1,2,3-Diheterocyclization reactions on the allenylidene ligand of a ruthenium complex

Article abstract of DOI:10.1021/om980230a

The allenylidene complex [Ru(η⁵-C₅H₅)(C=C=CPh ₂)(CO)(PPrⁱ₃)]BF₄ (1) reacts with pyrazole to afford [Ru(η⁵-C₅H₅){C=CHC(Ph) ₂N(CH)₃N}(CO)(PPrⁱ₃)]BF₄ (2) as a result of the addition of pyrazole to the allenylidene of 1. The structure of 2 was determined by an X-ray investigation, revealing a Ru-C(bicycle) distance of 2.073(4) A?. Treatment of 2 with sodium methoxide deprotonates the bicycle, which also undergoes an opening process to give the functionalized alkynyl derivative Ru(η⁵-C₅H₅){CC(Ph)₂N(CH) ₃N}(CO)PPrⁱ₃) (3). The reactions of 1 with 3,5-dimethylpyrazole and 3-methylpyrazole lead to [Ru(η⁵-C₅H₅)-{C=CHC(Ph) ₂NC(R)CHC(CH₃)N}(CO)(PPrⁱ₃)]BF ₄ (R = CH₃ (8), H (9)). In the presence of sodium methoxide, complex 9 affords Ru(η⁵-C₅H₅){C=CC(Ph)₂N(CH) ₂C(CH₃)N}(CO)PPrⁱ₃) (10). The allenylidene ligand of 1 also adds pyridine-2-thiol. In this case, the reaction product is [Ru(η⁵-C₅H₅){C=CHC(Ph) ₂N(CH)₄CS}(CO)(PPrⁱ₃)]BF₄ (11), which yields the allenyl derivative Ru(η⁵-C₅H₅){C[SC(CH) ₄N]=C=CPh₂}(CO)(PPrⁱ₃) (12) by reaction with sodium methoxide.

Full text of DOI:10.1021/om980230a

Organometallics 1998, 17, 3567-3573
3567
1,2,3-Dih eter ocycliza tion Rea ction s on th e Allen ylid en e
Liga n d of a Ru th en iu m Com p lex
Miguel A. Esteruelas,* Angel V. Go´mez, Ana M. Lo´pez, and Enrique On˜ate
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received March 26, 1998
The allenylidene complex [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri3)]BF4 (1) reacts with pyrazole
to afford [Ru(η5-C5H5){CdCHC(Ph)2N(CH)3N}(CO)(PPri )]BF4 (2) as a result of the addition
3
of pyrazole to the allenylidene of 1. The structure of 2 was determined by an X-ray
investigation, revealing a Ru-C(bicycle) distance of 2.073(4) Å. Treatment of 2 with sodium
methoxide deprotonates the bicycle, which also undergoes an opening process to give the
functionalized alkynyl derivative Ru(η5-C5H5){CtCC(Ph)2N(CH)3N}(CO)(PPri ) (3). The
3
reactions of 1 with 3,5-dimethylpyrazole and 3-methylpyrazole lead to [Ru(η5-C5H5)-
{CdCHC(Ph)2NC(R)CHC(CH3)N}(CO)(PPri )]BF4 (R ) CH3 (8), H (9)). In the presence of
3
sodium methoxide, complex 9 affords Ru(η5-C5H5){CtCC(Ph)2N(CH)2C(CH3)N}(CO)(PPri )
3
(10). The allenylidene ligand of 1 also adds pyridine-2-thiol. In this case, the reaction product
is [Ru(η5-C5H5){CdCHC(Ph)2N(CH)4CS}(CO)(PPri3)]BF4 (11), which yields the allenyl deriva-
tive Ru(η5-C5H5){C[SC(CH)4N]dCdCPh2}(CO)(PPri3) (12) by reaction with sodium methoxide.
In tr od u ction
the allenylidene of 1. By deprotonation, the hydroxy-
carbene compound gives an acyl derivative and the
alkoxycarbene, thioalkoxycarbene, and 2-azaallenyl com-
plexes yield allenyl derivatives.2
As a part of our study on the chemistry of the five-
coordinate complex RuHCl(CO)(PPri ) ,1 we have previ-
3 2
ously shown that this compound is a useful starting
material for the preparation of new cyclopentadienyl-
ruthenium compounds, including the allenylidene de-
The reactions of 1 with the RXH molecules require
transition states which favor the transfer of the elec-
trophilic hydrogen atom from the RXH substrates to the
Câ atom of the allenylidene, by means of an X- - -CR
interaction. Thus, RH molecules such as phenylacety-
lene and methane, which do not contain an X nucleo-
philic leading heteroatom, do not react with 1. The
products resulting from the formal addition of the
H-C(sp) bond of phenylacetylene and a H-C(sp3) bond
of methane to the CR-Câ and Câ-Cγ double bonds of
the allenylidene of 1, [Ru(η5-C5H5){C(CtCPh)CHdCPh2}-
rivative [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri )]BF4 (1).2
3
An analysis of the electronic structure of this complex3
suggests that 60% of the LUMO is located on the
allenylidene ligand, mainly on the CR (23%) and Cγ
(31%) carbon atoms, while 20% of the HOMO is located
on the Câ atom of the same ligand. So, the CR and Cγ
atoms are electrophilic centers and Câ is nucleophilic.4
In agreement with this, complex 1 reacts with water,
alcohols, thiols, and benzophenone imine to afford R,â-
unsaturated-hydroxycarbene, -alkoxycarbene, -(alkyl-
thio)carbene, and -2-azaallenyl compounds, which are
a result of the addition of the H-X bond of the above-
mentioned RXH molecules to the CR-Câ double bond of
(CO)(PPri )]+ and [Ru(η5-C5H5){CdCHC(Ph)2CH3}(CO)-
3
(PPri )]+, respectively, are obtained by a general syn-
3
thetic strategy, which is in agreement with the electronic
character of the carbon atoms of the allenylidene, and
involves the initial nucleophilic attack of a carbanion
at the CR or Cγ atoms of the allenylidene ligand and the
subsequent protonation of the resulting allenyl or al-
kynyl derivatives.4
(1) Buil, M. L.; Elipe, S.; Esteruelas, M. A.; On˜ate, E.; Peinado, E.;
Ruiz, N. Organometallics 1997, 16, 5748 and references therein.
(2) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
Because the allenylidene of 1 has two electrophilic
and one nucleophilic centers, we asked ourselves whether
the reactions of this compound with molecules contain-
ing two nucleophilic heteroatoms and an electrophilic
hydrogen atom could give rise to 1,2,3-diheterocycliza-
tions. Although the reactivity of transition-metal allen-
ylidene compounds is presently attracting considerable
(3) (a) EHT-MO calculations on the allenylidene complexes Mn(η5-
C5H5)(CdCdCH2)(CO)2 and [Ru(η5-C9H7)(CdCdCPh2)(PPh3)2]+ have
been also carried out, see refs 3b and 3c, respectively. (b) Berke, H.;
Huttner, G.; von Seyerl, J . Z. Naturforsch. 1981, 36b, 1277. (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.
(4) Esteruelas, M. A.; Go´mez A. V.; Lo´pez, A. M.; Modrego, J .; On˜ate,
E. Organometallics 1997, 16, 5826.
S0276-7333(98)00230-1 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 07/18/1998

3568 Organometallics, Vol. 17, No. 16, 1998
Esteruelas et al.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex [Ru (η5-C5H5)-
{CdCHC(P h )2N(CH)3N}(CO)(P P r i3)]BF 4 (2)
Ru-P
2.350(1)
2.073(4)
1.843(3)
1.323(5)
1.522(5)
1.531(5)
1.518(6)
1.461(5)
N(1)-C(16)
N(1)-N(2)
N(2)-C(3)
N(2)-C(18)
C(16)-C(17)
C(17)-C(18)
O-C(19)
1.354(6)
1.357(4)
1.479(5)
1.341(5)
1.395(7)
1.382(6)
1.158(4)
Ru-C(1)
Ru-C(19)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(3)-C(10)
N(1)-C(1)
P-Ru-G(1)a
127.1(2)
92.4(1)
90.9(2)
118.8(2)
124.1(2)
94.9(2)
174.6(3)
135.2(3)
116.1(3)
121.3(2)
N(1)-C(1)-C(2)
N(1)-N(2)-C(3)
N(2)-N(1)-C(1)
N(2)-C(3)-C(2)
N(2)-C(3)-C(4)
N(2)-C(3)-C(10)
C(2)-C(3)-C(4)
C(2)-C(3)-C(10)
C(4)-C(3)-C(10)
103.3(3)
110.8(3)
111.5(3)
97.9(3)
111.2(3)
108.4(3)
106.8(3)
117.4(3)
114.1(3)
P-Ru-C(1)
P-Ru-C(19)
G(1)-Ru-C(1)a
G(1)-Ru-C(19)a
C(1)-Ru-C(19)
Ru-C(19)-O
Ru-C(1)-C(2)
C(1)-C(2)-C(3)
Ru-C(1)-N(1)
F igu r e 1. Molecular diagram for complex [Ru(η5-C5H5)-
{CdCHC(Ph)2N(CH)3N}(CO)(PPri )]BF4 (2). Thermal el-
3
lipsoids are shown at 50% probability.
interest,5 related reactions have not been previously
carried out. In this paper we report the answer to this
question.
a
G(1) is the midpoint of the C(20)-C(24) Cp ligand.
The unsaturated η1-carbon ligand can be described
as a cationic 1,1-diphenylpyrazolo[1,2-a]pyrazol-3-yl
group.6 The Ru-C(1) distance (2.073(4) Å) is slightly
Resu lts a n d Discu ssion
1. Rea ction of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
longer than those found in the alkenyl complexes Ru(η5-
C5H5){C(dCHCO2CH3)OC(O)CH3}(PPh3) (2.002(2) Å),7
(P P r i )]BF 4 w ith P yr a zole. Treatment of red dichlo-
3
romethane solutions of 1 with 2 equiv of pyrazole at
room temperature leads, after 5 min, to colorless solu-
Ru{C[dC(CO2CH3)CHdCHC(CH3)3]C(O)OCH3}Cl(CO)-
(PPh3)2 (2.03(1) Å),8 Ru{(E)-CHdCHC3H7}Cl(CO)-
(Me2Hpz)(PPh3)2 (2.05(1) Å),9 Ru{(E)-CHdCHCMe3}-
Cl(CO)(Me2Hpz)(PPh3)2 (2.063(7) Å),10 and [Ru{(E)-
CHdCHCMe3}(CO){NHdC(Me)(Me2pz)}(PPh3)2]PF6
(2.067(8) Å)11 and slightly shorter than the Ru-C bond
lengths in the complexes Ru(η5-C5H5){C(dCHPh)OPri}-
(CO)(PPh3) (2.103(6) Å),12 [Ru{C(dCHCO2CH3)CO2-
CH3}(CO)(NCCH3)2(PPh3)2]ClO4 (2.12(5) Å),13 and
tions from which the complex [Ru(η5-C5H5){CdCHC-
(Ph)2N(CH)3N}(CO)(PPri )]BF4 (2) is isolated as a result
3
of the addition of pyrazole to the allenylidene ligand of
1 (eq 1).
Ru(CH3){(E)-CHdCHPh}(CO)2(PPri ) (2.141(3) Å),14
3 2
where a Ru-C(sp2) single bond has been also proposed.
The C(1)-C(2) distance of 1.323(5) Å is in agreement
with the sample mean of carbon-carbon bond lengths
for double bonds (1.32(1) Å).15 In accordance with the
sp2 hybridization for C(1), the angles Ru-C(1)-N(1) and
Ru-C(1)-C(2) are 121.3(2)° and 135.2(3)°, respectively.
The C(1)-N(1) (1.461(5) Å) and C(3)-N(2) (1.479(5)
Å) distances are statistically identical and similar to the
N-C single-bond distances found in Schiff bases (about
1.47 Å) and amides (between 1.46 and 1.48 Å). How-
Complex 2 was obtained as a white solid in 86% yield
and characterized by elemental analysis, IR and 1H,
31P{1H}, and 13C{1H} NMR spectroscopies, and X-ray
diffraction. A view of the molecular geometry is shown
in Figure 1. Selected bond distances and angles are
listed in Table 1.
The geometry around the ruthenium center is close
to octahedral with the cyclopentadienyl ligand occupying
three sites of a face, and the angles formed by the
triisopropylphosphine, the carbonyl group and the un-
saturated η1-carbon ligand are close to 90°.
(6) Transition-metal compounds containing ligands of this type have
not been previously reported.
(7) Daniel, T.; Mahr, N.; Braun, T.; Werner, H. Organometallics
1993, 12, 1475.
(8) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J . J . Organomet. Chem.
1987, 326, 413.
(9) Torres, M. R.; Santos, A.; Perales, A.; Ros, J . J . Organomet.
Chem. 1988, 353, 221.
(10) Romero, A.; Santos, A.; Vegas, A. Organometallics 1988, 7, 1988.
(11) Lo´pez, J .; Santos, A.; Romero, A.; Echavarren, A. M. J .
Organomet. Chem. 1993, 443, 221.
(12) Bruce, M. I.; Duffy, D. N.; Humphrey, M. G.; Swincer, A. G. J .
Organomet. Chem. 1985, 282, 383.
(13) Lo´pez, J .; Romero, A.; Santos, A.; Vegas, A.; Echavarren, A.
M.; Noheda, P. J . Organomet. Chem. 1989, 373, 249.
(14) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro,
L. A. Organometallics 1995, 14, 4685.
(15) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.
(5) For some recent examples, see: (a) Touchard, D.; Pirio N.;
Dixneuf, P. H. Organometallics 1995, 14, 4920. (b) Wiedemann, R.;
Steinert, P.; Gevert, O.; Werner, H. J . Am. Chem. Soc. 1996, 118, 2495.
(c) Braun, T.; Meuer, P.; Werner, H. Organometallics 1996, 15, 4075.
(d) Werner, H. J . Chem. Soc., Chem. Commun. 1997, 903. (e) Werner,
H.; Lass, R. W.; Gevert, V.; Wolf, J . Organometallics 1997, 16, 4077.
(f) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda,
S. Organometallics 1997, 16, 3178. (g) Crochet, P.; Demerseman, B.;
Vallejo, M. I.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda,
S. Organometallics 1997, 16, 5406. (h) Cadierno, V.; Gamasa, M. P.;
Gimeno, J .; Lo´pez-Gonza´lez, M. C.; Borge, J .; Garc´ıa-Granda, S.
Organometallics 1997, 16, 4453. (i) Bohanna, C.; Callejas, B.; Edwards,
A. J .; Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C.
Organometallics 1998, 17, 373.

1,2,3-Diheterocyclization Reactions
Organometallics, Vol. 17, No. 16, 1998 3569
Sch em e 1
ever, they are about 0.1 Å longer than the N(1)-C(16)
(1.354(6) Å) and N(2)-C(18) (1.341(5) Å) bond lengths,
which, between them, are also statistically identical and
similar to those found in bridge pyrazolato ligands of
binuclear transition-metal compounds (about 1.34 Å).15
The C(16)-C(17) (1.395(7) Å), C(17)-C(18) (1.382(6) Å),
and N(1)-N(2) (1.357(4) Å) distances also agree well
with those found in the later type of compounds.
Both five-membered rings of the bicycle are almost
planar. For the N(1)-N(2)-C(3)-C(2)-C(1) ring, the
deviations from the best plane are 0.003(3) [N(1)],
-0.021(3) [N(2)], 0.043(4) [C(3)], -0.039(4) [C(2)], and
0.028(4) [C(1)] Å and the related parameters for the
Complex 3 was isolated as a white solid in 74% yield.
The presence of an alkynyl group in this complex is
mainly supported by its IR and 13C{1H} NMR spectra.
In the IR spectrum in Nujol, the ν(CtC) band is
observed at 2098 cm-1. In the 13C{1H} NMR spectrum,
the resonance corresponding to the CR atom of the
alkynyl ligand appears at 100.2 ppm as a doublet with
a C-P coupling constant of 21.3 Hz and that due to the
Câ atom is observed at 107.1 ppm, also as a doublet but
with a C-P coupling constant of 0.9 Hz.
N(1)-N(2)-C(18)-C(17)-C(16) ring are 0.002(3) [N(1)],
-0.002(3) [N(2)], 0.000(4) [C(18)], 0.002(4) [C(17)], and
-0.005(5) [C(16)] Å. The dihedral angle formed by the
least-squares planes through the atoms of both cycles
is 5.0(1)°. Similar values for the dihedral angle have
been found in related organic bicycles.16
In agreement with the salt character of 2, its IR
spectrum in Nujol shows the absorption due to the
[BF4]- anion with Td symmetry centered at 1053 cm-1
.
Because both the CR and Cγ atoms of the allenylidene
unit of 1 are electrophilic centers, the formation of 2
could occur by the reaction pathways shown in Scheme
1. According to pathway a , the first step of the reaction
shown in eq 1 should be the attack of pyrazole to the
CR atom of the allenylidene to give an allenyl intermedi-
ate, which could evolve to a functionalized R,â-unsatur-
ated carbene derivative by hydrogen transfer from the
other nitrogen atom of the pyrazole group to the central
carbon atom of the allenyl unit. Finally, the attack of
the free nitrogen atom of the pyrazole group at the Cγ
atom of the carbene should afford the bicyclic ligand.
According to pathway b, the reaction shown in eq 1,
should proceed by the initial addition of pyrazole at the
Cγ atom of allenylidene ligand of 1. The alkynyl
intermediate formed could afford a functionalized vi-
nylidene species as a result of the intramolecular attack
of the acidic hydrogen atom of the pyrazole to the Câ
atom of the alkynyl unit. Finally, the nucleophilic
attack of the free nitrogen atom of the pyrazole to the
CR atom of the vinylidene should give the bicyclic group.
In the 1H NMR spectrum in chloroform-d, the most
noticeable resonance is a singlet at 6.12 ppm corre-
sponding to the RuCdCH proton. In the 13C{1H} NMR
spectrum, the resonance due to the Ru-Cd carbon atom
appears at 144.7 ppm as a doublet with a C-P coupling
constant of 13.6 Hz whereas the resonance correspond-
ing to the dCH- carbon atom is observed at 137.2 ppm
as a singlet. The 31P{1H} NMR spectrum shows a
singlet at 66.6 ppm.
Treatment of 2 with sodium methoxide in tetrahy-
drofuran at room temperature deprotonates the bicycle,
which also undergoes an opening process to give the
functionalized alkynyl derivative Ru(η5-C5H5){CtCC-
(Ph)2N(CH)3N}(CO)(PPri ) (3, eq 2). Ruthenium and
3
rhodium compounds containing functionalized alkynyl
ligands of the type M-CtC-C(OR)R′2 have been re-
cently prepared by nucleophilic addition at the Cγ atom
of allenylidene ligands.17
(16) (a) Adams, H.; Bailey, N. A.; Denti, G.; McCleverty, J . A.; Smith,
J . M. A.; Wlodarczyk, A. J . Chem. Soc., Chem. Commun. 1981, 348.
(b) Adams, H.; Bailey, N. A.; Denti, G.; McCleverty, J . A.; Smith, J .
M. A.; Wlodarczyk, A. J . Chem. Soc., Dalton Trans. 1983, 2287. (c)
Raston, C. L.; White, A. H. Aust. J . Chem. 1984, 37, 2577. (d) Fujimura,
Y.; Nawata, Y.; Hamana, M. Hetrocycles 1986, 24, 2771.
(17) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J .
Organomet. Chem. 1994, 474, C27. (b) Werner, H.; Wiedemann, R.;
Laubender, M.; Wolf, J .; Windmu¨ller, B. J . Chem. Soc., Chem.
Commun. 1996, 1413.

3570 Organometallics, Vol. 17, No. 16, 1998
Esteruelas et al.
The addition of electrophiles to the electron-rich Câ
atom of metal alkynyl complexes has been described on
many occasions and is the best known entry into the
synthesis of vinylidene derivatives.18 So, if the reaction
shown in eq 1 proceeds via the pathway b of Scheme 1,
the protonation of the alkynyl complex 3 should afford
a functionalized vinylidene intermediate 7, which sub-
sequently should evolve into 2.
The addition at room temperature of 1 equiv of HBF4‚
OEt2 to 3 using dichloromethane as the solvent initially
gives rise to a change of color in the solution, from
colorless to the characteristic red of the allenylidene,
to finally afford a new colorless solution from which the
bicyclic complex 2 was isolated. The presence of the red
color during the transformation suggests that the
formation of 2 by protonation of 3 in dichloromethane
involves the initial release of pyrazole and its subse-
quent condensation with the allenylidene of 1. In
agreement with this, the 1H NMR spectrum of the
reaction mixture in dichloromethane-d2 shows reso-
nances of 1, 2, and 3. Furthermore, we have also
observed that the addition of 1 equiv of HBF4‚OEt2 to
diethyl ether solutions of 3 produces the precipitation
of 1 and the formation of a diethyl ether solution of
pyrazole.
and 7.10 ppm (2.44%), whereas the resonance of the
cyclopentadienyl protons is not affected. According to
these NOE experiments, we assign the resonance at 2.92
ppm to the methyl group situated at the side of the
metallic fragment and the resonance at 1.93 ppm to the
methyl group located at the side of the phenyl groups.
In the 13C{1H} NMR spectrum, the resonances due to
the Ru-Cd and dC-H carbon atoms appear at 140.0
and 139.3 ppm as doublets with C-P coupling constants
of 12.9 and 4.6 Hz, respectively. The 31P{1H} NMR
spectrum shows a singlet at 64.0 ppm.
These observations suggest (i) the most nucleophilic
center of 3 is the free nitrogen atom of the pyrazole
group and (ii) the splitting of the N-C bond of 6 is faster
than the hydrogen transfer from the N-H nitrogen
atom to the Câ atom of the alkynyl unit. So, it appears
to be reasonable to reject pathway b.
In the 1H NMR spectrum of 9 in chloroform-d, the
most noticeable resonances are those due to the protons
RuCdCH, C5H5, and CH3 of the bicyclic ligand, which
appear as singlets at 6.05, 4.34, and 2.97 ppm. In the
13C{1H} NMR spectrum, the resonances due to the Ru-
Cd and dCH- carbon atoms appear at 142.3 and 138.6
ppm as doublets with C-P coupling constants of 12.9
and 4.1 Hz, respectively. The 31P{1H} NMR spectrum
contains a singlet at 64.2 ppm.
The position of the methyl group in this bicycle was
determined by means of a NOE experiment. Irradiation
of the methyl resonance (δ 2.97) gave an increase in the
resonance of the cyclopentadienyl protons (3.2%), whereas
the resonances of the phenyl groups were not affected.
The selective formation of 9 with the methyl group
at the side of the metallic fragment merits some further
comment. The pyrazoles exist in solution as mixtures
of annular tautomers in different proportions, depending
upon the nature of the substituents. In the majority of
cases, the difference of free energy between both tau-
tomers is low enough for the chemical reactivity to be
unrelated to the equilibrium constant. In all the known
3(5)-substituted pyrazoles, the 3-substituted tautomer
predominates with the possible exception of 3(5)-methyl-
pyrazole in which the 5-methyl tautomer slightly pre-
dominates.19 So, if the reactions shown in eqs 1 and 3
proceed via pathway a of Scheme 1, only the 3-methyl-
pyrazole tautomer, the minor one in the tautomeric
equilibrium, is active.
At first glance, one could also think that the formation
of 2, according to eq 1, takes place by initial electrophilic
attack of the N-H pyrazole proton at the Câ atom of
the allenylidene to give a dicationic R,â-unsaturated
carbyne intermediate and subsequent nucleophilic ad-
dition of the two nitrogen atoms of the pyrazolato anion
at the CR and Cγ atoms of the carbyne. This, which is
in agreement with the placement of 20% of the HOMO
of 1 in Câ, must be also rejected because complex 1 does
not show any nucleophilic character. In fact, the
treatment of dichloromethane solutions of 1 with 1 equiv
of HBF4‚OEt2 does not produce any change in 1.
Complex 1 also reacts with substituted pyrazoles.
The reactions of 1 with 3,5-dimethylpyrazole and 3-
methylpyrazole in dichloromethane lead to the bi-
cyclic complexes [Ru(η5-C5H5){CdCHC(Ph)2NC(R)CHC-
(CH3)N}(CO)(PPri )]BF4 (R ) CH3 (8), H (9)). Complex
3
8 was isolated as a colorless oil in 85% yield, while
complex 9 was obtained as a white solid in 83% yield
(eq 3).
The 1H NMR spectrum of 8 in chloroform-d shows
singlets at 2.92 and 1.93 ppm corresponding to the
methyl groups of the bicyclic ligand. Irradiation of the
resonance at 2.92 ppm gives an increase in the reso-
nance of the cyclopentadienyl protons (3.16%), whereas
the resonances of the phenyl groups are not affected.
However, irradiation of the resonance at 1.93 ppm gives
increases in the ortho-phenyl resonances at 6.95 (2.89%)
Similarly to 2, complex 9 reacts with sodium meth-
oxide in tetrahydrofuran at room temperature to afford
the functionalized alkynyl derivative Ru(η5-C5H5)-
{CtCC(Ph)2N(CH)2C(CH3)N}(CO)(PPri ) (10), which
3
was isolated as a pale yellow solid in 79% (eq 4).
(19) Elguero, J . In Comprehensive Heterocyclic Chemistry; Katritzky,
A. R., Rees, C. W., Potts, K. T., Eds.; Pergamon Press: Oxford, 1984;
Vol. 5, Chapter 4.04.
(18) Bruce, M. I. Chem. Rev. 1991, 91, 197.

1,2,3-Diheterocyclization Reactions
Organometallics, Vol. 17, No. 16, 1998 3571
The protonation of 12 with HBF4‚OEt2 in dichloro-
methane and diethyl ether as solvents regenerates 11.
This suggests that the formation of 11 according to eq
5 proceeds by the reaction pathway shown in Scheme
2. In this context, it should be mentioned that we have
previously proved that the addition of thiols to the
allenylidene ligand of 1 and the protonation of (alkyl-
thio)allenyl complexes leads to R,â-unsaturated (alkyl-
thio)carbene derivatives.2
The most characteristic spectroscopic features of 10
are the CtC stretching frequency in the IR spectrum
in Nujol, which is observed at 2105 cm-1, and two
doublets with C-P coupling constants of 0.9 and 21.6
Hz in the 13C{1H} NMR spectrum at 107.1 and 99.7
ppm, for the Câ and CR alkynyl carbon atoms, respec-
tively.
2. Rea ction of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
(P P r i3)]BF 4 w ith P yr id in e-2-th iol. Treatment of
dichloromethane solutions of 1 with 1 equiv of pyridine-
2-thiol leads, after 5 min, to the complex [Ru(η5-C5H5)-
Con clu d in g Rem a r k s
This study has shown that, in fact, the allenylidene
ligand of the complex [Ru(η5-C5H5)(CdCdCPh2)(CO)-
{CdCHC(Ph)2N(CH)4CS}(CO)(PPri )]BF4 (11), which is
3
(PPri )]BF4 (1) undergoes 1,2,3-diheterocyclization reac-
3
formed as a result of the addition of pyridine-2-thiol to
the allenylidene ligand of 1 (eq 5).
tions with organic molecules containing two nucleophilic
heteroatoms and one electrophilic hydrogen atom. The
reaction products contain bicyclic ligands formed by five-
and six-membered rings, depending upon the nature of
the organic substrate. One of the rings of the bicycle
can be opened by deprotonation with sodium methoxide
to give selectively functionalized alkynyl and allenyl
derivatives.
In conclusion, we report the discovery of a new
reaction which affords the preparation of a new type of
organometallic compounds containing η1-carbon di-
heterobicyclic ligands.
Complex 11 was isolated as a yellow solid in 92%
yield. The saline character of the compound is sup-
ported by the IR spectrum in Nujol, which contains the
absorption due to the [BF4]- anion with Td symmetry
Exp er im en ta l Section
1
centered at 1051 cm-1. In the H NMR spectrum, the
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.2
NMR spectra were recorded on either a Varian UNITY 300,
a Varian GEMINI 2000, 300 MHz, or a Bruker 300 ARX
spectrometer. Chemical shifts are expressed in ppm upfield
from Me4Si (1H and 13C) and 85% H3PO4 (31P). Coupling
constants, J , are given in hertz. IR spectra were run on a
Nicolet 550 spectrophotometer (Nujol mulls on polyethylene
sheets or KBr pellets). Elemental analyses were carried out
on a Perkin-Elmer 2400 CHNS/O analyzer.
most noticeable resonance is that corresponding to the
RuCdCH proton, which appears at 6.38 ppm as a
singlet. In the 13C{1H} NMR spectrum, the resonance
due to the RuCd carbon atom appears at 142.1 ppm as
a doublet with a C-P coupling constant of 12.8 ppm
while that corresponding to the RuCdCH carbon is
observed at 132.1 ppm as a singlet. The 31P{1H} NMR
spectrum contains a singlet at 66.3 ppm.
Similarly to 2 and 9, complex 11 undergoes deproton-
ation in the presence of sodium methoxide. However,
in contrast to 2 and 9, the reaction product is not an
alkynyl derivative but the allenyl complex Ru(η5-C5H5)-
P r ep a r a tion of [Ru (η5-C5H5){CdCHC(P h )2N(CH)3N}-
{C[SC(CH)4N]dCdCPh2}(CO)(PPri ) (12), which was
3
(CO)(P P r i3)]BF 4 (2). A dark red solution of 1 (140 mg, 0.22
mmol) in 5 mL of dichloromethane was treated with pyrazole
(31 mg, 0.44 mmol), and the mixture was stirred for 5 min.
The solution became colorless, and the solvent was removed
in vacuo. The residue was washed with diethyl ether to afford
isolated as a yellow solid in 62% yield (eq 6).
The IR spectrum of 12 in Nujol shows the character-
istic CdCdC stretching frequency at 1869 cm-1, and
the 13C{1H} NMR spectrum contains the resonances due
to the carbon atoms of the allenyl unit at 198.3 (Câ),
103.9 (Cγ), and 88.6 (CR) ppm. The first and second
resonances appear as singlets, while the third one is
observed as a doublet with a C-P coupling constant of
12.1 Hz.
a white solid. Yield: 134 mg (86%). Anal. Calcd for C33H40
-
BF4N2OPRu: C, 56.67; H, 5.76; N, 4.00. Found: C, 56.69; H,
5.90; N, 4.00. IR (Nujol, cm-1): ν(CO) 1929 (vs), ν(CdC) 1541
(m), ν(BF4) 1053 (vs, br). 1H NMR (300 MHz, 293 K, CDCl3):
δ 8.39 (d, 1H, J (HH) ) 2.7, pz), 8.02 (d, 1H, J (HH) ) 2.7, pz),

3572 Organometallics, Vol. 17, No. 16, 1998
Esteruelas et al.
134.4 (both s, Cipso,pz), 129.5, 129.2, 129.0, 128.4, 128.1, 125.8
(all s, Ph), 113.9 (all s, pz), 85.8 (s, Cp), 78.9 (s, CPh2), 25.3 (d,
J (PC) ) 23.0, PCHCH3), 19.8 (s, PCHCH3), 18.8 (d, J (PC) )
1.4, PCHCH3), 14.3, 11.5 (both s, pz-CH3).
Sch em e 2
P r ep a r a t ion of [R u (η5-C5H 5){CdCH C(P h )2N(CH )2C-
(CH3)N}(CO)(P P r i3)]BF 4 (9). A dark red solution of 1 (80
mg, 0.13 mmol) in 5 mL of dichloromethane was treated with
3-methylpyrazole (11 µL, 0.14 mmol), and the mixture was
stirred for 10 min. The solution became colorless, and the
solvent was removed in vacuo. The residue was washed with
diethyl ether to afford a white solid. Yield: 75 mg (83%). Anal.
Calcd for C34H42BF4N2OPRu: C, 57.23; H, 5.93; N, 3.93.
Found: C, 56.90; H, 6.05; N, 3.84. IR (Nujol, cm-1): ν(CO)
1927 (vs), ν(CdC) 1549 (m), ν(BF4) 1049 (vs, br). 1H NMR (300
MHz, 293 K, CDCl3): δ 7.84 (d, 1H, J (HH) ) 3.0, pz), 7.34 (m,
6H, Ph), 7.12 (m, 2H, Ph), 6.90 (m, 2H, Ph), 6.80 (d, 1H, J (HH)
) 3.0, pz), 6.05 (s, 1H, Ru-CdCH), 4.34 (s, 5H, Cp), 2.97 (s,
3H, CH3), 2.16 (m, 3H, PCHCH3), 0.99 (dd, 9H, J (HH) ) 7.1,
J (PH) ) 13.3, PCHCH3), 0.98 (dd, 9H, J (HH) ) 6.9, J (PH) )
14.7, PCHCH3).31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ
64.2 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus dept):
δ 207.5 (d, J (PC) ) 20.7, CO), 142.3 (d, J (PC) ) 12.9, Ru-
Cd), 141.5, 140.0 (both s, CipsoPh), 138.6 (d, J (PC) ) 4.1, Ru-
CdCH), 137.5 (s, Cipso,pz), 129.7, 129.6, 129.3, 127.4, 125.6 (all
s, Ph), 128.4, 114.4 (both s, pz), 85.9 (s, Cp), 80.8 (s, CPh2),
25.5 (d, J (PC) ) 23.4, PCHCH3), 19.9 (s, PCHCH3), 18.9 (d,
J (PC) ) 1.4, PCHCH3), 14.4 (s, pz-CH3).
7.37 (m, 6H, Ph), 7.08 (vt, 1H, J (HH) ) 2.7, pz), 7.04 (m, 2H,
Ph), 6.97 (m, 2H, Ph), 6.12 (s, 1H, Ru-CdCH), 5.32 (s, 5H,
Cp), 2.09 (m, 3H, PCHCH3), 1.00 (dd, 9H, J (HH) ) 7.1, J (PH)
) 13.5, PCHCH3), 0.97 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.7,
PCHCH3).31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ 66.6
(s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3): δ 206.4 (d, J (PC)
) 18.1, CO), 144.7 (d, J (PC) ) 13.6, Ru-Cd), 138.9, 137.7
(both s, CipsoPh), 137.2 (s, Ru-CdCH), 130.8, 128.6, 112.5 (all
s, pz), 129.4, 129.3, 129.1, 126.8, 125.9 (all s, Ph), 85.6 (s, Cp),
80.8 (s, CPh2), 26.5 (d, J (PC) ) 26.5, PCHCH3), 19.7 (s,
PCHCH3), 19.0 (d, J (PC) ) 1.3, PCHCH3).
P r ep a r a tion of Ru (η5-C5H5){CtCC(P h )2N(CH)3N}(CO)-
(P P r i3) (3). A suspension of 2 (381 mg, 0.57 mmol) in 15 mL
of tetrahydrofuran was treated with sodium methoxide (62 mg,
1.14 mmol) and stirred for 48 h. The mixture became orange,
and the solvent was removed in vacuo. Toluene (15 mL) was
added, and the suspension was filtered to eliminate sodium
tetrafluoroborate. Solvent was evaporated, and the residue
was washed with methanol to afford a white solid. Yield: 257
mg (74%). Anal. Calcd for C33H39ON2PRu: C, 64.79; H, 6.43;
N, 4.58. Found: C, 64.60; H, 5.94; N, 4.65. IR (Nujol, cm-1):
ν(CtC) 2098 (m), ν(CO) 1928 (vs). 1H NMR (300 MHz, 293
K, C6D6): δ 8.80 (d, 1H, J (HH) ) 2.3, pz), 7.81 (m, 4H, Ph),
7.19 (m, 7H, Ph + pz), 6.27 (vt, 1H, J (HH) ) 2.3, pz), 4.83 (s,
5H, Cp), 1.89 (m, 3H, PCHCH3), 1.00 (dd, 9H, J (HH) ) 7.1,
J (PH) ) 14.7, PCHCH3), 0.79 (dd, 9H, J (HH) ) 7.1, J (PH) )
13.2, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ
74.6 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus apt): δ
205.4 (d, J (PC) ) 17.9, CO), 145.3, 145.1 (both s, CipsoPh), 139.5,
130.7 (both s, pz), 128.4, 128.1, 127.2, 127.1, 126.7, 126.6 (all
s, Ph), 107.1 (d, J (PC) ) 0.9, Ru-CtC), 103.5 (s, pz), 100.2
(d, J (PC) ) 21.3, Ru-CtC), 85.3 (d, J (PC) ) 0.9, Cp), 71.1 (s,
CPh2), 29.8 (d, J (PC) ) 23.9, PCHCH3), 19.9 (s, PCHCH3), 19.2
(d, J (PC) ) 1.8, PCHCH3).
P r ep a r a t ion of R u (η5-C5H 5){CtCC(P h )2N(CH )2C-
(CH3)N}(CO)(P P r i3) (10). A suspension of 9 (308 mg, 0.45
mmol) in 12 mL of tetrahydrofuran was treated with sodium
methoxide (49 mg, 0.90 mmol) and stirred for 2 h. The solution
became orange, and the solvent was removed in vacuo.
Toluene (15 mL) was added, and the mixture was filtered to
eliminate sodium tetrafluoroborate. Solvent was evaporated,
and the residue was washed with pentane to afford a pale
yellow solid. Yield: 222 mg (79%). Anal. Calcd for C34H41
-
ON2PRu: C, 65.26; H, 6.60; N, 4.47. Found: C, 64.93; H, 6.17;
N, 4.52. IR (Nujol, cm-1): ν(CtC) 2105 (m), ν(CO) 1931 (vs).1H
NMR (300 MHz, 293 K, C6D6): δ 8.22 (d, 1H, J (HH) ) 2.2,
pz), 7.36 (m, 2H, Ph), 7.25-7.11 (m, 8H, Ph), 5.92 (d, 1H,
J (HH) ) 2.2, pz), 5.12 (d, 5H, J (PH) ) 0.9, Cp), 2.17 (s, 3H,
pz-CH3), 2.03 (m, 3H, PCHCH3), 0.99 (dd, 9H, J (HH) ) 7.2,
J (PH) ) 14.7, PCHCH3), 0.94 (dd, 9H, J (HH) ) 7.2, J (PH) )
13.2, PCHCH3).31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ 75.2
(s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus dept): δ
205.8 (d, J (PC) ) 18.4, CO), 148.8 (s, Cipso,pz), 145.5, 145.4 (both
s, CipsoPh), 131.5 (pz), 128.6, 128.3, 127.4, 127.3, 126.7, 126.6
(all s, Ph), 107.1 (d, J (PC) ) 0.9, Ru-CtC), 103.2 (pz), 99.7
(d, J (PC) ) 21.6, Ru-CtC), 85.4 (s, Cp), 70.7 (s, CPh2), 26.8
(d, J (PC) ) 24.4, PCHCH3), 19.8 (s, PCHCH3), 19.2 (d, J (PC)
) 1.8, PCHCH3), 14.1 (s, pz-CH3).
P r ep a r a t ion of [R u (η5-C5H 5){CdCH C(P h )2NC(CH 3)-
P r ep a r a tion of [Ru (η5-C5H5){CdCHC(P h )2N(CH)4CS}-
CHC(CH3)N}(CO)(P P r i3)]BF 4 (8). A dark red solution of 1
(CO)(P P r i3)]BF 4 (11). A solution of 1 (150 mg, 0.24 mmol)
in 5 mL of dichloromethane was treated with pyridine-2-thiol
(27 mg, 0.24 mmol), and the mixture was stirred for 5 min.
The color turned from dark red to orange, and the solvent was
removed in vacuo. The residue was washed with diethyl ether
to afford a yellow solid. Yield: 162 mg (92%). Anal. Calcd
for C35H41BF4NOPRuS: C, 56.61; H, 5.56; N, 1.89; S, 4.32.
Found: C, 56.62; H, 5.90; N, 1.84; S, 4.76. IR (Nujol, cm-1):
ν(CO) 1939 (vs), ν(CdC) 1561 (m), ν(BF4) 1051 (vs, br). 1H
NMR (300 MHz, 293 K, CDCl3): δ 8.38 (m, 1H, py), 7.81 (m,
1H, py), 7.71 (m, 2H, py), 7.39 (m, 6H, Ph), 6.85 (m, 4H, Ph),
6.38 (s, 1H, Ru-CdCH), 5.14 (s, 5H, Cp), 2.27 (m, 3H,
PCHCH3), 1.14 (dd, 9H, J (HH) ) 6.5, J (PH) ) 13.6, PCHCH3),
1.12 (dd, 9H, J (HH) ) 5.9, J (PH) ) 12.7, PCHCH3).31P{1H}
(110 mg, 0.17 mmol) in 5 mL of dichloromethane was treated
with 3,5-dimethylpyrazole (33 mg, 0.35 mmol), and the mixture
was stirred for 30 min. The solution became colorless, and
the solvent was removed in vacuo. The residue was washed
with diethyl ether to afford a colorless oil. Yield: 107 mg
(85%). 1H NMR (300 MHz, 293 K, CDCl3): δ 7.37 (m, 6H, Ph),
7.10 (m, 2H, Ph), 6.95 (m, 2H, Ph), 6.51 (s, 1H, pz), 5.79 (s,
1H, Ru-CdCH), 5.25 (s, 5H, Cp), 2.92 (s, 3H, CH3), 2.07 (m,
3H, PCHCH3), 1.93 (s, 3H, CH3), 0.94 (dd, 9H, J (HH) ) 7.2,
J (PH) ) 14.1, PCHCH3), 0.91 (dd, 9H, J (HH) ) 6.9, J (PH) )
14.1, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ
64.0 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3): δ 207.5 (d,
J (PC) ) 21.2, CO), 142.5, 141.6 (both s, CipsoPh), 140.0 (d, J (PC)
) 12.9, Ru-Cd), 139.3 (d, J (PC) ) 4.6, Ru-CdCH), 136.3,

1,2,3-Diheterocyclization Reactions
Organometallics, Vol. 17, No. 16, 1998 3573
Ta ble 2. Cr ysta l Da ta a n d Da ta Collection a n d
(m, 1H, py), 7.99-7.39 (m, 5H, Ph + py), 7.32-7.06 (m, 6H,
Ph), 6.80 (m, 1H, py), 6.40 (m, 1H, py), 5.04 (s, 5H, Cp), 1.98
(m, 3H, PCHCH3), 1.02 (dd, 9H, J (HH) ) 7.1, J (PH) ) 14.3,
PCHCH3), 0.80 (dd, 9H, J (HH) ) 6.9, J (PH) ) 13.0,
PCHCH3).31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ 50.5 (s).
13C{1H} NMR (75.4 MHz, 293 K, C6D6, plus dept): δ 206.7 (d,
J (PC) ) 19.6, CO), 198.3 (s, dCd), 162.3 (s, Cipso,py), 149.6 (s,
py), 140.6, 140.5 (both s, CipsoPh), 135.3 (s, py), 128.8, 128.7,
128.3, 128.2, 125.9, 125.9 (all s, Ph), 127.3 (s, py), 120.5 (s,
py), 103.9 (s, dCPh2), 88.6 (d, J (PC) ) 12.1, Ru-Cd), 86.2 (s,
Cp), 27.2 (d, J (PC) ) 22.6, PCHCH3), 20.3, 19.3 (both s,
PCHCH3).
Refin em en t for th e Com p lex [Ru (η5-C5H5)-
{CdCHC(P h )2N(CH)3N}(CO)(P P r i3)]BF 4 (2)
Crystal Data
formula
mol wt
C33H40BF4N2OPRu
699.54
color and habit
symmetry
space group
a, Å
yellow, prismatic block
orthorombic
Aba2
19.150(3)
17.293(3)
19.642(3)
6505(2); 8
1.429
X-r a y St r u ct u r e An a lysis of Com p lex [R u (η5-C5H 5)-
b, Å
c, Å
{CdCHC(P h )2N(CH)3N}(CO)(P P r i3)]BF 4 (2). Crystals suit-
V, Å3; Z
D
calc, g cm-3
able for the X-ray diffraction study were obtained by slow
diffusion of diethyl ether into a saturated solution of 2 in
dichlorometane. A summary of crystal data and refinement
parameters is reported in Table 2. The yellow, prismatic
crystal, of approximate dimensions 0.38 × 0.27 × 0.19 mm,
was glued on a glass fiber and mounted on a Siemens-STOE
AED-4 diffractometer. A group of 62 reflections in the range
20° e 2θ e 40° was carefully centered at 223 K and used to
obtain the unit cell dimensions by least-squares methods.
Three standard reflections were monitored at periodic intervals
throughout data collection: no significant variations were
observed. All data were corrected for absorption using a
numerical absorption correction.20 The structure was solved
by Patterson (Ru atom, SHELXTL-PLUS20) and conventional
Fourier techniques and refined by full-matrix least-squares.
Anisotropic parameters were used in the last cycles of refine-
ment for all non-hydrogen atoms. The hydrogen atoms were
located from difference Fourier maps or calculated in idealized
positions and refined riding on carbon atoms with a common
isotropic thermal parameter. Atomic scattering factors, cor-
rected for anomalous dispersion for Ru and P, were taken from
ref 21. The refinement converged to R ) 0.030 and Rw ) 0.027
[F g 4σ(F)], with weighting parameter w-1 ) σ2F + 0.000152F2.
Data Collection and Refinement
diffractometer
λ(MoKR), Å; technique
monochromator
µ, mm-1
four-circle Siemens-STOE AED-2
0.710 73; bisecting geometry
graphite oriented
0.58
scan type
2θ range, deg
temp, K
ω/2θ
3° e 2θ e 50°
223.0(2)
no. of data collect
no. of unique data
no. of obsd data
no. of params refined
6504
5297(Rint ) 0.0164)
4530 (Fo g 4.0 σ(Fo))
389
0.030, 0.027
0.0391, 0.0301
1.233
b
Ra, Rw (obsd data)
R, wR (all data)
goodness of fitc
a
b
R ) ∑|[Fo - Fc)]|/∑Fo. Rw ) ∑w1/2|[Fo - Fc)]|/∑w1/2Fo. c S )
{∑(w[Fo - Fc)])2/(M - N)}1/2, where M is the number of observed
reflections and N is the number of parameters refined.
NMR (121.4 MHz, 293 K, CDCl3): δ 66.3 (s). 13C{1H} NMR
(75.4 MHz, 293 K, CDCl3): δ 205.9 (d, J (PC) ) 18.1, CO),
154.9, 143.1 (both s, py), 142.1 (d, J (PC) ) 12.8, Ru-Cd), 140.2
(s, py), 139.6, 139.4 (both s, CipsoPh), 132.1 (s, Ru-CdCH),
129.5, 129.4, 128.8, 128.5, 125.4, 123.9 (all s, Ph), 129.1 (s,
py), 85.9 (s, Cp), 78.8 (s, CPh2), 27.6 (d, J (PC) ) 23.3,
PCHCH3), 20.0, 19.6 (both s, PCHCH3).
Ack n ow led gm en t. We thank the DGES (Project
PB-95-0806, Programa de Promocio´n General del Cono-
cimiento) for financial support.
P r ep a r a tion of Ru (η5-C5H5){C[SC(CH)4N]dCdCP h 2}-
(CO)(P P r i3) (12). A suspension of 11 (162 mg, 0.22 mmol) in
15 mL of tetrahydrofuran was treated with sodium methoxide
(16 mg, 0.30 mmol) and stirred for 2 h. The color changed
from orange to yellow, and the solvent was removed in vacuo.
Toluene (15 mL) was added, and the mixture was filtered to
eliminate sodium tetrafluoroborate. Solvent was evaporated,
and the residue was washed with diethyl ether to afford a
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, anisotropic and isotropic thermal parameters,
experimental details of the X-ray study, bond distances and
angles and selected least-squares planes (17 pages). Ordering
information is given on any current masthead page.
OM980230A
yellow solid. Yield: 89 mg (62%). Anal. Calcd for C35H40
-
(20) Sheldrick, G. SHELXTL-PLUS; Siemens Analitical X-ray In-
struments Inc.: Madison, WI, 1990.
(21) International Tables for X-ray Crystallography; Kynoch Press:
Birmingham, England, 1979; Vol IV.
NOPRuS: C, 64.20; H, 6.16; N, 2.14; S, 4.90. Found: C, 64.12;
H, 5.74; N 2.19; S, 5.19. IR (Nujol, cm-1): ν(CO) 1913 (vs),
ν(CdCdC) 1869 (m).1H NMR (300 MHz, 293 K, C6D6): δ 8.35