and n-hexane (2 mL) was added to remove the salt
after filtration. Then the solvent was removed under vacuum
and the residue recrystallized in two stages from dichlo-
romethane/n-hexane to give red crystals of 6a (67 mg, 60%
yield); OPPh3 (11 mg, 30% yield) was obtained as a byproduct.
Spectroscopic data of 6a are as follows. 1H NMR (CDCl3): δ
7.69-6.97 (m, 35H, Ph), 6.27 (br, 1H, OH), 4.31 (br, 1H, Cp),
4.08 (br, 1H, Cp), 3.73 (br, 1H, Cp), 3.32 (br, 1H, Cp), 1.79 (s,
3H, CH3). 13C NMR (CDCl3): δ 138.1-123.4 (m, Ph), 121.1
(chiral carbon), 92.8 (s, CtCPh), 84.2 (s, CtCPh), 73.8, 77.6,
72.8, 77.2, 67.0 (s, Cp), 33.8 (s, CH3). 31P NMR (CDCl3): δ 39.01
(d, J P-P ) 41.4 Hz), 38.20 (d, J P-P ) 41.4 Hz). MS (FAB): m/z
870.1 (M+), 834.2 (M+ - Cl), 733.2 (M+ - Cl, CCPh). A
satisfactory elemental analysis was not obtained due to the
instability of the complex. The same reaction in THF or in
CH2Cl2 under nitrogen gave a complicated mixture of products.
Preparation of 6b was similarly carried out using the same
procedure. A mixture containing diastereomers of 6b was
obtained after purification. No attempt was made to separate
these diastereomers. Spectroscopic data for 6b (chiraphos) are
as follows. Major product: 1H NMR (CDCl3) δ 8.05-7.04 (m,
25H, Ph), 5.64 (br, 1H, OH), 5.15 (br, 1H, Cp), 5.07 (br, 1H,
Cp), 4.58 (br, 1H, Cp), 4.23 (br, 1H, Cp), 2.63-2.50 (m, 1H,
PCH(CH3)), 2.06-1.95 (m, 1H, PCH(CH3)), 1.71 (s, 3H, CH3),
1.03-0.94 (m, 3H, PCH(CH3)), 0.87-0.82 (m, 3H, PCH(CH3));
13C NMR (CDCl3) δ 136.5-127.1 (m, Ph), 118.4 (s, chiral
carbon), 92.8 (s, CtCPh), 82.8 (s, CtCPh), 81.8, 81.3, 80.8,
72.3, 67.0 (s, Cp), 37.7-36.2 (m, PCH(CH3)), 34.1 (s, CH3),
15.5-14.1 (m, PCH(CH3)); 31P NMR (CDCl3) δ 85.13 (d, J P-P
) 40.6 Hz), 64.96 (d, J P-P ) 40.6 Hz). Minor product: 1H NMR
(CDCl3) δ 8.05-7.04 (m, 25H, Ph), 7.14 (br, 1H, OH), 4.70 (br,
1H, Cp), 3.58 (br, 1H, Cp), 3.18 (br, 1H, Cp), 2.58 (br, 1H, Cp),
2.63-2.50 (m, 1H, PCH(CH3)), 2.06-1.95 (m, 1H, PCH(CH3)),
1.80 (s, 3H, CH3), 1.03-0.94 (m, 3H, PCH(CH3)), 0.87-0.82
(m, 3H, PCH(CH3)); 13C NMR (CDCl3) δ 136.5-127.1 (m, Ph),
118.3 (s, chiral carbon), 93.0 (s, CtCPh), 83.0 (s, CtCPh), 75.9,
74.6, 72.2, 67.5, 66.6 (s, Cp), 37.7-36.2 (m, PCH(CH3)), 31.5
(s, CH3), 15.5-14.1 (m, PCH(CH3)); 31P NMR (CDCl3) δ 84.30
(d, J P-P ) 42.7 Hz), 65.80 (d, J P-P ) 42.7 Hz).
) 36.5 Hz), 91.32 (d, J P-P ) 36.5 Hz). Anal. Calcd for C43H40
-
OP2Ru: C, 70.19; H, 5.48. Found: C, 70.41; H, 5.79.
P r ep a r a t ion of [η5η1-C5H 4C(CH 3)dC(P h )C(O)](R-BI-
NAP )Ru (3c). To a suspension of 2c (100 mg, 0.12 mmol) in
anhydrous MeOH (20 mL) was added phenylacetylene (39 µL,
0.36 mmol). The orange solution was heated to reflux for 5 h
and subsequently cooled to room temperature. The solvent was
removed under vacuum and the residue recrystallized from
CH2Cl2/n-hexane to give 3c as a microcrystalline yellow solid
(yield: 81 mg, 72%). Spectroscopic data for 3c are as follows.
1H NMR (CDCl3): δ 7.66-6.09 (m, 37H, Ph), 5.00, 4.89, 4.37,
3.63 (br, 4H, Cp), 1.96 (s, 3H, CH3). 13C NMR (CDCl3): δ 245.7
(dd, J C-P ) 10.2, 6.4 Hz, CdO), 168.3 (s, COCPh), 145.6 (s,
CCH3), 145.1-127.0 (m, Ph), 94.1, 90.0, 89.0, 87.2, 84.5 (s, Cp),
19.6 (s, CH3). 31P NMR (CDCl3): δ 63.36 (d, J P-P ) 47.5 Hz),
56.76 (d, J P-P ) 47.5 Hz). MS (FAB): m/z 932.3 (M+). Anal.
Calcd for C59H44OP2Ru: C, 76.03; H, 4.76. Found: C, 76.15;
H, 4.87.
P r ep a r a tion of [η5η1-C5H4C(CH3)dC(P h )C(O)](d p p e)-
Ru (3d ). To a solution of 2d (25 mg, 0.04 mmol) in anhydrous
methyl alcohol (20 mL) was added phenylacetylene (45 µL, 0.40
mmol), and the mixture was heated to reflux for 6 h. Then
the yellow solution was evaporated to dryness and the residue
was recrystallized with CH2Cl2/n-hexane to give a yellow
powder identified as 3d (15 mg, 65% yield). Spectroscopic data
for 3d are as follows. 1H NMR (CDCl3): δ 7.69-6.95 (m, 25H,
Ph), 5.59 (br, 2H, Cp), 4.72 (br, 2H, Cp), 2.72-2.29 (m, 4H,
PCH2CH2P), 1.82 (s, 3H, CH3). 13C NMR (CDCl3): δ 254.9 (t,
J C-P ) 14.0 Hz, CdO), 167.9 (s, COCPh), 144.1 (s, CCH3),
138.6-125.4 (m, Ph), 92.8, 86.4, 68.8 (s, Cp), 29.7-27.5 (t,
PCH2CH2P, J C-P ) 21.4 Hz), 19.8 (s, CH3). 31P NMR
(CDCl3): δ 96.50 (s). MS (FAB): m/z 708.2 (M+). Anal. Calcd
for C41H36OP2Ru: C, 69.58; H, 5.13. Found: C, 69.44; H, 4.98.
Sp ectr oscop ic Obser va tion of {(η5-C5H4COCH3)-
(P P h 3)2Ru dCdCHP h }Cl (4a ). The same reaction was car-
ried out in an oil bath with the temperature maintained at 50
°C for 3 h to give an orange mixture. The solvent of this
mixture was removed under vacuum, and the residue was
redissolved in CDCl3. The 31P NMR spectrum of this solution
indicated formation of the intermediate 4a as well as 3a in a
ratio of roughly 1:1. Attempts to isolate 4a by column chro-
matography led to decomposition. Only a yellow band, identi-
fied as 3a , was obtained. Spectroscopic data for 4a were
obtained from the mixture of products. 1H NMR (CDCl3): δ
7.69-6.95 (m, 35H, Ph), 5.03 (br, 2H, Cp), 4.74 (s, 1H,
CdCH(Ph)), 4.56 (br, 2H, Cp), 2.28 (s, 3H, CH3). 31P NMR
(CDCl3): δ 42.87 (s). Further heating of the mixture in MeOH
converted this intermediate to 3a .
Isola tion of (η5-C5H4COCH3)(P P h 3)2Ru CtCP h (5a ). In
the presence of NaOMe (20 mg), the reaction of 2a (0.051 g,
0.064 mmol) with excess HCtCPh (72 µL, 0.65 mmol) in
MeOH gave 3a and the acetylide complex 5a in a 1:2 ratio.
Column chromatographic separation of the mixture eluted by
n-hexane/CH2Cl2 (1:5) gave two yellow bands, 5a and 3a .
Spectroscopic data of 5a are as follows. 1H NMR (CDCl3): δ
7.30-6.89 (m, 35H, Ph), 4.59 (br, 2H, Cp), 3.80 (br, 2H, Cp),
2.57 (s, 3H, CH3). 31P NMR (CDCl3): δ 51.85 (s). MS (FAB):
m/z 834.4 (M+), 692.3 (M+ - CCPh, COCH3). In the presence
of CF3COOH, 5a in CDCl3 cleanly converted to 3a in a NMR
tube in 4 h. Anal. Calcd for C51H42OP2Ru: C, 73.45; H, 5.08.
P r ep a r a tion of [η5-C5H4C(CCP h )(OH)CH3](P P h 3)2Ru Cl
(6a ). To a solution of 2a (102 mg, 0.13 mmol in 10 mL of
CH2Cl2) exposed to air was added lithium phenylacetylide (390
Spectroscopic data for 6c (BINAP) are as follows. Major
product: 1H NMR (CDCl3) δ 7.29-6.17 (m, 37H, Ph), 6.24 (br,
1H, OH), 4.33 (br, 1H, Cp), 4.32 (br, 1H, Cp), 4.25 (br, 1H,
Cp), 3.46 (br, 1H, Cp), 1.77 (s, 3H, CH3); 13C NMR (CDCl3) δ
142.5-119.2 (m, Ph), 118.2 (s, chiral carbon), 92.8 (s, CtCPh),
83.1 (s, CtCPh), 85.0, 81.1, 75.9, 69.3, 66.6 (s, Cp), 31.2 (s,
CH3); 31P NMR (CDCl3) δ 53.17 (d, J P-P ) 52.1 Hz), 37.23 (d,
J P-P ) 52.1 Hz). Minor product: 1H NMR (CDCl3) δ 7.29-
6.17 (m, 37H, Ph), 6.18 (br, 1H, OH), 4.20 (br, 1H, Cp), 3.72
(br, 1H, Cp), 3.59 (br, 1H, Cp), 3.55 (br, 1H, Cp), 1.70 (s, 3H,
CH3); 13C NMR (CDCl3) δ 142.5-119.2 (m, Ph), 118.0 (s, chiral
carbon), 93.2 (s, CtCPh), 83.0 (s, CtCPh), 86.1, 81.4, 72.8,
67.5, 65.4, (s, Cp), 35.5 (s, CH3); 31P NMR (CDCl3) δ 53.69 (d,
J P-P ) 52.3 Hz), 41.67 (d, J P-P ) 52.3 Hz); MS (FAB) m/z 968.0
(M+), 932.3 (M+ - Cl), 831.3 (M+ - Cl, CCPh).
Spectroscopic data for 6d (dppe) are as follows. 1H NMR
(CDCl3): δ 8.01-6.96 (m, 25H, Ph), 5.55 (br, 1H, OH), 5.33
(br, 1H, Cp), 5.26 (br, 1H, Cp), 3.88 (br, 1H, Cp), 2.89 (br, 1H,
Cp), 2.72-2.31 (m, 4H, PCH2CH2P), 1.87 (s, 3H, CH3). 13C
NMR (CDCl3): δ 142.1-23.2 (m, Ph), 116.6 (s, chiral carbon),
92.9 (s, CtCPh), 83.4 (s, CtCPh), 72.6, 79.5, 77.8, 70.0, 67.0
(s, Cp), 33.8 (s, CH3), 27.9-26.5 (m, PCH2CH2P). 31P NMR
(CDCl3): δ 80.95 (d, J P-P ) 26.4 Hz), 76.43 (d, J P-P ) 26.4
Hz). MS (FAB): m/z 744.3 (M+), 727.3 (M+ - OH), 708.8 (M+
- Cl), 691.3 (M+ - Cl, OH), 607.2 (M+ - Cl, CCPh). Anal.
Calcd for C43H37OP2RuCl: C, 66.17; H, 5.01. Found: C, 66.35;
H, 5.12.
Tr a n sfor m a tion of 6a to 3a . Complex 6a (88 mg) was
passed through a column packed with neutral aluminum oxide

Ru Complexes with an Acetyl-Substituted Cp Ligand
Organometallics, Vol. 21, No. 7, 2002 1361
Ta ble 3. Cr ysta l a n d In ten sity Collection Da ta for
[η5:η1-C5H4C(CH3)dC(P h )C(O)](P P h 3)2Ru (3a ) a n d
[(η5-C5H4C(CCP h )(OH)CH3)](Ch ir a p h os)Ru Cl (6b)
through an alumina-packed column. The yellow band was
eluted with CH2Cl2. The solvent of this yellow band was
removed under vacuum. The product was recrystallized from
CH2Cl2/n-hexane to give 7d (62 mg, 60%). Spectroscopic data
for 7d are as follows. 1H NMR (CDCl3): δ 7.89-7.02 (m, 25H,
Ph), 5.59 (s, 1H, dCH2), 5.46 (s, 1H, dCH2), 4.98 (br, 2H, Cp),
4.06 (br, 2H, Cp), 2.69-2.64 (m, 2H, PCH2CH2P), 2.49-2.43
(m, 2H, PCH2CH2P). 13C NMR (CDCl3): δ 141.8-123.9 (m, Ph),
123.2 (s, C5H4CdCH2), 118.3 (s, C5H4CdCH2), 94.6, 83.7, 74.8
(s, Cp), 89.2 (s, CtCPh), 88.9 (s, CtCPh), 27.7 (t, PCH2CH2P,
J C-P ) 22.3 Hz). 31P NMR (CDCl3): δ 79.66 (s). MS (FAB):
m/z 726.2 (M+), 691.2 (M+ - Cl). Anal. Calcd for C41H35P2-
RuCl: C, 67.81; H, 4.86. Found: C, 67.76; H, 4.81. Protonation
of 7d in CDCl3 with excess CF3COOH gave a single product
(8d ). Spectroscopic data for 8d are as follows. 1H NMR
(CDCl3): δ 7.69-7.12 (m, 25H, Ph), 6.27, 6.11, 5.65, 3.85 (br,
3a
6b
mol formula
mol wt
space group
a, Å
b, Å
c, Å
R (deg)
â (deg)
γ (deg)
V, Å3
C
51H42OP2Ru
C43H41ClOP2Ru
772.22
P21
9.3200(3)
19.1980(5)
11.2600(2)
90
109.39(3)
90
833.86
Pnma
18.5681(4)
15.2878(2)
14.1439(3)
90
90
90
4014.96(13)
4
0.20 × 0.10 × 0.10 0.35 × 0.30 × 0.25
1900.39(9)
2
Z
cryst dimens, mm3
Mo KR radiation: λ, Å 0.710 73
θ range for data
collection, deg
0.710 73
1.92-27.50
4H, Cp), 3.06-2.76 (m, 4H, PCH2CH2P), 1.26 (s, 3H, CH3). 31
P
1.81-23.29
NMR (CDCl3): δ 86.46 (d, J P-P ) 24.1 Hz), 73.93 (d, J P-P
)
24.1 Hz). FAB mass: m/z 727.4 (M+), 691.8 (M+ - Cl).
limiting indices (h, k, l) -20 to +18;
-12 to +11;
-24 to +23;
-14 to +14
53 516
7138
0.865 and 0.686
-12 to +16;
X-r a y Str u ctu r e Deter m in a tion of 3a a n d 6b. For 3a , a
single crystal of dimensions 0.20 × 0.10 × 0.10 mm3 was
mounted on a glass fiber with epoxy. Data were collected at
room temperature on a Siemens SMART CCD area detector
system employing a 3 kW sealed-tube X-ray source operating
at 1.5 kW. Data were collected using a narrow frame method.
The total data collection yielded 11 876 data after integration
using SAINT. Laue symmetry revealed a orthorhombic crystal
system, and unit cell parameters were determined from the
least-squares refinement of three-dimensional centroids of 25
unique reflections. Data were corrected for absorption with the
SADABS21 program. The space group was assigned as Pnma
on the basis of systematic absences and intensity statistics
using XPREP, and the structure was solved and refined using
direct methods included in the SHELXTL22 package. For a Z
value of 4 there is one independent molecule within the
asymmetric unit. In the final model, non-hydrogen atoms were
refined anisotropically, with hydrogen atoms included in
idealized locations. The structure was refined to R1 ) 0.0551
and wR2 ) 0.0798 for all data (R1 ) 0.0330 and wR2 ) 0.0702
for I > 2σ(I)).23 Fractional coordinates and thermal parameters
are given in the Supporting Information. The structure de-
termination of 6b was similarly carried out on a SMART CCD
diffractometer. Relevant data for both crystals are given in
Table 3.
-15 to +8
no. of rflns collected
no. of indep rflns
max and min
11 876
2969
0.639 and 0.585
transmission
refinement method
no. of data/restraints/
params
full-matrix least squares on F2
2730/0/263
7138/1/434
GOF
1.167
1.320
final R indices
for I > 2σ(I)
0.0330/0.0702
0.0551/0.0798
0.3570, -0.354
0.0418/0.1035
0.0432/0.1082
0.8350, -0.968
for all data
∆F (in final map), e/Å3
eluted by CH2Cl2. The red band changed to yellow in the
column. The solvent of the yellow fraction collected was
removed under vacuum to give 3a (65 mg, 78% yield). This
transformation is also observed in CDCl3 when NaOMe was
added to a solution of 6a in a NMR tube. The NMR yield was
about 50%.
Isola tion of (η5-C5H4COCH3)(R-BINAP )Ru CtCP h (5c).
Transformation of 6c to 5c was performed by chromatography
on an alumina-packed column, and CH2Cl2 was used as eluent;
the product was isolated as a yellow solid and was purified by
recrystallization from CH2Cl2/n-hexane. Spectroscopic data for
5c are as follows. 1H NMR (CDCl3): δ 7.96-6.20 (m, 37H, Ph),
4.83, 4.68, 4.35, 4.30 (br, 4H, Cp), 2.31 (s, 3H, CH3). 13C NMR
(CDCl3): δ 197.1 (s, CdO), 150.2-121.5 (m, Ph), 118.3 (t, J C-P
) 22.6 Hz, CtCPh), 114.2 (s, CtCPh), 95.9, 93.4, 88.9, 85.3,
83.9 (s, Cp), 29.0 (s, CH3). 31P NMR (CDCl3): δ 57.60 (d, J P-P
) 47.6 Hz), 47.40 (d, J P-P ) 47.6 Hz). MS (FAB): m/z 932.3
(M+), 831.2 (M+ - CCPh). Anal. Calcd for C59H44OP2Ru: C,
76.03, H, 4.76. Found: C, 76.00; H, 4.67.
Ack n ow led gm en t. Financial support from the Na-
tional Science Council of Taiwan is gratefully acknowl-
edged.
Su p p or tin g In for m a tion Ava ila ble: Details of the struc-
tural determinations for complex 3a and 6b, including tables
of crystal and intensity collection data, positional and aniso-
tropic thermal parameters, and all of the bond distances and
angles. This material is available free of charge via the
Internet at http://pubs.acs.org.
P r ep a r a t ion of [(η5-C5H 4COCH 3)(R-BINAP )R u dCd
CHP h ]CF 3COO (4c). A tube was charged with 5c (25 mg,
0.027 mmol), and excess trifluoroacetic acid (CF3COOH) and
chloroform-d were introduced into this tube. The 1H and 31P
NMR spectra were collected. Complex 4c transformed to 3c
(5% NMR yield) and other intractable products in 20 min at
room temperature. No attempt was made to isolate 4c.
OM010893J
(21) The SADABS program is based on the method of Blessing;
see: Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(22) SHELXTL: Structure Analysis Program, version 5.04; Siemens
Industrial Automation Inc., Madison, WI, 1995
1
Spectroscopic data for 4c are as follows. H NMR (CDCl3): δ
7.61-6.28 (m, 37H, Ph), 5.79, 5.48, 5.36, 4.97 (br, 4H, Cp),
4.34 (s, 1H, CdCH(Ph)), 2.32 (s, 3H, CH3). 31P NMR (CDCl3):
δ 51.92 (d, J P-P ) 36.8 Hz), 35.73 (d, J P-P ) 36.8 Hz).
P r epar ation of [η5-C5H4C(dCH2)CCP h ](dppe)Ru Cl (7d).
Complex 6d (105 mg, 0.14 mmol) in CH2Cl2 was passed
(23) R1 ) (∑||Fo| - |Fc||)/∑|Fo|. wR2 ) [∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]]1/2
,
where w ) 1/[σ2(Fo2) + (aP)2 + bP] and P ) [(Max; 0, Fo2) + 2Fc2]/3.
GOF ) [∑[w(Fo - Fc2)2]/(n - p)]1/2, where n and p denote the number
2
of data and parameters, respectively.