Synthesis of Novel Organometallic Compounds Containing η1-Carbon Polycyclic Ligands: Condensation of Propargyl Alcohol with the Allenylidene Ligand of [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PPri3)]BF4

Article abstract of DOI:10.1021/om990456t

The allenylidene complex [Ru(η⁵-C₅H₅){C=C=CPh ₂}(CO)(PPrⁱ₃)]BF₄ (1) reacts with propargyl alcohol to give the α,β-unsaturated alkoxycarbene derivative [Ru(η⁵-C₅H₅){C(OCH₂C≡ CH)CH=CPh₂}(CO)(PPrⁱ₃)]BF₄ (2). The structure of 2 was determined by an X-ray investigation, revealing a Ru-C distance of 1.965(4) A?. Treatment of 2 with 1 equiv of Na₂-CO₃ affords [Ru(η⁵-C₅H ₅){9-phenyl-1,3-dihydronaphtho[2,3-c]-1-furanylidene}(CO)(PPr ⁱ₃)]BF₄ (3), which reacts with NaBH₄ to give Ru(η⁵-C₅H₅){CH ₂(1-phenyl-3-hydroxymethyl-2-naphthyl)}-(CO)(PPrⁱ ₃) (4). The structure of 3 was determined by an X-ray diffraction analysis, revealing a Ru-C bond length of 2.004(2) A?. Treatment of 2 with 3 equiv of NaOCH₃ leads to a mixture of compounds containing the racemic form (Ru_R,C_R;Ru_S,C_S)-Ru(η ⁵-C₅H ₅){9-phenyl-1,3-dihydronaphtho[2,3-c]-1-furanyl}(CO)(PPr ⁱ₃) (5) as the main component. This racemic form was obtained as a pure solid by passing the crude products through an Al₂O₃ column using diethyl ether as eluent. The structure of 5 was also determined by an X-ray diffraction analysis. In this case, the investigation reveals a Ru-C distance of 2.203(3) A?. When the crude products were passed through an Al₂O₃ column using a pentane/diethyl ether (5:1) mixture, the epimerization of 5 into (Ru_R,C_S;Ru_S,C_R)-Ru(η ⁵-C₅H ₅){9-phenyl-1,3-dihydronaphtho[2,3-c]-1-furanyl}(CO)(PPr ⁱ₃) (6) was observed. When the above-mentioned chromatography is carried out using an increasing polarity mixture of toluene/diethyl ether (from 10:1 to 1:10) as eluent, the transformation of 5 into its isomer Ru(η⁵-C₅H₅){CH ₂(1-phenyl-3-carboxa-2-naphthyl)}(CO)(PPrⁱ₃) (7) occurs. The complex Ru(η⁵-C₅H ₅){9-phenyl-3,3a-dihydronaphtho[2,3-c]-1-furanyl}(CO)(PPr ⁱ₃) (8) was also synthesized, by passing 2 through an Al₂O₃ column using a tetrahydrofuran/dichloromethane (5:1) mixture as eluent.

Full text of DOI:10.1021/om990456t

4
Organometallics 2000, 19, 4-14
Articles
Syn th esis of Novel Or ga n om eta llic Com p ou n d s
Con ta in in g η1-Ca r bon P olycyclic Liga n d s: Con d en sa tion
of P r op a r gyl Alcoh ol w ith th e Allen ylid en e Liga n d of
[Ru (η5-C5H5)(CdCdCP h 2)(CO)(P P r i )]BF 4
3
Miguel A. Esteruelas,* Angel V. Go´mez, Ana M. Lo´pez,* Montserrat Oliva´n,
Enrique On˜ate, and Natividad Ruiz
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received J une 11, 1999
The allenylidene complex [Ru(η5-C5H5){CdCdCPh2}(CO)(PPri )]BF4 (1) reacts with pro-
3
pargyl alcohol to give the R,â-unsaturated alkoxycarbene derivative [Ru(η5-C5H5){C(OCH2Ct
CH)CHdCPh2}(CO)(PPri )]BF4 (2). The structure of 2 was determined by an X-ray
3
investigation, revealing a Ru-C distance of 1.965(4) Å. Treatment of 2 with 1 equiv of Na2-
CO3 affords [Ru(η5-C5H5){9-phenyl-1,3-dihydronaphtho[2,3-c]-1-furanylidene}(CO)(PPri3)]BF4
(3), which reacts with NaBH4 to give Ru(η5-C5H5){CH2(1-phenyl-3-hydroxymethyl-2-naphthyl)}-
(CO)(PPri ) (4). The structure of 3 was determined by an X-ray diffraction analysis, revealing
3
a Ru-C bond length of 2.004(2) Å. Treatment of 2 with 3 equiv of NaOCH3 leads to a mixture
of compounds containing the racemic form (RuR,CR;RuS,CS)-Ru(η5-C5H5){9-phenyl-1,3-
dihydronaphtho[2,3-c]-1-furanyl}(CO)(PPri ) (5) as the main component. This racemic form
3
was obtained as a pure solid by passing the crude products through an Al2O3 column using
diethyl ether as eluent. The structure of 5 was also determined by an X-ray diffraction
analysis. In this case, the investigation reveals a Ru-C distance of 2.203(3) Å. When the
crude products were passed through an Al2O3 column using a pentane/diethyl ether (5:1)
mixture, the epimerization of 5 into (RuR,CS;RuS,CR)-Ru(η5-C5H5){9-phenyl-1,3-dihydronaph-
tho[2,3-c]-1-furanyl}(CO)(PPri ) (6) was observed. When the above-mentioned chromatog-
3
raphy is carried out using an increasing polarity mixture of toluene/diethyl ether (from 10:1
to 1:10) as eluent, the transformation of 5 into its isomer Ru(η5-C5H5){CH2(1-phenyl-3-
carboxa-2-naphthyl)}(CO)(PPri ) (7) occurs. The complex Ru(η5-C5H5){9-phenyl-3,3a-dihy-
3
dronaphtho[2,3-c]-1-furanyl}(CO)(PPri ) (8) was also synthesized, by passing 2 through an
3
Al2O3 column using a tetrahydrofuran/dichloromethane (5:1) mixture as eluent.
In tr od u ction
the intramolecular addition of the terminal OH group
to the Câ-Cγ double bond of the transient allenylidene
and the subsequent nucleophilic addition of the allylic
alcohol to the resulting functionalized vinylidene inter-
mediate (Scheme 1). That ring closure of the function-
Transition metal allenylidene complexes (MCdCd
CR2) have attracted a great deal of attention in recent
years1,2 as a new type of organometallic intermediate
that may have unusual reactivity in stoichiometric3 and
catalytic4 processes. Thus, cyclization of diols via tran-
sient allenylidene complexes concomitant with the ad-
dition of allylic alcohols represents a novel way to build
heterocycles (eq 1).5
(3) (a) Esteruelas, M. A.; Oro, L. A.; Schrickel, J . Organometallics
1997, 16, 796. (b) Bohanna, C.; Callejas, B.; Edwards, A. J .; Esteruelas,
M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C. Organometallics
1998, 17, 373. (c) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate,
E. Organometallics 1998, 17, 3567. (d) Esteruelas, M. A.; Go´mez, A.
V.; Lo´pez, A. M.; Puerta, M. C.; Valerga, P. Organometallics 1998, 17,
4959. (e) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J .;
On˜ate, E. Organometallics 1998, 17, 5434. (f) Roth, G.; Reindl, D.;
Gockel, M.; Troll, C.; Fischer, H. Organometallics 1998, 17, 1393. (g)
Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Pe´rez-Carren˜o, E.; Ienco, A.
Organometallics 1998, 17, 5216. (h) Winter, R. F. Chem. Commun.
1998, 2209. (i) Bianchini, C.; Peruzzini, M.; Zanobini, F.; Lo´pez, C.; de
los Rios, I.; Romerosa, A. Chem. Commun. 1999, 443. (j) Bruce, M. I.;
Low, P. J .; Tiekink, E. R. T. J . Organomet. Chem. 1999, 572, 3. (k)
Buriez, B.; Burns, I. D.; Hill, A. F.; White, A. J . P.; Williams, D. J .;
Wilton-Ely, J . D. E. T. Organometallics 1999, 18, 1504. (l) Esteruelas,
M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz, N. Organometallics
1999, 18, 1606.
The formation of these heterocycles, which is cata-
lyzed by the fragment [Ru(η5-C5H5)(PPh3)2]+, involves
(1) Bruce, M. I. Chem. Rev. 1998, 98, 2797.
(2) Touchard, D.; Dixneuf, P. H.; Coord. Chem. Rev. 1998, 178, 409.
10.1021/om990456t CCC: $19.00 © 2000 American Chemical Society
Publication on Web 12/11/1999

Organometallic Compounds Containing Polycyclic Ligands
Organometallics, Vol. 19, No. 1, 2000
5
Sch em e 1
Sch em e 2
alized allenylidene precedes addition of allyl alcohol is
suggested by the total lack of reactivity of the stoichi-
ometrically formed complexes [Ru(η5-C5H5)(CdCdCHR)-
(PPh3)2]+ with allyl alcohols.5a The selectivity observed
for the ring closure agrees well with EHT-MO calcula-
tions, indicating that the CR and Cγ atoms of the
allenylidene ligands are electrophilic centers, while the
Câ atom is nucleophilic.
EHT-MO calculations also indicate that allenylidenes
coordinate to metal centers as σ-donor and π-acceptor
ligands. The interaction between the HOMO of the
allenylidene and the LUMO of the metallic fragment
produces a lower charge transfer than the interaction
between the HOMO of the metallic fragment and the
LUMO of the allenylidene. Then, the π-acceptor com-
ponent of the metal-allenylidene bond is stronger than
the σ-donor one.6
lead to functionalized alkynyl complexes as a result of
the regioselective addition of the reagents at the Cγ atom
of the diphenylallenylidene group. In this respect, it
should be mentioned that, in general, the net charge
on the CR atom is significantly higher than that on the
Cγ atom.6d
The behavior of these ruthenium compounds is simi-
lar to that of other cationic allenylidene complexes of
the iron triad stabilized by relatively basic metallic
fragments.1,2,9 Three years ago, interest in the change
of properties of the diphenylallenylidene ligand on
moving from the more basic metallic fragments led us
to prepare the complex [Ru(η5-C5H5)(CdCdCPh2)(CO)-
(PPri )]BF4 (1),10 where the carbonyl group increases the
3
electrophilicity of the C3-organic fragment.11 As a con-
sequence of this increment, complex 1 adds water,
methanol, and ethanol at the CR-Câ double bond of the
allenylidene to afford the corresponding R,â-unsaturated
hydroxy- and alkoxycarbene compounds, respectively.
By deprotonation the alkoxycarbene complexes give
alkoxyallenyl derivatives.10
As a result of this bonding situation, there are marked
differences in reactivity depending on the particular
metallic fragment which stabilizes the allenylidene unit.
This is nicely illustrated by the behavior of the diphe-
nylallenylidene moiety in the iron triad complexes. The
C3-organic fragment of the osmium complex Os(η5-
C5H5)Cl(CdCdCPh2)(PPri ) has a marked nucleophilic
3
character, as revealed by its lack of reactivity toward
water, alcohols, phosphines, amines, etc. and its reac-
tions with HBF4 and dimethyl acetylenedicarboxylate,
which afford [Os(η5-C5H5)Cl(CCHdCPh2)(PPri3)]BF4 and
Os(η5-C5H5)Cl{CdC(CO2Me)C(CO2Me)dCdCPh2}(P-
Complex 1 reacts not only with saturated alcohols but
also with allyl alcohol without precoordination of the
olefinic moiety. The reaction gives rise to the alkoxy-
carbene derivative [Ru(η5-C5H5){C(OCH2CHdCH2)CHd
CPh2}(CO)(PPri )]BF4, which by deprotonation at low
3
Pri ), respectively.7 In contrast to this complex, the
temperature affords the alkoxyallenyl complex Ru(η5-
3
C5H5){C(OCH2CHdCH2)dCdCPh2}(CO)(PPri ). In so-
diphenylallenylidene organic moiety stabilized by the
metallic fragments [Ru(η5-C5H5)(PPh3)2]+ 5a and [Ru(η5-
C9H7)L2]+ (L2 ) 2 PPh3, dppe, dppm)8 has a moderated
electrophilic character. These complexes do not undergo
intermolecular addition of weak nucleophilic reagents
(i.e. water and alcohols), and the reactions with strong
nucleophiles, such as methoxide, alkyl, and acetylide,
3
lution, at room temperature, this compound evolves into
the naphtho-furanyl derivative Ru(η5-C5H5)(9-phenyl-
3,3a,4,4a-tetrahydronaphtho[2,3-c]-1-furanyl)(CO)(P-
Pri ) (Scheme 2) by an intramolecular Diels-Alder
3
reaction, where the Câ-Cγ double bond and one of the
two phenyl groups of the allenyl unit act as an inner-
outer ring diene and the CHdCH2 double bond of the
alkoxy unit acts as dienophile.12
(4) (a) Fu¨rstner, A.; Picquet, M.; Bruneau, C.; Dixneuf, P. H. Chem.
Commun. 1998, 1315. (b) Picquet, M.; Touchard, D.; Bruneau, C.;
Dixneuf, P. H. New J . Chem. 1999, 141. (c) Fu¨rstner, A.; Hill, A. F.;
Liebl, M.; Wilton-Ely, J . D. E. T. Chem. Commun. 1999, 601. (d)
Harlow, K. J .; Hill, A. F.; Wilton-Ely, J . D. E. T. J . Chem. Soc., Dalton
Trans 1999, 285.
(5) (a) Trost, B. M.; Flygare, J . A. J . Am. Chem. Soc. 1992, 114, 5476.
(b) Trost, B. M.; Flygare, J . A. Tetrahedron Lett. 1994, 35, 4059.
(6) (a) Berke, H.; Huttner, G.; Von Seyerl, J . Z. Naturforsch. 1981,
36B, 1277. (b) Edwards, A. J .; Esteruelas, M. A.; Lahoz, F. J .; Modrego,
J .; Oro, L. A.; Schrickel, J . Organometallics 1996, 15, 3556. (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. Organometallics
1996, 15, 2137. (d) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.;
Modrego, J .; On˜ate, E. Organometallics 1997, 16, 5826.
As a part of our program directed toward designing
new models for homogeneous systems effective in the
synthesis of functionalized organic fragments from basic
hydrocarbon units, we describe now the cycloaddition
products resulting of the condensation of propargyl
alcohol with the allenylidene ligand of 1.
(9) Touchard, D.; Haquette, P.; Daridor, A.; Romero, A.; Dixneuf,
P. H. Organometallics 1998, 17, 3844.
(10) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
(11) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Borge, J .;
Garc´ıa-Granda, S. Organometallics 1997, 16, 2483.
(12) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz,
N. Organometallics 1998, 17, 2297.
(7) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J .
I. Organometallics 1998, 17, 3479.
(8) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lo´pez-Gonza´lez, M.
C.; Borge, J .; Garc´ıa-Granda, S. Organometallics 1997, 16, 4453.

6
Organometallics, Vol. 19, No. 1, 2000
Esteruelas et al.
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex {Ru (η5-C5H5){C-
(OCH2CtCH)CHdCP h 2}(CO)(P P r i3)}BF 4 (2)
Ru-P
2.373(11)
3.240(4)
2.253(4)
2.272(4)
2.295(4)
2.279(4)
1.965(4)
1.851(4)
O(1)-C(33)
O(2)-C(1)
O(2)-C(16)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(3)-C(10)
C(16)-C(17)
C(17)-C(18)
1.145(5)
1.321(4)
1.469(4)
1.473(5)
1.342(5)
1.485(5)
1.482(5)
1.471(6)
1.157(6)
Ru-C(28)
Ru-C(29)
Ru-C(30)
Ru-C(31)
Ru-C(32)
Ru-C(1)
Ru-C(33)
P-Ru-Ga
124.22(14) C(1)-O(2)-C(16)
92.63(11) C(1)-C(2)-C(3)
93.72(13) C(2)-C(3)-C(4)
121.0(3)
127.6(4)
120.8(4)
121.9(4)
117.3(3)
116.8(3)
110.9(3)
P-Ru-C(1)
P-Ru-C(33)
G-Ru-C(1)
G-Ru-C(33)
C(1)-Ru-C(33)
124.6(2)
121.6(2)
91.1(2)
C(2)-C(3)-C(10)
C(4)-C(3)-C(10)
O(2)-C(1)-C(2)
O(2)-C(16)-C(17)
Ru-C(33)-O(1) 173.3(4)
Ru-C(1)-C(2)
Ru-C(1)-O(2)
F igu r e 1. Molecular diagram of the cation of 2, [Ru(η5-
127.0(3)
116.2(3)
C(16)-C(17)-C(18) 177.8(5)
C5H5){C(OCH2CtCH)CHdCPh2}(CO)(PPri )]+.
3
a
G is the centroid of the C(28)-C(32) Cp ligand.
Resu lts a n d Discu ssion
1. Nu cleop h ilic Ad d ition of P r op a r gyl Alcoh ol
The Ru-C(1) distance is slightly longer than the
related bond length in the alkoxycarbene complex [Ru-
(κ3-HBpz3){C(OCH3)CH2CO2CH3}(dippe)]BPh4 (1.86(2)
Å)13 and in the R,â-unsaturated carbene compound
[RuCl(CHCHdCPh2)(CO)(PPri3)2]BF4 (1.874(3) Å),14 simi-
lar to that found in other cyclopentadienylruthenium
carbene complexes such as [Ru(η5-C5H5){C(OCH3)CH2-
CH3}(PPh3)2]PF6 (1.956(6) Å)15 and [Ru(η5-C5H5){C-
(OCH3)CH2Ph}(CHIRAPHOS)]PF6 (1.93(2) Å)16 and
shorter than the ruthenium-carbon distances in the
to th e Allen ylid en e Liga n d of [Ru (η5-C5H5)(CdCd
CP h 2)(CO)(P P r i )]BF 4. The allenylidene ligand of [Ru-
3
(η5-C5H5)(CdCdCPh2)(CO)(PPri )]BF4 (1) reacts not
3
only with water, methanol, and allyl alcohol but also
with propargyl alcohol. After 30 h at 40 °C, the prop-
argyl alcohol solutions of 1 afford the R,â-unsaturated
alkoxycarbene derivative [Ru(η5-C5H5){C(OCH2CtCH)-
CHdCPh2}(CO)(PPri3)]BF4 (2) as a result of the addition
of the O-H bond of the alcohol to the CR-Câ double
bond of the allenylidene unit (eq 2). The selectivity
complexes [Ru{C(dCHPh)OC(O)CH3}(CO){κ1-OC(CH3)2}-
(PPri ) ]BF4 (1.967(8) Å),17 Ru3(CO)10(µ2-SMe)(µ2-η2-
3 2
NC6H4SC) (2.075(9) Å),18 [{Ru(η5-C5Me5)(µ-SPri)}2(µ-
C18H15)]BF4 (2.04(3) and 1.98(2) Å),19 and [{Ru(η5-
C5Me5)(µ-SPri)}2(µ-C16H18)]OTf (2.06(1) and 2.04(1) Å),20
where a ruthenium-carbon bond between single and
double has been proposed.
The bond lengths and angles within the unsaturated
η1-carbon ligand are consistent with the alkenylcarbene
proposal. In agreement with the values reported for
related compounds,21 the bond angles around C(2) and
C(3) are in the range 117.3(4)-127.6(4)°. Furthermore,
C(1) and C(2) are separated by 1.473(5) Å and C(2) and
C(3) by 1.342(5) Å. These values agree well with the
observed for the addition agrees well with EHT-MO
calculations on the model cation [Ru(η5-C5H5)(CdCd
CH2)(CO)(PH3)]+, indicating that CR of the allenylidene
is an electrophilic center, while the Câ is nucleophilic.6d
Complex 2 was isolated as an orange solid in 88%
yield and characterized by MS, elemental analysis, IR
(13) J ime´nez-Tenorio, M. A.; J ime´nez-Tenorio, M.; Puerta, M. C.;
Valerga, P. Organometallics 1997, 17, 55528.
(14) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier, B.
Organometallics 1994, 13, 4258.
(15) Bruce, M. I.; Humprey, M. G.; Snow, M. R.; Tiekink, E. R. T. J .
Organomet. Chem. 1986, 314, 213.
1
and H, 31P{1H}, and 13C{1H} NMR spectroscopy, and
an X-ray crystallographic study. A view of the molecular
geometry of the cation of 2 is shown in Figure 1. Selected
bond distances and angles are listed in Table 1.
The geometry around the ruthenium center of 2 is
close to octahedral, with the cyclopentadienyl ligand
occupying three sites of a face. The angles formed by
the triisopropylphosphine, the carbonyl group, and the
carbene ligand are all close to 90°. The most conspicuous
features of the structure are, first, the Ru-C(1) bond
length (1.965(4) Å), which is consistent with a Ru-C(1)
double-bond formulation, and, second, the Ru-C(1)-
C(2) (127.0(3)°) and Ru-C(1)-O(2) (116.2(3)°) angles,
which clearly indicate sp2 hybridization for the C(1)
carbon atom.
(16) Consiglio, G.; Morandini, F.; Ciani, G. F.; Sironi, A. Organo-
metallics 1986, 5, 1976.
(17) Esteruelas, M. A.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate, E.; Oro,
L. A. Organometallics 1994, 13, 1669.
(18) Renouard, C.; Stoeckli-Evans, H.; Su¨ss-Fink, G. J . Organomet.
Chem. 1995, 492, 179.
(19) Matsuzaka, H.; Hirayama, Y.; Nishio, M.; Mizobe, Y.; Hidai,
M. Organometallics 1993, 12, 36.
(20) Matsuzaka, H.; Takagi, Y.; Hidai, M. Organometallics 1994,
13, 13.
(21) (a) Selegue, J . P. J . Am. Chem. Soc. 1983, 105, 5921. (b) Clark,
G. R.; Hodgson, D. J .; Ng, M. M. P.; Rickard, C. E. F.; Roper, W. R. J .
Chem. Soc., Chem. Commun. 1988, 1552. (c) Irvine, G. J .; Rickard, C.
E. F.; Roper, W. R.; Wright, L. S. J . Organomet. Chem. 1990, 387, C9.
(d) Irvine, G. J .; Rickard, C. E. F.; Roper, W. R.; Wright, L. S. J .
Organomet. Chem. 1990, 387, C5. (e) Pilette, D.; Ouzzine, K.; Le Bozec,
H.; Dixneuf, P. H.; Rickard, C. E. F.; Roper, W. R. Organometallics
1992, 11, 809.

Organometallic Compounds Containing Polycyclic Ligands
Organometallics, Vol. 19, No. 1, 2000
7
mean values reported for single and double C(sp2)-
C(sp2) bonds (1.48 and 1.34 Å, respectively)22 and
suggest that there is not delocalization of the π-electron
density along the C(1)-C(2)-C(3) chain.
The separation between the oxygen atom O(2) and the
C(1) and C(16) atoms reflects the different hybridiza-
tions of these carbons. The separation between O(2) and
the sp2 C(1) carbon atom (1.321(4) Å) is about 0.14 Å
shorter than that between O(2) and the sp3 C(16) carbon
atom (1.469(4) Å). The C(16)-C(17) bond length (1.471-
(6) Å) is consistent with a single bond between a sp3 C
and an sp C, whereas the C(17)-C(18) distance (1.157-
(6) Å) and the C(16)-C(17)-C(18) angle (177.8(5)°)
support the alkyne formulation.
F igu r e 2. Molecular diagram of the cation of 3, [Ru(η5-
C5H5){9-phenyl-1,3-dihydronaphtho[2,3-c]-1-furanylidene}-
In solution, the spectroscopic data of 2 agree well with
the structure shown in Figure 1. In the IR spectrum in
Nujol, the most noticeable feature is the presence of a
(CO)(PPri )]+.
3
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex {Ru (η5-C5H5)(9-p h en yl-1,3-
d ih yd r on a p h th o[2,3-c]-1-fu r a n ylid en e)(CO)-
(P P r i3)}BF 4 (3)
1
ν(CtC) band at 2126 cm-1. The H NMR spectrum in
chloroform-d shows the characteristic dCH resonance
of the alkenyl unit at 6.59 ppm, which is observed as a
singlet, and at 2.75 ppm the tCH resonance. The latter
appears as a triplet with a J (HH) of 2.4 Hz by spin
Ru-P
2.3857(6)
2.286(2)
2.301(2)
2.277(3)
2.232(2)
2.248(2)
2.004(2)
1.850(3)
O(1)-C(24)
O(2)-C(6)
O(2)-C(23)
C(6)-C(7)
C(7)-C(22)
C(22)-C(23)
1.146(3)
1.323(3)
1.465(3)
1.482(3)
1.424(3)
1.480(3)
Ru-C(1)
Ru-C(2)
Ru-C(3)
Ru-C(4)
Ru-C(5)
Ru-C(6)
Ru-C(24)
1
coupling with the OCH2- group, according to the H-
1H COSY NMR spectrum. In the 13C{1H} NMR spec-
trum the resonance corresponding to the RudC carbon
atom is observed at 305.1 ppm as a broad signal. The
resonances due to the C(2), C(3), C(17), and C(18) carbon
atoms appear as singlets at 136.0, 137.6, 79.6, and 75.3
ppm, respectively.
P-Ru-Ga
125.84(8)
91.73(6)
91.31(7)
119.61(10) C(8)-C(7)-C(22)
123.96(11) C(6)-O(2)-C(23)
95.86(10) C(7)-C(22)-C(21)
O(2)-C(23)-C(22)
C(6)-C(7)-C(8)
C(6)-C(7)-C(22)
102.8(2)
133.0(2)
107.2(2)
119.8(2)
113.9(2)
123.2(2)
108.7(2)
P-Ru-C(6)
P-Ru-C(24)
G-Ru-C(6)
G-Ru-C(24)
C(6)-Ru-C(24)
We have previously mentioned that similarly to the
alkoxy carbene complexes [Ru(η5-C5H5){C(OR)CHd
CPh2}(CO)(PPri )]BF4 (R ) Me, Et), the treatment of
3
the allyloxycarbene derivative [Ru(η5-C5H5){C(OCH2-
Ru-C(24)-O(1) 173.7(2)
C(7)-C(22)-C(23)
C(21)-C(22)-C(23) 128.1(2)
C(22)-C(23)-O(2) 102.8(2)
Ru-C(6)-O(2)
Ru-C(6)-C(7)
112.9(2)
139.0(2)
CHdCH2)CHdCPh2}(CO)(PPri )]BF4 with base pro-
3
duces the deprotonation of the alkenyl unit to give the
O(2)-C(6)-C(7) 107.4(2)
allenyl complex Ru(η5-C5H5){C(OCH2CHdCH2)dCd
a
G is the centroid of the C(1)-C(5) Cp ligand.
CPh2}(CO)(PPri ), which evolves by a Diels-Alder reac-
3
tion into a naphtho-furanyl compound. In this case, all
attempts to obtain a related allenyl derivative starting
from 2 were unsuccessful. Instead, depending upon the
reaction conditions, different cycloaddition products
were obtained.
2. Rea ction of 2 w ith Na 2CO3. Treatment at room
temperature of a yellow suspension of 2 with 1 equiv of
sodium carbonate in tetrahydrofuran affords after 4 h
an orange suspension, from which an orange solid was
isolated in 30% yield. The remaining yellow solution
contains five neutral compounds, as revealed by its 31P-
{1H} NMR spectrum in C6D6, which shows five singlets
at about 67, 68.5 (two of them), 70, and 72 ppm (vide
infra). The orange solid was characterized as the cat-
ionic complex [Ru(η5-C5H5)(9-phenyl-1,3-dihydronaph-
by the triisopropylphosphine, the carbonyl group, and
the cyclic carbene ligand are all close to 90°.
The skeleton of the polycyclic ligand is almost planar,
and the maximum deviation (-0.0443(16) Å) is found
for the O(2) oxygen atom. The ruthenium atom lies
0.2740(3) Å out from the best plane through the 13
atoms forming the polycyclic skeleton. The Ru-C(6)
distance (2.004(2) Å) is about 0.04 Å longer than the
Ru-C(1) bond length in 2 and is comparable to the
related distance in the cyclic carbene complex [Ru(η5-
tho[2,3-c]-1-furanylidene)(CO)(PPri )]BF4 (3; eq 3) by
3
elemental analysis, IR and 1H, 31P{1H}, and 13C{1H}
NMR spectroscopy, and an X-ray crystallographic study.
A view of the molecular geometry of the cation of 3 is
shown in Figure 2. Selected bond distances and angles
are listed in Table 2.
C5H5){CCHdC(OEt)OCdCPh}(CO)(PPri )]BF4 (2.017-
3
(6) Å).3d The bond angles around C(6), 112.9(2)° (Ru-
C(6)-O(2)) and 139.0(2)° (Ru-C(6)-C(7)), support the
sp2 hybridization of this atom. As in 2, the separation
between C(6) and the oxygen atom O(2) (1.323(3) Å) is
0.14 Å shorter than that between O(2) and the sp3 C(23)
carbon atom (1.465(3) Å).
As for 2, the geometry around the ruthenium center
in 3 is close to octahedral with the cyclopentadienyl
ligand occupying three sites of a face. The angles formed
(22) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G.; Taylor, R. J . Chem. Soc., Perkin Trans. 2 1987, S1.

8
Organometallics, Vol. 19, No. 1, 2000
Esteruelas et al.
In solution, the spectroscopic data of 3 agree well with
the structure shown in Figure 2. In the 1H NMR
spectrum in chloroform-d, the most noticeable reso-
nances are those corresponding to the OCH2- protons,
which appear at 6.27 and 6.03 ppm as doublets with a
J (HH) value of 18.9 ppm. The 13C{1H} NMR spectrum
shows the resonance due to the RudC carbon atom at
293.3 ppm as a doublet with a J (CP) value of 9.7 Hz.
The formation of 3 involves the loss of two hydrogen
atoms, and the formation of two C-C bonds. The
formation of one of them takes place by coupling of the
terminal C(sp) carbon atom of the propargyloxy unit
with an ortho carbon atom of one of the two phenyl
groups, whereas the formation of the other is the result
of the coupling of the internal C(sp) carbon atom of the
propargyloxy fragment with the CH carbon atom of the
alkenyl unit.
F igu r e 3. Molecular diagram of the complex Ru(η5-C5H5)-
{9-phenyl-1,3-dihydronaphtho[2,3-c]-1-furanyl}(CO)(P-
Pri ) (5).
3
Although in the five-membered heterocycle the C(6)-
O(2) bond is significantly shorter than the O(2)-C(23)
bond, the first is more reactive than the second one
toward the reduction of 3 with NaBH4. Thus, the
treatment at room temperature of tetrahydrofuran
suspensions of 3 with 2 equiv of NaBH4 leads to the
neutral alkyl compound Ru(η5-C5H5){CH2(1-phenyl-3-
furans, without opening of the heterocyclic ring.24 Even
the reduction of 1,3-diphenylbenzo[c]furan with sodium
leads to 1,3-diphenyldihydrobenzo[c]furan. Ring opening
of the heterocycle to yield alcohols occurs only in
epoxides.25
3. Rea ction of 2 w ith Na OCH3. Treatment at room
temperature of a yellow suspension of 2 with 1 equiv of
sodium methoxide leads after 3 h to 3 and a mixture of
the same neutral compounds as in the case of the
reaction with sodium carbonate, according to the 31P-
{1H} NMR spectrum of the mixture. When the treat-
ment of 2 is carried out with 3 equiv of sodium
methoxide, complex 3 disappears and the mixture of
neutral products contains, as the main component, a
complex displaying a signal at 67.3 ppm in the 31P{1H}
NMR spectrum.
hydroxymethyl-2-naphthyl}(CO)(PPri ) (4), which was
3
isolated as a yellow solid in 36% yield, according to eq
4.
This complex was obtained as a pure yellow crystal-
line solid in 53% yield by passing a diethyl ether solution
of the mixture through an Al2O3 (neutral, activity grade
V) column and characterized as a RuR,CR;RuS,CS race-
mic mixture of the dihydronaphtho-furanyl complex
Ru(η5-C5H5)(9-phenyl-1,3-dihydronaphtho[2,3-c]-1-fura-
The presence of a -CH2OH group in the alkyl ligand
of 4 is strongly supported by the IR spectrum of this
complex in Nujol, which contains a ν(OH) band at 3572
cm-1. In the 1H NMR spectrum in benzene-d6, the
resonances corresponding to the -CH2O- group are
observed at 5.42 and 5.21 ppm, as complex multiplets,
whereas the resonance due to the -OH group appears
at 1.42 ppm as a triplet with a J (HH) value of 5.4 Hz.
In addition, we should mention the resonances corre-
sponding to the RuCH2- protons, which are observed
at 2.78 and 2.42 ppm, as a broad signal and as a broad
doublet with a J (HP) value of 8.7 Hz, respectively. In
the 13C{1H} NMR spectrum, the most noticeable reso-
nance is a doublet with a J (CP) value of 8.7 Hz, at -6.7
ppm, which was assigned to the RuCH2- carbon atom,
nyl)(CO)(PPri ) (5; eq 5) by MS, elemental analysis, IR
3
1
and H, 31P{1H}, and 13C{1H} NMR spectroscopy, and
an X-ray crystallographic study. A view of the molecular
geometry of the RuR,CR enantiomer is shown in Figure
3. Selected bond distances and angles are listed in Table
3.
As for 2 and 3, the geometry around the ruthenium
center in 5 is close to octahedral with the cyclopenta-
1
on the basis of a H-13C HETCOR NMR spectrum. In
benzene-d6 as solvent, the 31P{1H} NMR spectrum
shows a singlet at 68.5 ppm. This chemical shift is the
same as one of the five neutral compounds formed from
the reaction of 2 with sodium carbonate, suggesting that
during the formation of 3, a part of this compound
decomposes to give 4.
(23) Kreissl, F. R. In Transition Metal Carbene Complexes; Verlag
Chemie, Weinheim, Germany, 1983; p 180.
(24) Gribble, G. W. In Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Eds.; Pergamon Press: Oxford, U.K., 1991; Vol. 8, p
627.
(25) Sweeney, J . B. In Comprehensive Organic Functional Group
Transformations; Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.;
Elsevier: Oxford, U.K., 1995; Vol. 2, p 82.
The formation of 4 is noteworthy. In this context, it
should be mentioned that, in general, the treatment of
carbene complexes with metal hydrides affords hy-
dride-alkyl derivatives23 and that the reduction of
benzofurans with NaBH4/TFA yields dihydrobenzo-

Organometallic Compounds Containing Polycyclic Ligands
Organometallics, Vol. 19, No. 1, 2000
9
1
F igu r e 4. Partial view of the H-13C HETCOR NMR spectrum of the complex Ru(η5-C5H5){9-phenyl-1,3-dihydronaphtho-
[2,3-c]-1-furanyl}(CO)(PPri ) (5).
3
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex Ru (η5-C5H5)(9-p h en yl-1,3-
d ih yd r on a p h th o[2,3-c]-1-fu r a n yl)(CO)(P P r i3) (5)
Both six-membered rings of the dihydronaphtho-
furanyl ligand are almost planar, while the five-
membered heterocycle adopts an envelope conformation
with the O(2) atom out of the plane defined by the other
four atoms. In contrast to 3, the separation between the
O(2) atom and the carbon atom bonded to the metal
(O(2)-C(16) ) 1.479(3) Å) is longer than the separation
between O(2) and the other adjacent carbon atom (O(2)-
C(19) ) 1.434(4) Å).
Ru(1)-P(1)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Ru(1)-C(4)
Ru(1)-C(5)
Ru(1)-C(15)
Ru(1)-C(16)
2.3434(7)
2.284(3)
2.285(3)
2.274(3)
2.260(3)
2.283(3)
1.836(3)
2.203(3)
O(1)-C(15)
O(2)-C(16)
O(2)-C(19)
C(16)-C(17)
C(17)-C(18)
C(18)-C(19)
1.168(3)
1.479(3)
1.434(4)
1.509(4)
1.431(4)
1.506(4)
The phenyl group bonded to the C(27) carbon atom is
rotated by 64.4(1)° with regard to the plane defined by
the 10 carbon atoms of the naphthyl group. However,
P(1)-Ru(1)-Ga
126.97(10) O(2)-C(16)-C(17)
101.5(2)
104.6(2)
P(1)-Ru(1)-C(15)
P(1)-Ru(1)-C(16)
G-Ru(1)-C(15)
G-Ru(1)-C(16)
C(15)-Ru(1)-C(16)
Ru(1)-C(15)-O(1)
91.07(8)
89.98(7)
121.2(2)
O(2)-C(19)-C(18)
C(16)-C(17)-C(27) 132.2(2)
C(16)-C(17)-C(18) 107.5(2)
1
the H and 13C{1H} NMR spectra of 5 suggest that in
solution the phenyl is parallel to the furanyl plane.
126.48(13) C(18)-C(17)-C(27) 120.2(2)
1
Figure 4 shows a partial view of the H-13C HETCOR
90.45(11) C(16)-O(2)-C(19)
107.3(2)
1
172.0(3)
C(17)-C(18)-C(19) 107.4(2)
C(17)-C(18)-C(20) 121.7(3)
C(19)-C(18)-C(20) 130.9(3)
NMR spectrum of 5. In the H part of the spectrum the
Ru(1)-C(16)-C(17) 114.6(2)
Ru(1)-C(16)-O(2)
most noticeable signals are a doublet at 7.50 ppm, with
a J (HP) value of 10.8 Hz, corresponding to the Ru-CH
proton, and two double doublets at 5.53 and 5.05 ppm,
with J (HH) values of 12.7 and 1.2 and of 12.7 and 0.9
Hz, respectively, due to the OCH2 protons. In the 13C-
{1H} NMR part of the spectrum, the equivalent carbons
are a doublet at 71.3 ppm with a J (CP) value of 9.7 Hz
for the doublet at 7.50 ppm and a singlet at 69.2 ppm
for both double doublets. The above-mentioned chemical
shifts are displaced toward lower field with regard to
those expected for MCHO and CH2O groups. In this
context, it should be noted that these groups of the five-
membered heterocycle lie in the region of a negative
shielding contribution produced by the ring current
effect of the central ring of the naphthofuranyl ligand.
In addition, it should be noted that the resonances of
the RuCHO group appear at lower fields that those
112.2(2)
a
G is the centroid of the C(1)-C(5) Cp ligand.
dienyl ligand occupying three sites of a face. The angles
formed by the triisopropylphosphine, the carbonyl group,
and the heterocyclic ligand are all close to 90°.
The five-membered heterocycle is coordinated to the
ruthenium center with a Ru(1)-C(16) bond length of
2.203(3) Å. This value is comparable to the ruthenium-
carbon bond lengths reported for the methyl complexes
Ru(CH3){(E)-CHdCHPh}(CO)(PPri3)2 (2.205(4) Å),26 Ru-
(CH3)I(η4-NBD)(dad) (NBD ) norbornadiene, dad )
glyoxalbis(isopropylimine); 2.222(13) Å),27 (+)-[Ru(CH3)-
(CO)(CNBut)(triphos)]+ (2.209(5) Å),28 and [cis-Ru(CH3)-
(PMe3)4]2Hg (2.205(4) Å).29
(26) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro,
L. A. Organometallics 1995, 14, 4685.
(27) Rohde, W.; tom Dieck, H. J . Organomet. Chem. 1990, 385, 101.
(28) Hommeltoft, S. I.; Cameron, A. D.; Shackleton, T. A.; Fraser,
M. E.; Fortier, S.; Baird, M. C. Organometallics 1986, 5, 1380.
(29) Statler, J . A.; Wilkinson, G.; Thornton-Pett, M.; Hursthonse,
M. B. J . Chem. Soc., Dalton Trans. 1984, 1731.

10 Organometallics, Vol. 19, No. 1, 2000
Esteruelas et al.
corresponding to the CH2O group. According to the
structure shown in Figure 3, the RuCHO group lies in
the region of a positive shielding contribution produced
by the ring current effect of the phenyl group, while the
CH2O group is out of this region. This should produce
a selective decrease of the effect of the central ring on
the RuCHO chemical shifts. Therefore, it is only possible
to explain the chemical shifts observed for the RuCHO
group by assuming that in solution the disposition of
the phenyl group is not that shown in Figure 3, but
parallel to the naphtho-furanyl ring. In this way, the
RuCHO group would lie in the region of a negative
shielding contribution of the phenyl ring, increasing the
effect of the naphtho-furanyl ring instead of decreasing
it.
new isomerization of 5 is observed. Under these condi-
tions, the complex Ru(η5-C5H5){CH2(1-phenyl-3-carboxa-
2-naphthyl}(CO)(PPri ) (7) is obtained as a yellow solid
3
in 29% yield (eq 7). This isomerization involves a
Treatment in a Schlenk tube of a pentane/diethyl
ether (5:1) suspension of 5 with Al2O3 results in the
epimerization of the RuR,CR;RuS,CS racemic mixture (eq
6). The new pair of enantiomers (6), which is also
hydrogen transfer, within the heterocycle of 5, from
C(19) to C(16). The process could proceed via the
zwitterionic carbene intermediate A. Using a molecular
model, it can be observed that in this intermediate the
hydrogen transfer from the -CH2O- group into the Rud
C carbon atom is highly favored from a geometrical
point of view.
The presence of an aldehyde group in the alkyl ligand
of 7 is strongly supported by the IR and 1H and 13C-
{1H} NMR spectra of this compound. The IR spectrum
in Nujol contains a ν(CdO) band at 1681 cm-1. In the
1H NMR spectrum in benzene-d6 the HCO resonance
appears at 11.33 ppm as a singlet. In addition, the
spectrum shows at 3.07 ppm a doublet with a J (HH)
value of 9.0 Hz and at 2.74 ppm a double doublet with
both J (HH) and J (HP) values of 9.0 Hz. Both resonances
were assigned to the alkyl protons. In the 13C{1H} NMR
spectrum, the resonance corresponding to the HCO
carbon atom appears at 193.3 ppm as a singlet, whereas
that due to the RuCH2 carbon atom is observed at -5.5
ppm as a doublet with a J (CP) value of 9.3 Hz. The 31P-
{1H} NMR spectrum contains a singlet at 68.5 ppm.
present as a very minor component in the crude
products resulting from the treatment of 2 with sodium
carbonate and sodium methoxide (31P{1H} NMR: δ
70.0), is obtained as a pure crystalline solid in 33% yield
with regard to 2, when the crude products resulting
from the treatment of 2 with sodium methoxide are
purified by column chromatography using a pentane/
diethyl ether (5:1) mixture as eluent. The epimerization
process could involve the cleavage of the O(2)-C(16)
bond of 5 to give the zwitterionic carbene A (Scheme
3). Thus, the approach of the oxygen atom over or under
the Ru-C double bond should give rise to 5 or 6.
This chemical shift is as that of one of the minor
components of the initial crude products, suggesting
that complex 7 is also formed during the treatment of
2 with bases.
Sch em e 3
4. Rea ction of 2 w ith Al2O3. The complex Ru(η5-
C5H5){9-phenyl-3,3a-dihydronaphtho[2,3-c]-1-furanyl}-
(CO)(PPri ) (8), which is another isomer of 5, can be
3
obtained directly from 2 by passing this complex through
an alumina column using a tetrahydrofuran/dichlo-
romethane (5:1) mixture as eluent. By this procedure,
complex 8 was obtained as a yellow solid in 38% yield
(eq 8).
1
In the H NMR spectrum of 6, the RuCHO resonance
appears at 7.21 ppm, as a doublet with a J (HP) value
of 4.5 Hz, whereas the resonances due to the CH2O
group are observed at 4.97 and 4.76 ppm, as doublets
with a J (HH) value of 13.2 Hz. In the 13C{1H} NMR
spectrum the Ru-C carbon atom gives rise to a doublet
at 75.9 ppm with a J (CP) value of 8.3 Hz, and the CH2
carbon atom displays a singlet at 69.0 ppm.
When the purification of the crude products contain-
ing 5 as the main component is carried out by column
chromatography using an increasing polarity mixture
of toluene/diethyl ether (from 10:1 to 1:10) as eluent, a
The position of the C-C double bond within the
unsaturated η1-carbon ligand of 8 is strongly supported

Organometallic Compounds Containing Polycyclic Ligands
Organometallics, Vol. 19, No. 1, 2000 11
Sch em e 4
mediate B could evolve via an intramolecular Diels-
Alder reaction similar to that previously described for
the allyloxyallenyl complex Ru(η5-C5H5){C(OCH2CHd
CH2)dCdCPh2}(CO)(PPri ) (Scheme 2), where the Câ-
3
Cγ double bond and one of the two phenyl groups of the
alkenyl-carbene unit of B act as an inner-outer ring
diene, while the terminal C-C double bond of the allene
moiety should act as a dienophile. Subsequently, a 1,3-
hydrogen shift from the CH2 group of the central six-
membered ring to the OCH- carbon atom in the
resulting intermediate C would give D. A further step
of aromatization32 of D should afford complex 3.
The formation of complex 5 can be explained as
follows. Deprotonation of intermediate D at the carbon
C9a would give intermediate E. Subsequently, a 1,5-
hydrogen shift from carbon C4a to C1 should afford 5.
There is precedent for this hydrogen migration. We have
previously shown that the protonation of Ru(η5-C5H5)-
{9-phenyl-3,3a,4,4a-tetrahydronaphtho[2,3-c]-1-furanyl}-
(CO)(PPri ) affords the cation [Ru(η5-C5H5){9-phenyl-
3
1,3,3a,4,4a,9a-hexahydronaphtho[2,3-c]-1-furanylidene}-
(CO)(PPri )]+, which is stable in solution at low tem-
3
perature. At room temperature, it evolves into the
cationic acyclic alkoxycarbene derivative Ru(η5-C5H5)-
{C(OCH2[1-phenyl-3,4-dihydro-3-naphthyl])H}(CO)(P-
Pri ) as a result of the intramolecular hydrogen transfer
3
from C4a to C1.12 Alternatively, complex 5 could be
formed by deprotonation of intermediate D at C4a and
a hydrogen migration from C9a to C1.
Complex 8 could be the result of a 1,3-hydrogen
migration from C3 to C4 on intermediate E.
by the 1H and 13C{1H} NMR spectra of this compound.30
The 1H NMR spectrum shows the resonances corre-
sponding to the triisopropylphosphine and cyclopenta-
dienyl ligands, along with eight signals at 7.38, 6.14,
5.89, 5.67, 5.46, 3.40, 2.61, and 2.36 ppm, which accord-
1
ing to a H-1H COSY NMR spectrum correspond to the
Con clu d in g Rem a r k s
H(3), H(8), H(6), H(5), H(7), H(4a), H(4), and H(4′)
protons, respectively. In the 13C{1H} NMR spectrum the
most noticeable resonances are a doublet at 170.0 ppm
with a J (PC) value of 12.4 Hz, assigned to C(1), and
three singlets at 138.0, 40.3, and 28.4 ppm, which
correspond to the carbon atoms C(3), C(4a), and C(4),
We have previously shown that the allenylidene
complex [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri )]BF4 (1)
3
reacts with methanol, ethanol, and allyl alcohol to give
the R,â-unsaturated alkoxycarbene derivatives [Ru(η5-
C5H5){C(OR)CHdCPh2}(CO)(PPri )]BF4 (R ) Me, Et,
3
CH2CHdCH2), which by deprotonation afford the cor-
responding alkoxy-allenyl compounds. This study has
revealed that complex 1 also adds propargyl alcohol. The
reaction is similar to those with the above-mentioned
alcohols, and the R,â-unsaturated propargyloxycarbene
1
respectively, according to the H-13C HETCOR NMR
spectrum.
The 31P{1H} NMR spectrum of 8 in benzene-d6 shows
a singlet at 72.0 ppm. Although this chemical shift
seems to indicate that complex 8 is also a minor
component of the crude products resulting from the
treatment of 2 with sodium carbonate and sodium
methoxide, the aromatic character of the six-membered
rings of its isomers 5-7 suggests that it is not derived
from these compounds.
[Ru(η5-C5H5){C(OCH2CtCH)CHdCPh2}(CO)(PPri )]-
3
BF4 (2) is obtained. However, the treatment of 2 with
bases does not afford an allenyl derivative but a mixture
of six different cycloaddition products. The main com-
ponent of the mixture depends on the nature of the base
used.
5. Com m en ts on th e F or m a tion of Der iva tives
3, 5, a n d 8. The formation of complexes 3, 5, and 8 can
be rationalized according to Scheme 4. Since the forma-
tion of these compounds occurs under basic conditions,
and it is well-known that bases catalyze the isomeriza-
tion of propargylic into allenic moieties,31 it seems
reasonable to propose an alkyne-allene rearrangement
to give B as the first step of the reaction. This inter-
In the presence of 1 equiv of sodium carbonate the
polycyclic carbene complex [Ru(η5-C5H5){9-phenyl-1,3-
dihydronaphtho[2,3-c]-1-furanylidene}(CO)(PPri )]BF4
3
(3) is obtained, which by reaction with NaBH4 affords
Ru(η5-C5H5){CH2(1-phenyl-3-hydroxymethyl-2-naph-
thyl)}(CO)(PPri ) (4).
3
Treatment of 2 with 3 equiv of sodium methoxide
gives rise to the RuR,CR;RuS,CS racemic mixture of the
dihydronaphtho-furanyl complex Ru(η5-C5H5){9-phen-
(30)
(31) Huntsman, W. D. In The chemistry of Ketenes, Allenes, and
Related Compounds; Patai, S., Ed.; Wiley: Chichester, U.K., 1980;
Chapter 15.
(32) (a) March, J . In Advanced Organic Chemistry, 2nd ed.; McGraw-
Hill: New York, 1984; p 1077. (b) Bruce, M. I.; Hinterding, P.; Ke, M.;
Low, P. J .; Skelton, B. W.; White, A. H. Chem. Commun. 1997, 715.

12 Organometallics, Vol. 19, No. 1, 2000
Esteruelas et al.
yl-1,3-dihydronaphtho[2,3-c]-1-furanyl}(CO)(PPri ) (5),
J (PH) ) 14.7, PCHCH3), 1.05 (dd, 9H, J (HH) ) 7.2, J (PH) )
14.4, PCHCH3). 31P{1H} NMR (121.4 MHz, 20 °C, CDCl3): δ
69.1 (s). 13C{1H} NMR (75.4 MHz, 20 °C, CDCl3, plus HET-
COR): δ 293.3 (d, J (PC) ) 9.7, RudC), 202.0 (d, J (PC) ) 18.4,
CO), 146.5, 143.4, 138.1, 136.4, 135.8, 133.9 (all s, Cipso), 132.5,
132.3, 130.6, 129.2, 129.1, 128.8, 128.3, 128.0, 127.3, 120.9 (all
a, CH), 87.2 (s, Cp), 86.1 (s, CH2O), 26.9 (d, J (PC) ) 23.4,
PCHCH3), 19.5 (s, PCHCH3).
3
which within a chromatography column epimerizes to
the corresponding RuR,CS;RuS,CR racemic form (6) or
is transformed into its isomer Ru(η5-C5H5){CH2(1-phen-
yl-3-carboxa-2-naphthyl}(CO)(PPri3) (7), depending upon
the polarity of the eluent used.
Complex 2 is also deprotonated by Al2O3. When this
complex is passed through an alumina column using a
tetrahydrofuran/dichloromethane (5:1) mixture as elu-
ent, the isomer of 5, Ru(η5-C5H5){9-phenyl-3,3a-dihy-
P r epar ation of Ru (η5-C5H5){CH2(1-ph en yl-3-h ydr oxym -
eth yl-2-n a p h th yl)}(CO)(P P r i3) (4). An orange suspension of
3 (250 mg, 0.36 mmol) in 10 mL of tetrahydrofuran at room
temperature was treated with sodium borohydride (27 mg, 0.72
mmol). The mixture was stirred for 5 min to obtain a yellow
suspension, which was concentrated to ca. 1 mL and chro-
matographed on alumina. Tetrahydrofuran eluted a yellow
fraction, from which solvent was removed in vacuo. The
residue was washed with cold pentane to afford 4 as a yellow
solid. Yield: 76 mg (36%). Anal. Calcd for C33H41O2PRu: C,
65.87; H, 6.87. Found: C, 65.58; H, 6.84. IR (Nujol, cm-1): ν-
(OH) 3572 (vs); ν(CO) 1887 (vs); ν(Ph, CdC) 1619, 1595 (w).
1H NMR (300 MHz, 20 °C, C6D6, plus COSY): δ 8.10-7.13
(8H, Ar), 5.42 (m, 1H, CHHO), 5.21 (m, 1H, CHHO), 4.36 (s,
5H, Cp), 2.78 (br, 1H, Ru-CHH), 2.42 (br d, 1H, J (PH) ) 8.7,
Ru-CHH), 1.78 (m, 3H, PCHCH3), 1.42 (t, 1H, J (HH) ) 5.4,
OH), 0.85 (dd, 9H, J (HH) ) 7.2, J (PH) ) 13.8, PCHCH3), 0.72
(dd, 9H, J (HH) ) 6.9, J (PH) ) 12.3, PCHCH3). 31P{1H} NMR
(121.4 MHz, 20 °C, C6D6): δ 68.5 (s). 13C{1H} NMR (75.4 MHz,
20 °C, C6D6, plus HETCOR): δ 209.8 (br, CO), 152.3, 142.0,
138.9, 133.2, 130.9, 125.2 (all s, Cipso), 132.6, 132.1, 129.1,
128.4, 128.3, 126.5, 126.0, 125.5, 125.2, 123.2 (all s, CH), 86.1
(s, Cp), 64.1 (s, CH2O), 26.4 (d, J (PC) ) 21.6, PCHCH3), 19.9,
18.9 (both s, PCHCH3), -6.7 (d, J (PC) ) 8.7, Ru-CH2). MS
(FAB+): m/z 602 ([M]+).
dronaphtho[2,3-c]-1-furanyl}(CO)(PPri ) (8), is formed.
3
In conclusion, in the presence of bases, the carbene
complex 2 evolves into novel organometallic products
which are the result of the loss of two (3) or one (5 and
8) hydrogen atom and the intramolecular formation of
two C-C bonds, the terminal C(sp) carbon atom of the
propargyl alkoxy unit with an ortho carbon atom of one
of the two phenyl groups, and the internal C(sp) carbon
atom of the propargyloxy fragment with the CH carbon
atom of the alkenyl unit.
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting material [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri3)]BF4 (1)
was prepared by the published method.10
In the NMR spectra, chemical shifts are expressed in ppm
downfield from Me4Si (1H and 13C) and 85% H3PO4 (31P).
Coupling constants, J , are given in hertz.
P r ep a r a tion of (Ru R,CR;Ru S,CS)-Ru (η5-C5H5)(9-p h en yl-
1,3-d ih yd r on a p h th o[2,3-c]-1-fu r a n yl)(CO)(P P r i3) (5). A
yellow suspension of 2 (250 mg, 0.36 mmol) in 10 mL of
tetrahydrofuran at -78 °C was treated with sodium methoxide
(59 mg, 1.09 mmol). The mixture was stirred for 2 h, while
the temperature was slowly increased to 25 °C. The color
changed to deep red, and the solvent was evaporated in vacuo.
The residue was extracted with 2 mL of diethyl ether and
chromatographed on alumina. Diethyl ether eluted a yellow
fraction from which solvent was evaporated in vacuo. The
residue was washed with cold pentane to afford 5 as a yellow
solid. Yield: 116 mg (53%). Anal. Calcd for C33H39O2PRu: C,
66.09; H, 6.55. Found: C, 66.00; H, 6.47. IR (Nujol, cm-1): ν-
(CO) 1913 (vs); ν(Ph) 1622 (w). 1H NMR (300 MHz, 20 °C,
C6D6): δ 7.83-7.67 (2H, Ar), 7.50 (d, 1H, J (PH) ) 10.8, Ru-
CH), 7.52-7.08 (8H, Ar), 5.53 (dd, 1H, J (HH) ) 12.7, J (HH)
) 1.2, CHHO), 5.05 (dd, 1H, J (HH) ) 12.7, J (HH) ) 0.9,
CHHO), 4.31 (s, 5H, Cp), 1.97 (m, 3H, PCHCH3), 1.01, 0.87
(both dd, 18H, J (HH) ) 7.2, J (PH) ) 13.2, PCHCH3). 31P{1H}
NMR (121.4 MHz, 20 °C, C6D6): δ 67.3 (s). 13C{1H} NMR (75.4
MHz, 20 °C, C6D6, plus HETCOR): δ 208.3 (d, J (PC) ) 21.2,
CO), 156.6, 141.6, 140.2, 132.3, 132.2, 125.4 (all s, Cipso), 132.1,
131.7, 129.5, 128.4, 127.8, 127.1, 125.6, 125.5, 124.3, 118.9 (all
s, CH), 85.7 (d, J (PC) ) 0.9, Cp), 71.3 (d, J (PC) ) 9.7, Ru-
CH), 69.2 (s, CH2O), 27.9 (d, J (PC) ) 21.2, PCHCH3), 19.8,
19.7 (both s, PCHCH3).
P r ep a r a tion of (Ru R,CS;Ru S,CR)-Ru (η5-C5H5)(9-p h en yl-
1,3-d ih yd r on a p h th o[2,3-c]-1-fu r a n yl)(CO)(P P r i3) (6). A
yellow suspension of 2 (250 mg, 0.36 mmol) in 10 mL of
tetrahydrofuran at -78 °C was treated with sodium methoxide
(59 mg, 1.09 mmol). The mixture was stirred for 2 h, while
the temperature was slowly increased to 25 °C. The color
changed to deep red, and solvent was evaporated in vacuo.
The suspension was extracted with 2 mL of dichloromethane
and chromatographed on alumina. A pentane/diethyl ether
mixture (5:1) eluted a yellow fraction from which solvent was
evaporated in vacuo. The residue was washed with pentane
at 193 K to afford 6 as a yellow solid. Yield: 73 mg (33%).
P r epar ation of [Ru (η5-C5H5){C(OCH2CtCH)CHdCP h 2}-
(CO)(P P r i3)]BF 4 (2). A 350 mg portion of 1 was dissolved in
10 mL of propargyl alcohol, and the solution was stirred for
30 h at 40 °C. The color changed from deep red to brown, and
the solvent was removed in vacuo. The residue was repeatedly
washed, first with diethyl ether and then with a diethyl ether/
tetrahydrofuran (1/2) mixture, to afford an orange solid.
Yield: 334 mg (88%). Anal. Calcd for C33H40BF4O2PRu: C,
57.65; H, 5.86. Found: C, 57.24; H, 5.47. IR (Nujol, cm-1): ν-
(tCH) 3255 (m); ν(CtC) 2126 (w); ν(CO) 1973 (s); ν(Ph, CdC)
1590, 1570 (both w); ν(C-O) 1269, 1174 (s); ν(BF4) 1061 (br).
1H NMR (300 MHz, 20 °C, CDCl3): δ 7.52-7.17 (m, 10H, Ph),
6.59 (s, 1H, HCd), 5.50, 5.12 (both br, OCH2), 5.01 (s, 5H, Cp),
2.75 (t, 1H, J (HH) ) 2.4, tCH), 2.29 (m, 3H, PCHCH3), 1.27
(dd, 9H, J (HH) ) 7.2, J (PH) ) 15.3, PCHCH3), 1.22 (dd, 9H,
J (PH) ) 7.2, J (PH) ) 15.3, PCHCH3). 31P{1H} NMR (121.4
MHz, 20 °C, CDCl3): δ 65.6 (br). 13C{1H} NMR (75.4 MHz, 20
°C, CDCl3, plus HETCOR): δ 305.1 (br, RudC), 202.8 (d, J (PC)
) 15.5, CO), 139.7, 137.6 (both s, Cipso-Ph + HCdCPh2), 136.0
(br s, HCdCPh2) 131.7, 129.8, 128.8, 128.7, 128.5 (all s, Ph),
89.8 (s, Cp), 79.6 (s, OCH2CtCH), 75.3 (s, OCH2CtCH), 66.3
(s, OCH2CtCH), 29.3 (d, J (PC) ) 24.2, PCHCH3), 19.8, 19.5
(both s, PCHCH3). MS (FAB+): m/z 601 ([M]+).
P r epar ation of [Ru (η5-C5H5)(9-ph en yl-1,3-dih ydr on aph -
th o[2,3-c]-1-fu r a n ylid en e)(CO)(P P r i3)]BF 4 (3). A yellow
suspension of 2 (250 mg, 0.36 mmol) in 10 mL of tetrahydro-
furan at room temperature was treated with sodium carbonate
(39 mg, 0.36 mmol). The mixture was stirred for 4 h, and the
color changed to deep orange. Solvent was evaporated in vacuo,
and 10 mL of dichloromethane was added. The mixture was
filtered, and the solvent was evaporated. The residue was
washed with tetrahydrofuran to afford 3 as an orange solid.
Yield: 75 mg (30%). Anal. Calcd for C33H38BF4O2PRu: C,
57.82; H, 5.59. Found: C, 57.77; H, 5.58. IR (Nujol, cm-1): ν-
(CO) 1964 (vs); ν(Ph) 1624 (w); ν(BF4) 1050 (br). 1H NMR (300
MHz, 20 °C, CDCl3): δ 8.20-7.29 (10H, Ar), 6.27 (d, 1H, J (HH)
) 18.9, CHHO), 6.03 (d, 1H, J (HH) ) 18.2, CHHO), 5.15 (s,
5H, Cp), 2.26 (m, 3H, PCHCH3), 1.10 (dd, 9H, J (HH) ) 7.2,

Organometallic Compounds Containing Polycyclic Ligands
Organometallics, Vol. 19, No. 1, 2000 13
Ta ble 4. Cr ysta l Da ta a n d Da ta Collection a n d Refin em en t for
{Ru (η5-C5H5){C(OCH2CtCH)CHdCP h 2}(CO)(P P r i3)}BF 4 (2),
{Ru (η5-C5H5)(9-p h en yl-1,3-d ih yd r on a p h th o[2,3-c]-1-fu r a n ylid en e)(CO)(P P r i3)}BF 4 (3), a n d
Ru (η5-C5H5)(9-p h en yl-1,3-d ih yd r on a p h th o[2,3-c]-1-fu r a n yl)(CO)(P P r i3) (5)
2
3
5
Crystal Data
formula
mol wt
C
33H40BF4O2PRu
C33H38BF4O2PRu
685.48
C33H39O2PRu
599.68
687.50
color and habit
symmetry, space group
a, Å
b, Å
yellow prism
monoclinic
11.121(1)
22.074(3)
13.558(2)
90.0
103.66(1)
90.0
3234.1(9)
4
orange prism
monoclinic
14.046(1)
12.430(1)
17.299(2)
90.0
97.36(2)
90.0
2995.4(7)
4
yellow prism
triclinic, P1h
9.330(1)
12.283(1)
14.073(2)
80.336(6)
74.546(6)
70.784
c, Å
R, deg
â, deg
γ, deg
V, Å3
·
1462.1(3)
2
1.362
D
calcd, g cm-3
1.412
1.520
Data Collection and Refinement
diffractometer
λ(Mo KR), Å
monochromator
µ, mm-1
Siemens-STOE AED-2
0.710 73
graphite oriented
0.585
Siemens-STOE AED-2
0.710 73
graphite oriented
0.632
Siemens-P4
0.710 73
graphite oriented
0.618
ω/2θ
scan type
ω/2θ
ω/2θ
2θ range, deg
temp, K
3 e 2θ e 50
3 e 2θ e 50
3 e 2θ e 50
293.0(2)
200.0(2)
200.0(2)
no. of data collect
6133 (h, -13 to 0; k, 0-26;
6551 (h, -16 to +16; k, -24 to +2;
5718 (h, -10 to +1; k, -14 to +13;
l, -15 to +16)
l, 0-20)
l, -16 to +16)
no. of unique data
no. of params refined
R1a (F2 > 2σ(F2))
wR2b (all data)
5683 (merging R factor 0.0361)
386
0.0437
0.0792
1.012
5269 (merging R factor 0.0179)
386
0.0282
0.0740
1.068
5138 (merging R factor 0.0292)
335
0.0310
0.0837
1.042
Sc (all data)
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2
.
c GOF ) S ) {∑[w(Fo - Fc2)2]/(n - p)2]}1/2, where n is the
a
b
2
2
number of reflections and p is the number of refined parameters.
Anal. Calcd for C33H39O2PRu: C, 66.09; H, 6.55. Found: C,
6.9, J (PH) ) 12.6, PCHCH3). 31P{1H} NMR (121.4 MHz, 20
°C, C6D6): δ 68.5 (s). 13C{1H} NMR (75.4 MHz, 20 °C, C6D6):
δ 208.8 (br, J (PC) ) 21.2, CO), 193.3 (s, HCO), 156.0, 140.8,
136.0, 134.2, 133.6, 130.0 (all s, Cipso), 132.4, 131.8, 130.3,
130.1, 129.2, 128.5, 128.2, 126.8, 126.2, 124.3 (all s, CH), 86.3
(s, J (PC) ) 1.4, Cp), 26.5 (d, J (PC) ) 22.1, PCHCH3), 19.8,
18.9 (both s, PCHCH3), -5.5 (d, J (PC) ) 9.3, Ru-CH).
Complex 7 could also be obtained, but not totally pure, by
stirring a suspension of 5 and alumina for 4 days. Pentane
was used as solvent.
P r epar ation of Ru (η5-C5H5)(9-ph en yl-3,3a-dih ydr on aph -
th o[2,3-c]-1-fu r a n yl)(CO)(P P r i3) (8). 2 (250 mg, 0.36 mmol)
was chromatographed on alumina. A tetrahydrofuran/dichlo-
romethane mixture (5:1) eluted a yellow fraction, from which
solvent was evaporated in vacuo. The residue was washed with
methanol at -78 °C to afford 8 as a yellow solid. Yield: 84
mg (38%). Anal. Calcd for C33H39O2PRu: C, 66.09; H, 6.55.
Found: C, 66.04; H, 6.91. IR (Nujol, cm-1): ν(CO) 1927 (vs);
ν(Ph, CdC) 1597, 1525 (both w). 1H NMR (300 MHz, 20 °C,
CD2Cl2, plus COSY): δ 7.38 (d, 1H, J (H3H4′) ) 1.5, H3), 7.37-
7.23 (5H, Ph), 6.14 (dd, 1H, J (H7H8) ) 9.6, J (H6H8) ) 0.9, H8),
5.89 (dddd, 1H, J (H5H6) ) 9.6, J (H7H6) ) 5.7, J (H4aH6) ) 2.4,
J (H6H8) ) 0.9, H6), 5.67 (ddd, 1H, J (H5H6) ) 9.6, J (H4aH5) )
4.5, J (H7H5) ) 2.1, H5), 5.46 (dddd, 1H, J (H7H8) ) 9.6, J (H7H2)
) 5.7, J (H7H5) ) 2.1, J (H4aH7) ) 1.2, H7), 4.73 (s, 5H, Cp),
3.40 (m, 1H, H4a), 2.61 (dd, 1H, J (H4′H4) ) 14.1, J (H4H4a) )
4.5, H4), 2.36 (ddd, 1H, J (H4′H4) ) 14.1, J (H4′H4a) ) 14.1,
J (H3H4′) ) 1.5, H4′), 2.07 (m, 3H, PCHCH3), 1.05 (dd, 9H,
J (HH) ) 7.2, J (PH) ) 12.9, PCHCH3), 1.03 (dd, 9H, J (HH) )
6.9, J (PH) ) 14.1, PCHCH3). 31P{1H} NMR (121.4 MHz, 20
°C, C6D6): δ 72.0 (s). 13C{1H} NMR (75.4 MHz, 20 °C, CD2Cl2,
plus HETCOR): δ 207.3 (d, J (PC) ) 19.5, CO), 170.0 (d, J (PC)
65.81; H, 6.80. IR (Nujol, cm-1): ν(CO) 1912 (vs); ν(Ph) 1626
1
(w). H NMR (300 MHz, 20 °C, C6D6): δ 7.94-7.72 (2H, Ar),
7.51-7.08 (8H, Ar), 7.21 (d, 1H, J (PH) ) 4.5, Ru-CH), 4.97,
4.76 (both d, 2H, J (HH) ) 13.2, CH2O), 4.60 (s, 5H, Cp), 2.35
(m, 3H, PCHCH3), 1.00 (dd, 9H, J (HH) ) 7.2, J (PH) ) 13.5,
PCHCH3), 0.97 (dd, 9H, J (HH) ) 7.2, J (PH) ) 12.3, PCHCH3).
31P{1H} NMR (121.4 MHz, 20 °C, C6D6): δ 70.0 (s). 13C{1H}
NMR (75.4 MHz, 20 °C, C6D6, plus HETCOR): δ 205.8 (d,
J (PC) ) 20.7, CO), 155.2, 139.9, 138.6, 133.1, 132.4, 127.9 (all
s, Cipso), 130.7, 130.4, 129.7, 128.6, 128.3, 127.8, 125.8, 125.6,
124.3, 118.2 (all s, CH), 85.8 (d, J (PC) ) 1.4, Cp), 75.9 (d, J (PC)
) 8.3, Ru-CH), 69.0 (s, CH2O), 26.3 (d, J (PC) ) 21.2,
PCHCH3), 20.2 (s, PCHCH3), 19.3 (d, J (PC) ) 0.9, PCHCH3).
Complex 6 could also be obtained, but not totally pure, by
stirring a suspension of 5 and alumina for 3 days. A pentane/
diethyl ether mixture (5:1) was used as solvent.
P r ep a r a tion of Ru (η5-C5H5)[CH2(1-p h en yl-3-ca r boxa -
2-n a p h th yl)](CO)(P P r i3) (7). A yellow suspension of 2 (250
mg, 0.36 mmol) in 10 mL of tetrahydrofuran at -78 °C was
treated with sodium methoxide (59 mg, 1.09 mmol). The
mixture was stirred for 2 h, while temperature was slowly
increased to 25 °C. The color changed to deep red, and solvent
was evaporated in vacuo. The residue was extracted with 2
mL of toluene and chromatographed on alumina. An increasing
polarity mixture of toluene/diethyl ether (from 10:1 to 1:10)
eluted a yellow fraction from which solvent was evaporated
in vacuo. The residue was washed with cold pentane to afford
7 as a yellow solid. Yield: 65 mg (29%). Anal. Calcd for
C
33H39O2PRu: C, 66.09; H, 6.55. Found: C, 65.93; H, 6.85. IR
(Nujol, cm-1): ν(CO) 1900 (vs); ν(HCdO) 1681 (s); ν(Ph, CdC)
1
1615, 1582 (m). H NMR (300 MHz, 20 °C, C6D6, plus COSY):
δ 11.33 (s, 1H, HCO), 8.56-7.02 (8H, Ar), 4.31 (s, 5H, Cp),
3.07 (d, 1H, J (HH) ) 9.0, Ru-CHH), 2.74 (dd, 1H, J (HH) )
J (PH) ) 9.0, Ru-CHH), 1.74 (m, 3H, PCHCH3), 0.81 (dd, 9H,
J (HH) ) 7.5, J (PH) ) 14.1, PCHCH3), 0.68 (dd, 9H, J (HH) )
) 12.4, C1), 140.8, 137.7, 135.3, 129.8, 121.1 (all s, Cipso-Ph
3a, C8a, C9, C9a), 132.4, 127.4, 126.3 (all s, Ph), 138.0 (s, C3),
131.3 (s, C5), 126.7 (s, C8), 123.3 (s, C6), 119.8 (s, C7), 85.8 (s,
,
C

14 Organometallics, Vol. 19, No. 1, 2000
Esteruelas et al.
Cp), 40.3 (s, C4a), 28.4 (s, C4), 27.8 (d, J (PC) ) 23.1, PCHCH3),
20.3, 19.8 (both s, PCHCH3).
the last cycles of refinement for all non-hydrogen atoms.
Hydrogen atoms were included in calculated or located posi-
tions and refined riding on their respective carbon atoms with
a fixed common thermal parameter. Atomic scattering factors,
corrected for anomalous dispersion, were implemented by the
program. Final convergence parameters are shown in Table
4.
X-r a y Str u ctu r e An a lysis of {Ru (η5-C5H5){C(OCH2Ct
CH)CHdCP h 2}(CO)(P P r i3)}BF 4 (2), [Ru (η5-C5H5)(9-p h en -
yl-1,3-dih ydr on aph th o[2,3-c]-1-fu r an yliden e)(CO)(P P r i )]-
3
BF 4 (3) a n d (Ru R,CR;Ru S,CS)-Ru (η5-C5H5)(9-p h en yl-1,3-
d ih yd r on a p h th o[2,3-c]-1-fu r a n yl)(CO)(P P r i3) (5). Crystals
suitable for the X-ray diffraction study were obtained by slow
diffusion of diethyl ether into a concentrated solution of 2 or
3 in dichloromethane or by diffusion of pentane into a concen-
trated solution of 5 in toluene. A summary of crystal data and
refinement parameters is reported in Table 4. Crystals of
approximate dimensions 0.40 × 0.23 × 0.15 mm (2), 0.40 ×
0.32 × 0.29 (3), and 0.62 × 0.36 × 0.16 (5) were glued on a
glass fiber and mounted on a Siemens-STOE (2 and 3) or
Siemens-P4 (5) diffractometer (sealed tube 2.4 kW, λ )
0.710 73 Å). All data were corrected for absorption using a
semiempirical method.33 The structures were solved by Patter-
son (Ru atoms) and conventional Fourier techniques and
refined by full-matrix least squares on F2 (SHELXL93 (2 and
3) and SHELXL9734 (5)). Anistropic parameters were used in
Ack n ow led gm en t. We acknowledge financial sup-
port from the DGES of Spain (Project PB98-1591).
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, experimental details of the
X-ray studies, and bond distances and angles for 2, 3, and 5.
This material is available free of charge via the Internet at
http://pubs.acs.org.
OM990456T
(34) Sheldrick, G. SHELX-93 and SHELX-97: Programs for Crystal
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