Addition of carbon nucleophiles to the allenylidene ligand of [Ru(η5-C5H5)(C=C=CPh2) (CO) (PiPr3)]BF4: Synthesis of new organic ligands by formal C-C coupling between mutually inert fragments

Article abstract of DOI:10.1021/om9708539

EHT-MO Calculations on the model cation [Ru(η⁵-C₅H₅)(C=C=CH ₂)(CO)(PH₃)]⁺ (1a) suggest that 23% and 31% of the LUMO and 26% of the HOMO of [Ru(η⁵-C₅H₅)(C=C=CPh ₂)-(CO)(PⁱPr₃)]BF₄ (1) are located on C_α, C_γ, and C_β of the allenylidene ligand, respectively. On the basis of these results, we report a new synthetic strategy for the preparation of compounds resulting from the formal addition of phenylacetylene, acetone, and methane to the allenylidene of 1. Treatment of 1 with LiC≡CPh leads to the allenyl complex Ru(η⁵-C₅H₅){C(C=CPh)=C=CPh ₂}(CO)(PⁱPr₃) (2) and the alkynyl derivative Ru(η⁵-C₅H₅){C≡C-C(Ph) ₂C≡CPh}(CO)(PⁱPr₃) (3). The reaction of 2 with HBF₄ affords the substituted carbene compound [Ru(η⁵-C₅H₅){C(C≡CPh)CH=CPh ₂}(CO)(PⁱPr₃)]BF₄ (4), which is a result from the formal addition of phenylacetylene to the C_α-C_β double bond of the allenylidene of 1. The molecular structure of 4 has been determined by X-ray crystallography. The geometry around the ruthenium center is close to octahedral with the cyclopentadienyl ligand occupying three sites of a face. The Ru=C bond length is 2.004(5) A?. In the presence of KOH, complex 1 reacts with acetone to give Ru(η⁵-C₅H₅){C≡C-C(Ph) ₂CH₂C(O)CH₃}(CO)(PⁱPr₃) (5). The reaction of 5 with HBF₄ leads to the unsaturated cyclic carbene complex [Ru(η⁵-C₅H₅)-{CCH₂C(Ph) ₂CH=C(CH₃)O}(CO)(PⁱPr₃)]BF ₄ (6). Complex 5 also reacts with 2 equiv of CF₃-CO₂D to give [Ru(η⁵-C₅H₅){CCD₂C(Ph) ₂CH=C(CH₃)O}(CO)(PⁱPr₃)](CF ₃CO₂) (6-d₂) and CF₃-CO₂H, and the reaction of Ru(η⁵-C₅H₅){C≡C-C(Ph) ₂CD₂C(O)CD₃}(CO)(PⁱPr₃) (5-d₅) with 2 equiv of HBF₄ affords [Ru(η⁵-C₅H₅){CCH₂C(Ph) ₂CD=C(CD₃)6}(CO)(PⁱPr₃)]BF ₄ (6-d₄) and DBF₄. On the basis of these isotope labeling experiments, the mechanism for the addition of acetone to the allenylidene ligand of 1 is discussed. Complex 1 also reacts with Na-(acac) and CH₃Li. The reaction with Na(acac) leads to Ru(η⁵-C₅H₅){C≡C-C(Ph) ₂CH[C(O)-CH₃]₂}(CO)(PⁱPr ₃) (7), while the treatment of 1 with CH₃Li gives a mixture of Ru(η⁵-C₅H₅){C(CH₃)=C=CPh ₂}(CO)(PⁱPr₃) (8) and Ru(η⁵-C₅H₅){C≡C-C(Ph) ₂CH₃}(CO)(PⁱPr₃) (9). Complex 9 reacts with HBF₄ to afford [Ru(η⁵-C₅H₅){C=CHC(Ph)₂CH ₃}(CO)(PⁱPr₃)]BF₄ (10), which is a result of the formal addition of a C-H bond of methane to the C_β-C_γ double bond of the allenylidene of 1.

Full text of DOI:10.1021/om9708539

5826
Organometallics 1997, 16, 5826-5835
Ad d ition of Ca r bon Nu cleop h iles to th e Allen ylid en e
Liga n d of [Ru (η5-C5H5)(CdCdCP h 2)(CO)(P iP r 3)]BF 4:
Syn th esis of New Or ga n ic Liga n d s by F or m a l C-C
Cou p lin g betw een Mu tu a lly In er t F r a gm en ts
Miguel A. Esteruelas,* Angel V. Go´mez, Ana M. Lo´pez, J avier Modrego, and
Enrique On˜ate
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received October 2, 1997X
EHT-MO Calculations on the model cation [Ru(η5-C5H5)(CdCdCH2)(CO)(PH3)]+ (1a ) sug-
gest that 23% and 31% of the LUMO and 26% of the HOMO of [Ru(η5-C5H5)(CdCdCPh2)-
(CO)(PiPr3)]BF4 (1) are located on CR, Cγ, and Câ of the allenylidene ligand, respectively.
On the basis of these results, we report a new synthetic strategy for the preparation of
compounds resulting from the formal addition of phenylacetylene, acetone, and methane to
the allenylidene of 1. Treatment of 1 with LiCtCPh leads to the allenyl complex Ru(η5-
C5H5){C(CtCPh)dCdCPh2}(CO)(PiPr3) (2) and the alkynyl derivative Ru(η5-C5H5){CtC-
C(Ph)2CtCPh}(CO)(PiPr3) (3). The reaction of 2 with HBF4 affords the substituted carbene
compound [Ru(η5-C5H5){C(CtCPh)CHdCPh2}(CO)(PiPr3)]BF4 (4), which is a result from the
formal addition of phenylacetylene to the CR-Câ double bond of the allenylidene of 1. The
molecular structure of 4 has been determined by X-ray crystallography. The geometry around
the ruthenium center is close to octahedral with the cyclopentadienyl ligand occupying three
sites of a face. The RudC bond length is 2.004(5) Å. In the presence of KOH, complex 1
reacts with acetone to give Ru(η5-C5H5){CtC-C(Ph)2CH2C(O)CH3}(CO)(PiPr3) (5). The
reaction of 5 with HBF4 leads to the unsaturated cyclic carbene complex [Ru(η5-C5H5)-
{CCH2C(Ph)2CHdC(CH3)O}(CO)(PiPr3)]BF4 (6). Complex 5 also reacts with 2 equiv of CF3-
CO2D to give [Ru(η5-C5H5){CCD2C(Ph)2CHdC(CH3)O}(CO)(PiPr3)](CF3CO2) (6-d 2) and CF3-
CO2H, and the reaction of Ru(η5-C5H5){CtC-C(Ph)2CD2C(O)CD3}(CO)(PiPr3) (5-d 5) with 2
equiv of HBF4 affords [Ru(η5-C5H5){CCH2C(Ph)2CD)C(CD3)O}(CO)(PiPr3)]BF4 (6-d 4) and
DBF4. On the basis of these isotope labeling experiments, the mechanism for the addi-
tion of acetone to the allenylidene ligand of 1 is discussed. Complex 1 also reacts with Na-
(acac) and CH3Li. The reaction with Na(acac) leads to Ru(η5-C5H5){CtC-C(Ph)2CH[C(O)-
CH3]2}(CO)(PiPr3) (7), while the treatment of 1 with CH3Li gives a mixture of Ru(η5-
C5H5){C(CH3)dCdCPh2}(CO)(PiPr3) (8) and Ru(η5-C5H5){CtC-C(Ph)2CH3}(CO)(PiPr3) (9).
Complex 9 reacts with HBF4 to afford [Ru(η5-C5H5){CdCHC(Ph)2CH3}(CO)(PiPr3)]BF4 (10),
which is a result of the formal addition of a C-H bond of methane to the Câ-Cγ double bond
of the allenylidene of 1.
In tr od u ction
(CdCdCPh2)(PPh3)2]PF6 underwent regioselective nu-
cleophilic attacks at Cγ by the anionic species
[(CO)5M)C(OMe)CH2]- (M ) Cr, Mo, W) to yield the
binuclear alkynyl-carbene complexes (PPh3)2(η5-C9H7)-
Ru-CtC-CPh2-CH2-C(OMe)dM(CO)5.3 Along this
line, Kolobova et al. have shown that the allenylidene
Owing to the increasing demand for new organic
products, the development of highly efficient selective
synthetic methods is one of the most urgent tasks for
chemical science. In this respect, the formation of car-
bon-carbon bonds mediated by transition metal com-
pounds has emerged in its own right over the last few
years as an important step in organic synthesis, which
has general interest.1
In this context, it should be mentioned that Werner
has recently proved that in the series carbene-vi-
nylidene-allenylidene not only carbene and vinylidene
complexes but also allenylidene compounds can be used
as starting materials for C-C coupling reactions.2 In
agreement with this, Gimeno et al. had observed that
the ruthenium-allenylidene derivative [Ru(η5-C9H7)-
(1) (a) Stille, J . K. Chemistry of the Metal-Carbon Bond; Hartley, F.
R., Patai, S., Eds.; Wiley: Chichester, 1985; Vol. 2. (b) Hagashi, T.;
Kumada, M. Asymmetric Synthesis; Morrison, J . D., Ed.; Academic:
New York, 1985; Vol. 5. (c) Yamamoto, A. Organotransition Metal
Chemistry; Wiley: New York, 1986. (d) Collman, J . P.; Hegedus, L. S.;
Norton, J . R.; Finke, R. G. Principles and Applications of Organ-
otransition-metal Chemistry; University Science Books: Mill Valey, CA,
1987. (e) Brown, J . M.; Cooley, N. A. Chem. Rev. 1988, 88, 1031. (f)
Brookhart, M.; Volpe, A. F., J r.; Yoon, J . Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Ed.; Pergamon Press: New York,
1991; Vol. 4. (g) Schmalz, H. G. Angew. Chem., Int. Ed. Engl. 1995,
34, 1833.
(2) (a) Wiedemann, R.; Steinert, P.; Gevert, O.; Werner, H. J . Am.
Chem. Soc. 1996, 118, 2495. (b) Braun, T.; Meuer, P.; Werner, H.
Organometallics 1996, 15, 4075. (c) Werner, H. J . Chem. Soc., Chem.
Commun. 1997, 903.
X Abstract published in Advance ACS Abstracts, December 1, 1997.
S0276-7333(97)00853-4 CCC: $14.00 © 1997 American Chemical Society

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 16, No. 26, 1997 5827
ligand of the complex Mn(η5-C5H5)(CdCdCPh2)(CO)2
can be coupled with tert-butyl isocyanide to form a
cumulenylidene derivative,4 and Fisher et al. have
reported on the formation of binuclear cyclobutenylidene
complexes by cycloaddition of the carbon-carbon triple
bond of alkynyl complexes to the CR-Câ double bond of
allenylidene compounds.5
Most recently, we have reported the synthesis of the
less basic compound [Ru(η5-C5H5)(CdCdCPh2)(CO)-
(PiPr3)]BF4 which, in contrast to the Gimeno’s complex,
adds water, alcohols, thiols, and benzophenone imine
at the CR-Câ double bond of the allenylidene group to
afford R,â-unsaturated hydroxycarbene, alkoxycarbene,
(alkylthio)carbene, and 2-azaallenyl compounds, respec-
tively.6 After observing this, we asked ourselves whether
products formally resulting from the addition to the
allenylidene group of kinetically inert molecules in the
presence of [Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
could be also obtained.
In this paper, we prove that, in fact, the products
resulting from the formal addition of phenylacetylene
(PhCtC- and H+), acetone (CH3COCH2- and H+), and
methane (CH3- and H+) to the CR-Câ or Câ-Cγ double
bonds of the allenylidene of [Ru(η5-C5H5)(CdCdCPh2)-
(CO)(PiPr3)]BF4 can be obtained by an easy method.
Resu lts a n d Discu ssion
E H T-MO Ca lcu la t ion s for [R u (η5-C5H 5)(CdCd
CP h 2)(CO)(P iP r 3)] BF 4. In order to design a synthetic
strategy to prepare the resultant compounds from the
formal addition of phenylacetylene, acetone, and meth-
ane to the allenylidene ligand of [Ru(η5-C5H5)(CdCd
CPh2)(CO)(PiPr3)]BF4 (1), we carried out an analysis of
the electronic structure of this complex. The study has
been performed using EHT-MO calculations7 on the
model cation [Ru(η5-C5H5)(CdCdCH2)(CO)(PH3)]+ (1a ).8
The molecular orbital diagram of 1a is shown in
Figure 1. Its orbital scheme is related to the interaction
of the electronic structures of the fragments [Ru(η5-
C5H5)(CO)(PH3)]+ and allenylidene (CdCdCH2), which
are well-known.9 The allenylidene coordinates to the
metal center as a σ-donor and π-acceptor ligand. The
σ-donor component of the bond, which takes place
between the HOMO of the allenylidene and the LUMO
of the metallic fragment, produces a charge transfer of
0.44 e from the ligand to the metallic fragment. How-
ever, the interaction between the HOMO of the metallic
fragment and the LUMO of the allenylidenesthe π-ac-
ceptor component of the metal-allenylidene bondsleads
to a charge transfer of 0.93 e, from the metallic moiety
to the η1-carbon ligand. So, from the point of view of
F igu r e 1. (b) Molecular orbital diagram of model complex
[Ru(η5-C5H5)(CdCdCH2)(CO)(PH3)]+, and interaction dia-
gram between fragments (a) [Ru(η5-C5H5)(CO)(PH3)]+ and
(c) (CdCdCH2).
the charge, the π-acceptor component of the bond is
stronger than the σ-donor one, and the resultant bond,
including all contributions, produces a total charge
transfer of 0.45 e from the metallic fragment to the
carbon atoms of the allenylidene.
According to a Mulliken population analysis, 60% of
the LUMO of 1a is located on the allenylidene ligand,
with a distribution on the carbon atoms of 23% (CR), 6%
(Câ), and 31% (Cγ) (Figure 2). From the same analysis,
it is inferred that the net charges on each carbon atom
are -0.36 (CR), -0.13 (Câ), and -0.05 (Cγ).
Nucleophilic attack reactions can be orbital and
charge directed and strongly depend on the character-
istic of the LUMO of the electrophile.10 So, the orbital-
controlled nucleophilic attacks to 1 should indistinctly
lead to addition products on the CR or Cγ atoms of the
allenylidene ligand.
The 26% of the HOMO of 1a is also located on the
allenylidene ligand, mainly on the â-carbon atom (20%)
(Figure 2). This implies that the allenylidene ligand of
1 should not only undergo attacks of nucleophiles at CR
and Cγ but also of electrophiles at Câ.
(3) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-
Granda, S. J . Chem. Soc., Chem. Commun. 1994, 2495.
(4) Kalinin, V. N.; Derunov, V. V.; Lusenkova, M. A.; Petrovsky, P.
V.; Kolobova, N. E. J . Organomet. Chem. 1989, 379, 303.
(5) Fischer, H.; Leroux, F.; Stumpt, R.; Roth, G. Chem. Ber. 1996,
129, 1475.
(6) Esteruelas, M. A.; Go´mez A. V.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate,
E.; Oro, L. A. Organometallics 1996, 15, 3423.
(7) (a) Klopman, G. In Chemical Reactivity and Reaction Paths;
Klopman, G., Ed.; Wiley: New York, 1974; pp 59-67. (b) Kostic, N.
M.; Fenske, R. F. J . Am. Chem. Soc. 1981, 103, 4677. (c) Kostic, N.
M.; Fenske, R. F. Organometallics 1982, 1, 489.
Ad d ition of P h en yla cetylen e. In agreement with
the theoretical results, the treatment of a tetrahydro-
furan solution of 1 with 1.1 equiv of lithium phenyl-
acetylide, between -40 and 10 °C, leads to a mixture of
the allenyl derivative Ru(η5-C5H5){C(CtCPh)dCd
CPh2}(CO)(PiPr3) (2) and its alkynyl isomer Ru(η5-
(8) Previously, EHT-MO calculations on the allenylidene complex
Mn(η5-C5H5)(CO)2(CdCdCH2) have been carried out, see: Berke, H.;
Huttner, G.; Von Seyerl, J . Z. Naturforsch. 1981, 36b, 1277.
(9) Albright, T. A.; Burdett, J . K.; Whangbo, M. H. Orbital Interac-
tions in Chemistry, Wiley: New York, 1985.
(10) (a) Hoffmann, R.; Lipscomb, W. N. J . Chem. Phys. 1962, 36,
2179. (b) Hoffmann, R.; Lipscomb, W. N. J . Chem. Phys. 1962, 36, 3489.
(c) Hoffmann, R.; Lipscomb, W. N. J . Chem. Phys. 1962, 37, 2872. (d)
Hoffmann, R. J . Chem. Phys. 1963, 39, 1397.

5828 Organometallics, Vol. 16, No. 26, 1997
Esteruelas et al.
F igu r e 2. Partial view of the frontier molecular orbitals of the model complex [Ru(η5-C5H5)(CdCdCH2)(CO)(PH3)]+ showing
the Ru and allenylidene contributions.
C5H5){CtC-C(Ph)2CtCPh}(CO)(PiPr3) (3, eq 1). The
propargyl or allenyl halides to electron-rich metal pre-
cursors.13 Recently, it has been also reported that the
alkynyl(hydrido) osmium complexes OsHCl{CtCC(OH)-
Ph2}(NO)(PR3)2 react with acidic alumina to afford the
allenylosmium(II) derivatives OsCl2{CHdCdCPh2}(NO)-
(PR3)2 (PR3 ) PiPr3, PPhiPr2).14 We have described that
both the deprotonation of R,â-unsaturated alkoxycar-
bene, (alkylthio)carbene, and 2-azaallenyl complexes as
well as the dehydration of alkoxyalkenyl yield allenyl
derivatives.6,15
In addition, [(PR3)-allenyl]+ complexes have been
synthesized. PMe3 adds regioselectively to the γ-carbon
atom of the allenylidene ligand of [Ru(η5-C9H7)(CdCd
CPh2)(dppm)]PF6 to give the alkynyl derivative [Ru-
(η5-C9H7){CtCC(PMe3)Ph2}(dppm)]PF6, which isomer-
izes into [Ru(η5-C9H7){C(PMe3)dCdCPh2}(dppm)]PF6.11
Fischer has reported that the allenylidene complex
Cr(CO)5{CdCdC(C6H4NMe2-p)2} adds phosphines at
the R-carbon atom to give ylide complexes Cr(CO)5-
{C(PR3)dCdC(C6H4NMe2-p)2} (PR3 ) PMe3, PHPh2,
PH2Mes). At room temperature, the complex Cr(CO)5-
{C(PHPh2)dCdC(C6H4NMe2-p)2} rearranges to Cr(CO)5-
{PPh2[CHdCdC(C6H4NMe2-p)2]}.16 The complexes
M(CO)5{C(PPh3)dCdC(CHMe2)2} (M ) Cr, W) have
been prepared by addition of PPh3 to the corresponding
allenylidene precursors.17
allenyl complex 2, which is a result of the attack of the
acetylide group at the R-carbon atom of the allenylidene
ligand of 1, is the main product from the reaction and
was isolated as a yellow solid in 41% yield. The isomer
3, which is a result of the attack of the acetylide group
at the γ-carbon atom of the allenylidene unit, is obtained
in 18% yield and was isolated as a white solid.
The formation of 2 according to eq 1 is noteworthy,
firstly, because transition metal compounds containing
(alkynyl)allenyl ligands have not previously been re-
ported and, secondly, because the formation of allenyl
complexes by attack of anionic nucleophiles to alle-
nylidene ligands has no precedent. We note that the
reactions of [Ru(η5-C9H7)(CdCdCPh2)(PPh3)2]PF6 with
LiCtCR (R ) Ph, n-C3H7) have been previously stud-
ied.11 In contrast to the reaction shown in eq 1, the
acetylide groups attack solely at the γ-carbon atom of
the allenylidene ligand of this indenyl complex. The
formation of related compounds to 2 is not observed. In
addition, it should be mentioned that rhodium com-
pounds containing γ-functionalized alkynyl groups have
been recently prepared by migratory insertion of an
allenylidene unit into Rh-OR (R ) Ph, CH3CO) bonds.12
η1-Allenyl transition metal compounds are rare, most
of them have been prepared by oxidative addition of
Complexes 2 and 3 were characterized by elemental
analysis and IR and 1H, 31P{1H}, and 13C{1H} NMR
spectroscopies. The IR spectrum of 2 in Nujol shows
the characteristic CdCdC stretching frequency at 1927
cm-1, along with two bands at 2168 and 1934 cm-1
corresponding to the ν(CtC) and ν(CO) vibrations,
respectively. The 13C{1H} NMR spectrum contains the
(13) (a) J acobs, T. L. The Chemistry of the Allenes; Landor, S. R.,
Ed.; Academic Press: London, 1982; Vol. 2, p 334. (b) Schuster, H. F.;
Coppola, G. M. Allenes in Organic Chemistry; Wiley-Interscience: New
York, 1984. (c) Wojcicki, A.; Shuchart, C. E. Coord. Chem. Rev. 1990,
105, 35. (d) Keng, R.-S.; Lin, Y.-C. Organometallics 1990, 9, 289. (e)
Shuchart, C. E.; Willis, R. R.; Wojcicki, A. J . Organomet. Chem. 1992,
424, 185. (f) Wouters, J . M. A.; Klein, R. E.; Elsevier, C. J .; Ha¨ming,
L.; Stam, C. H. Organometallics 1994, 13, 4586.
(14) Werner, H.; Flu¨gel, R.; Windmu¨ller, B.; Michenfelder, A.; Wolf,
J . Organometallics 1995, 14, 612.
(15) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Rodr´ıguez,
L. Organometallics 1996, 15, 3670.
(11) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J . Orga-
nomet. Chem. 1994, 474, C27.
(12) Werner, H.; Wiedemann, R.; Laubender, M.; Wolf, J .; Wind-
mu¨ller, B. J . Chem. Soc., Chem. Commun. 1996, 1413.
(16) Fischer, H.; Reindl, D.; Troll, C.; Leroux, F. J . Organomet.
Chem. 1995, 490, 221.
(17) Berke, H.; Haeter, P.; Huttner, G.; Zsolnai, L. Z. Naturforsch.
1981, 36b, 929.

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 16, No. 26, 1997 5829
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for [Ru (η5-C5H5){C(CtCP h )CHdCP h 2}-
(CO)(P iP r 3)]BF 4 (4)
Bond Lengths
Ru-C(24)
Ru-C(25)
Ru-C(26)
Ru-C(27)
Ru-C(28)
Ru-C(29)
C(29)-O
Ru-P
2.276(5)
2.242(5)
2.239(5)
2.285(5)
2.310(5)
1.834(5)
1.150(6)
2.381(1)
Ru-C(1)
2.004(5)
1.401(7)
1.212(7)
1.432(6)
1.441(6)
1.350(6)
1.485(7)
1.481(6)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(1)-C(10)
C(10)-C(11)
C(11)-C(12)
C(11)-C(18)
Bond Angles
P-Ru-C(1)
96.5(1)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
172.7(5)
174.5(6)
120.3(4)
130.7(5)
121.6(4)
120.6(4)
117.5(4)
P-Ru-C(29)
92.3(2)
124.0(2)
92.4(2)
121.9(2)
121.7(2)
125.5(3)
114.1(3)
P-Ru-G(1)a
C(2)-C(1)-C(10)
C(1)-C(10)-C(11)
C(10)-C(11)-C(12)
C(10)-C(11)-C(18)
C(12)-C(11)-C(18)
C(1)-Ru-C(29)
C(1)-Ru-G(1)a
C(29)-Ru-G(1)a
Ru-C(1)-C(10)
Ru-C(1)-C(2)
F igu r e 3. Molecular diagram of complex [Ru(η5-C5H5)-
{C(CtCPh)CHdCPh2}(CO)(PiPr3)]BF4 (4). Thermal el-
lipsoids are shown at 50% probability.
aG(1) is the midpoint of the C(24)-C(28) Cp ligand.
that one should expect if, in the presence of complex 1,
the phenylacetylene molecule had shown the same
behavior as the above-mentioned molecules. This sug-
gests that the inertia of the alkyne is kinetic in origin
and is connected with the transition state of the addition
to the CR-Câ double bond of the allenylidene. Because
the R- and â-carbon atoms of the allenylidene are
electrophilic and nucleophilic centers, respectively, and
the H-X (X ) O, S) hydrogen atom of the RXH
molecules is electrophilic, the transition state for the
RX-H addition most probably requires a heteroatom-
CR interaction, which labilizes the H-X bond, favoring
the migration of the H-X hydrogen atom to the â-carbon
atom of the allenylidene. Thus, the lower nucleophilic
character of the terminal carbon atom of the alkyne can
explain why the addition of phenylacetylene to the
allenylidene is kinetically disfavored.
resonances due to the sp2-carbon atoms of the allenyl
unit at 209.7 (Câ), 98.3 (Cγ), and 74.3 (CR) ppm. The
first and third resonances appear as doublets with P-C
coupling constants of 1.5 and 11.9 Hz, respectively,
while the second one is observed as a singlet. In
addition, two singlets at 94.7 and 91.3 should be
mentioned, corresponding to the sp-carbon atoms of the
acetylide group. In the IR spectrum of 3 in Nujol, the
most noticeable features are two ν(CtC) bands at 2109
and 2096 cm-1. In the 13C{1H} NMR spectrum, the
resonance of the Ru-Ct carbon atom appears at 90.9
ppm as a doublet with a P-C coupling constant of 22.2
Hz, while the Câ and Cγ carbon atoms of the alkynyl
group display singlets at 106.8 and 48.2 ppm. The
resonance of the sp-carbon atoms of the -CtCPh unit
are observed as singlets at 95.1 and 83.1 ppm.
Complex 4 was isolated as a dark brown solid in 89%
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 3. Selected bond distances and angles are
listed in Table 1.
The geometry around the ruthenium center is close
to octahedral, with the cyclopentadienyl ligand occupy-
ing three sites of a face, and the angles formed by the
triisopropylphosphine, the carbonyl group, and the
unsaturated η1-carbon ligand are close to 90°.
Complex 2 reacts with 1 equiv of HBF4 in dichlo-
romethane at room temperature to give the unusual
carbene complex [Ru(η5-C5H5){C(CtCPh)CHdCPh2}-
(CO)(PiPr3)]BF4 (4, eq 2), where the substituted carbene
ligand has two unsaturated groups, the acetylide
PhCtC- and the alkenyl-CHdCPh2.
The most conspicuous features of this structure are
firstly the Ru-C(1) bond length (2.004(5) Å), which is
consistent with a Ru-C(1) double bond formulation, and
secondly the bond angles around C(1) (between 114.1-
(3)° and 125.5(3)°) which clearly indicate sp2 hybridiza-
tion for the C(1) carbon atom. Similar values have been
reported for other ruthenium-carbene complexes.18 The
bond lengths and angles within the alkylidene ligand
are consistent with the R-â-alkenyl-(acetylide)carbene
proposal; e.g., C(1) and C(10) are separated by 1.441(6)
Å and C(10) and C(11) by 1.350(6) Å, and the bond
angles around C(11) are about 120°, while the C(2)-
C(3) bond length is 1.212(7) Å and the angles C(1)-
C(2)-C(3) and C(2)-C(3)-C(4) are 172.7(5)° and 174.5-
(6)°, respectively.
We have previously mentioned that complex 1 adds
water, alcohols, and thiols at the CR-Câ double bond of
the allenylidene to give the corresponding R,â-unsatur-
ated (functionalized)carbene derivatives. The R,â-
unsaturated (acetylide)carbene complex 4 is a result
In agreement with the presence of an acetylide group
in the carbene ligand, the IR spectrum of 4 in Nujol

5830 Organometallics, Vol. 16, No. 26, 1997
Esteruelas et al.
in vinylidene compounds is well-known.19 This prompted
us to add potassium hydroxide to the acetone solutions
of 1, and as expected, the functionalized alkynyl complex
Ru(η5-C5H5){CtC-C(Ph)2CH2C(O)CH3}(CO)(PiPr3) (5)
was formed (eq 3).
Sch em e 1
Complex 5 was isolated as a white solid, only in 25%
yield due to the partial decomposition of the starting
complex 1 in the basic medium. The presence of the
functionalized alkynyl ligand in 5 is mainly supported
by the IR and 1H and 13C{1H} NMR spectra of the
compound. The IR spectrum in Nujol shows the ν(CtC)
and ν(CdO) bands at 2108 and 1702 cm-1, respectively.
In the 1H NMR spectrum, the most noticeable reso-
nances are two singlets at 3.36 and 2.01 ppm, with a
2:3 intensity ratio, which were assigned to the -CH2-
and -CH3 protons of the alkynyl ligand. In the 13C-
{1H} NMR spectrum, the R-carbon atom of this ligand
displays a doublet at 90.9 ppm, with a P-C coupling of
21.1 Hz, while the resonance of the â-carbon atom is
observed as a singlet at 110.2 ppm.
Because the allenylidene complex 1 is thermodynami-
cally more stable than the vinylidene intermediate
shown in Scheme 1, protonation of the alkynyl complex
5 should regenerate 1. However, we have observed that
the treatment of a diethyl ether solution of 5 with HBF4
in ca. 1:2 molar ratio does not lead to 1 but affords the
unsaturated cyclic carbene complex [Ru(η5-C5H5)-
1
contains a ν(CtC) band at 2123 cm-1. In the H NMR
spectrum, the most noticeable resonance is a singlet at
8.31 ppm, which was assigned to the dCH- proton of
the alkenyl group of the unsaturated η1-carbon ligand.
In the 13C{1H} NMR spectrum, the resonance of the
RudC carbon atom appears at 283.0 ppm whereas the
olefinic resonances of the alkenyl group are observed
at 148.7 (CH)) and 122.5 ()CPh2) ppm and those of
the acetylide unit at 106.9 and 77.3 ppm.
Ad d ition of Aceton e. The previous results from the
reactions of 1 with water, alcohols, thiols, and phenyl-
acetylene seem to suggest that addition of neutral
molecules to the allenylidene of 1 requires a transition
state, which favors the transfer of an electrophilic
hydrogen atom from the substrate to the â-carbon atom
of the allenylidene by means of an heteroatom-CR
interaction. The hydrogen atom of the carbon contigu-
ous to the carbonyl group of a ketone is lightly acidic,
and the oxygen atom has nucleophilic character. So,
at first glance, one should expect a reaction between the
allenylidene ligand of 1 and acetone. The expected
reaction product should be a functionalized vinylidene
derivative, as a result of a Claysen-type rearrangement
(Scheme 1). However, the allenylidene complex 1 is
stable in acetone solution, and apparently, a reaction
is not observed.
{CCH2C(Ph)2CHdC(CH3)O}(CO)(PiPr3)]BF4 (6), which
was isolated as a pink solid in 86% yield (eq 4).
If we assume that the allenylidene complex 1 is
thermodynamically more stable than the functionalized
vinylidene and that in acetone solution complex 1 is in
equilibrium with no detectable concentrations of this
vinylidene, the addition of base to the acetone solutions
of 1 should lead to a functionalized alkynyl complex, as
a result of the deprotonation of the â-hydrogen atom of
the vinylidene. The fair acidic character of this atom
(18) (a) Clark, G. R.; Hodgson, D. J .; Ng, M. M. P.; Rickard, C. E.
F.; Roper, W. R.; Wright, L. J . J . Chem. Soc., Chem. Commun. 1988,
1552. (b) Adams, H.; Bailey, N. A.; Ridgway, C.; Taylor, B. F.; Walters,
S. J .; Winter, M. J . J . Organomet. Chem. 1990, 394, 349. (c) Pilette,
D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.; Rickard, C. E. F.; Roper,
W. R. Organometallics 1992, 11, 809. (d) Stockman, K. E.; Sabat, M.;
Finn, M. G.; Grimes, R. N. J . Am. Chem. Soc. 1992, 114, 8733. (e)
Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier, B.
Organometallics 1994, 13, 4258. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R.
H.; Ziller, J . W. J . Am. Chem. Soc. 1995, 117, 5503. (g) Schwab, P.;
France, M. B.; Ziller, J . W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl.
1995, 34, 2039. (h) Nombel, P.; Lugan, N.; Mathieu, R. J . Organomet.
Chem. 1995, 503, C22. (i) Morran, P. D.; Mawby, R. J .; Wilson, G. D.;
Moore, M. H. J . Chem. Soc., Chem. Commun. 1996, 261. (j) Grunwald,
C.; Gevert, O.; Wolf, J .; Gonzalez-Herrero, P.; Werner, H. Organome-
tallics 1996, 15, 1960.
From a methodological point of view, it should be
noted that the formation of an unsaturated cyclic car-
bene from an allenylidene and a ketone has no prece-
dent. Previously, heteroatom-containing cyclic metal-
carbene complexes have been conveniently prepared via
(19) Bruce, M. I. Chem. Rev. 1991, 91, 197.

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 16, No. 26, 1997 5831
F igu r e 5. 1H,13C-HETCOR NMR spectrum of complex
[Ru(η5-C5H5){CCH2C(Ph)2CHdC(CH3)O}(CO)(PiPr3)]BF4 (6).
five singlets at 149.9, 113.8, 66.4, 43.8, and 17.8 ppm
should be mentioned, which were assigned to the carbon
atoms -Cd, dCH, CH2, -CPh2, and CH3, respectively,
1
on the basis of the 13C{1H}-DEPT and H,13C-HETCOR
(Figure 5) spectra.
F igu r e 4. 1H,1H-COSY NMR spectrum of complex [Ru-
In order to rationalize the unexpected finding of 6,
we carried out the protonation of 5 with deuterated
trifluoroacetic acid. The addition of 2 equiv of deuter-
ated trifluoroacetic acid to an NMR tube containing a
chloroform-d solution of 5 produces the formation of ca.
1 equiv of trifluoroacetic acid and 1 equiv of complex
(η5-C5H5){CCH2C(Ph)2CHdC(CH3)O}(CO)(PiPr3)]BF4 (6),
showing the resonances of the dCH- and -CH2 protons
of the unsaturated cyclic carbene ligand.
metal ω-haloacyl, carbamoyl, alkoxycarbonyl, or imido
intermediates,20 opening of epoxides by deprotonated
Fischer-type carbene complexes,21 and activation of
homopropargylic alcohols with low-valent d6 com-
plexes,22 including ruthenium(II) derivatives.23 In gen-
eral, the preparation of unsaturated cyclic carbene
complexes requires the previous preparation of func-
tional carbenes to react with â-dicarbonyl derivatives,
acrylates, and enol ethers.24
[Ru(η5-C5H5){CCD2C(Ph)2CHdC(CH3)O}(CO)(PiPr3)]+ (6-
d 2) (eq 5), only traces of [Ru(η5-C5H5){CCHDC(Ph)2-
CHdC(CH3)O}(CO)(PiPr3)]+ (6-d 1) and 6 are detected.
Complex 6 was characterized by elemental analysis
and IR and 1H, 31P{1H}, and 13C{1H} NMR spec-
1
troscopies. In the H NMR spectrum, the most notice-
able resonances are a singlet at 5.67 ppm and two
doublets at 4.35 and 3.52 ppm with a H-H coupling
constant of 16.0 Hz. On the basis of the 1H-COSY NMR
spectrum shown in Figure 4, the first resonance was
assigned to the dCH- proton of the unsaturated cyclic
carbene ligand and the other two resonances to the
-CH2- protons of the same ligand. In the 13C{1H}
NMR spectrum, the resonance corresponding to the
RudC carbon atom appears at 308.1 ppm as a doublet
with a P-C coupling constant of 9.6 Hz. In addition,
The presence of two deuterium atoms in 6-d 2 is strongly
supported by the 2H NMR spectrum of the complex,
which contains two broad signals at 3.97 and 3.55 ppm.
In this spectrum, no other resonances were detected.
To preclude some substantial kinetic isotope effects
at the CH2 group of the unsaturated cyclic carbene, we
also studied the protonation with HBF4 of Ru(η5-
C5H5){CtC-C(Ph)2CD2C(O)CD3}(CO)(PiPr3) (5-d 5),
which was prepared similarly to 5 but starting from 1
and deuterated acetone. In this case, under the same
experimental conditions as those used for the formation
of 6-d 2, the main organometallic product is [Ru(η5-
(20) (a) King, R. B. J . Am. Chem. Soc. 1963, 85, 1922. (b) Casey, C.
P.; Anderson, R. L. J . Am. Chem. Soc. 1971, 93, 3554. (c) Motschi, H.;
Angelici, R. J . Organometallics 1982, 1, 343. (d) Michelin, R. A.;
Zanotto, L.; Braga, D.; Sabatino, P.; Angelici, R. J . Inorg. Chem. 1988,
27, 93.
(21) (a) Casey, C. P.; Brunsvold, W. R.; Scheck, D. M. Inorg. Chem.
1977, 16, 3059. (b) Lattuada, L.; Licandro, E.; Maiorana, S.; Molinari,
H.; Papagni, A. Organometallics 1991, 10, 807. (c) Baldoli, C.; Lattuada,
L.; Licandro, E.; Maiorana, S.; Papagni, A. Organometallics 1993, 12,
2994.
C5H5){CCH2C(Ph)2CD)C(CD3)O}(CO)(PiPr3)]BF4 (6-d 4)
(22) (a) Parlier, A.; Rudler, H. J . Chem. Soc., Chem. Commun. 1986,
514. (b) Do¨tz, K. H.; Sturm, W.; Alt, H. G. Organometallics 1987, 6,
1424. (c) Quayle, P.; Rahman, S.; Ward, E. L. M.; Herbert, J .
Tetrahedron Lett. 1994, 35, 3801.
(23) (a) Davies, S. G.; McNally, J . P.; Smallridge, A. J . Adv.
Organomet. Chem. 1990, 30, 1. (b) Le Bozec, H.; Ouzzine, K.; Dixneuf,
P. H. Organometallics 1991, 10, 2768. (c) Ruiz, N.; Pe´ron, D.; Dixneuf,
P. H. Organometallics 1995, 14, 1095.
(24) (a) Camps, F.; Moreto´, J . M.; Ricart, S.;Vin˜as, J . M.; Molins,
E.; Miravitlles, C. J . Chem. Soc., Chem. Commun. 1989, 1560. (b)
J uneau, K. N.; Hegedus, L. S.; Roepke, F. W. J . Am. Chem. Soc. 1989,
111, 4762. (c) Wang, S. L. B.; Wulff, W. D. J . Am. Chem. Soc. 1990,
112, 4550. (d) Faron, K. L.; Wulff, W. D. J . Am. Chem. Soc. 1990, 112,
6419. (e) Segundo, A.; Moreto, J . M.; Vin˜as, J . M.; Ricart, S.; Molins,
E. Organometallics 1994, 13, 2467.

5832 Organometallics, Vol. 16, No. 26, 1997
Esteruelas et al.
Sch em e 2
in addition to ca. 1 equiv of DBF4 (eq 6). The position
The reaction of 1 with sodium acetylacetonate was
carried out with tetrahydrofuran as the solvent, and
complex 7 was isolated as a white solid in 79% yield.
The presence of the alkynyl ligand in 7 is supported by
the IR and 1H and 13C{1H} NMR spectra. The IR
spectrum in Nujol shows the ν(CtC) band at 2105 cm-1
along with two ν(CdO) absorptions at 1710 and 1699
cm-1. In the 1H NMR spectrum, the most noticeable
resonances of the alkynyl ligand are three singlets with
a 1:3:3 intensity ratio at 4.90, 2.11, and 2.07 ppm which
were assigned to the CH proton and both methyl groups.
In the 13C{1H} NMR spectrum, the R-carbon atom of
the alkynyl group appears at 94.8 ppm as a doublet with
a P-C coupling constant of 19.5 Hz, while the resonance
of the â-carbon atom is observed as a singlet at 108.0
ppm.
Ad d ition of Meth a n e. Complex 1 does not react
with methane. However, the product resulting from the
formal addition of this unreactive molecule to the Câ-
Cγ double bond of the allenylidene ligand of 1 can be
obtained by means of a synthetic strategy similar to that
previously described for the carbene complex 4. Similar
to the reaction shown in eq 1, treatment of the alle-
nylidene compound 1 with ca. 1 equiv of methyllithium
with tetrahydrofuran as the solvent leads to a mixture
of the allenyl complex Ru(η5-C5H5){C(CH3)dCdCPh2}-
(CO)(PiPr3) (8) and the alkynyl isomer Ru(η5-C5H5)-
{CtC-C(Ph)2CH3}(CO)(PiPr3) (9), according to eq 8.
2
of the deuterium atoms in 6-d 4 is supported by the H
NMR spectrum, which shows two singlets at 5.90
()CD-) and 2.30 (-CD3) ppm.
The formation of 6-d 2 and 6-d 4 can be rationalized
according to Scheme 2. One equivalent of acid proto-
nates the alkynyl group to afford a vinylidene interme-
diate, whereas the other equivalent catalyzes the keto-
enol conversion. Finally, the addition of the enol to the
C-C double bond of the vinylidene intermediate yields
the unsaturated cyclic carbene ligand.
The formation of 6 appears to be possible because the
keto-enol conversion is faster than the elimination of
acetone from the vinylidene intermediate. In contrast
to simple carbonyl compounds, the 1,3-dicarbonyl com-
pounds exist in their enol form in appreciable concen-
tration. For instance, acetylacetone has an enol content
of about 80%. Furthermore, it has two nucleophilic
leading groups (the carbonyls) and an electrophilic
hydrogen atom. So, at first glance, this diketone should
be an adequate substrate to give a related compound
to 6, by simple addition to complex 1. However, all our
attempts were unsuccessful.
Although complex 1 was recovered unchanged from
its acetylacetone solutions, it reacts with sodium acetyl-
acetonate to give the alkynyl derivative Ru(η5-C5H5)-
{CtC-C(Ph)2CH[C(O)CH3]2}(CO)(PiPr3) (7), related to
5. On the other hand, in contrast to 5, the reaction of
7 with HBF4 regenerates 1, with the formation of
acetylacetone (eq 7). This suggests that the inertia of
the acetylacetone is thermodynamic in origin and it
seems to be associated to the low stability of a vinylidene
intermediate, similar to that shown in Scheme 2.
The isomers were separated by fractional recrystal-
lization in n-hexane. Complex 8 (the minor product of

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 16, No. 26, 1997 5833
the reaction) was obtained in 18% yield as a yellow solid,
whereas the alkynyl isomer 9 (the main product of the
reaction) was obtained in 64% yield as a white solid. In
addition, the different selectivity between the reaction
shown in eq 8 and that observed for the reaction
summarized in eq 1 should be noted. While the addition
of the acetylide is favored in a 2.3:1 ratio toward the
R-carbon atom of the allenylidene, the addition of the
methyl group is favored in a 1:3.5 ratio toward the
γ-carbon atom of the unsaturated η1-carbon ligand.
Complexes 8 and 9 were characterized by elemental
analysis and IR and 1H, 13C{1H}, and 31P{1H} NMR
spectroscopies. Similar to the allenyl complex 2, the
most characteristic spectroscopic features of 8 are the
CdCdC stretching frequency in the IR spectrum, which
is observed at 1889 cm-1, and the three resonances in
the 13C{1H} NMR spectrum at 200.0 (d, J (PC) ) 2.3 Hz),
97.7 (s), and 88.3 (d, J (PC) ) 10.1 Hz) ppm for the Câ,
Cγ, and CR allenyl carbon atoms, respectively. In the
IR spectrum of 9, the most noticeable absorption is that
corresponding to the ν(CtC) vibration, which is ob-
served at 2114 cm-1. In the 13C{1H} NMR spectrum,
the resonance of the R-carbon atom of the alkynyl ligand
appears at 85.6 ppm as a doublet, with a P-C coupling
constant of 21.8 Hz. In addition, the singlets at 113.2,
47.3 and 32.4, corresponding to Câ, CPh2, and CH3
carbon atoms of the alkynyl ligand, should be men-
tioned.
Because in the allenylidene ligand of 1, the R- and
γ-carbon atoms are electrophilic centers and the â-car-
bon atom is nucleophilic; the general synthetic strategy
involves the initial nucleophilic attack of a carbanion
at the R- or γ-atom of the allenylidene group and the
subsequent protonation of the resulting allenyl or alky-
nyl derivatives.
In conclusion, we report a new synthetic strategy that
allows the formation of products, which are a result of
the formal C-C coupling between mutually inert frag-
ments.
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)(PiPr3)]BF4 (1)
was prepared by the published method.6
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). Elemental analyses were carried out on a Perkin-
Elmer 2400 CHNS/O analyzer. MS data were recorded on a
VG Autospec double-focusing mass spectrometer operating in
the positive mode; ions were produced with the standard Cs+
gun at ca. 30 kV, and 3-nitrobenzyl alcohol (NBA) was used
as the matrix.
The alkynyl complex 9 reacts with 1 equiv of HBF4
in diethyl ether to afford the vinylidene derivative [Ru-
(η5-C5H5){CdCHC(Ph)2CH3}(CO)(PiPr3)]BF4 (10, eq 9),
which is a result of the formal addition of a H-C bond
of methane to the Câ-Cγ double bond of the allenylidene
group of 1.
P r epa r a tion of Ru (η5-C5H5){C(CtCP h )dCdCP h 2}(CO)-
(P iP r 3) (2) a n d R u (η5-C5H 5){CtCC(P h )2CtCP h }(CO)-
(P iP r 3) (3). A solution of 1 (310 mg, 0.49 mmol) in 10 mL of
tetrahydrofuran at 233 K was treated with lithium phenyl-
acetylide (58 mg, 0.54 mmol), and the mixture was stirred for
1 h while the temperature was slowly increased to 263 K. The
color turned from dark red to orange, and the solvent was
removed in vacuo. Toluene (12 mL) was added, and the
mixture was filtered to eliminate LiBF4. The solvent was
evaporated at room temperature, and the residue was washed
with n-hexane, dried in vacuo, and washed with methanol to
afford 2 as a yellow solid. Yield: 130 mg (41%). Anal. Calcd
for C38H41OPRu: C, 70.67; H, 6.40. Found: C, 70.23; H, 6.66.
IR (Nujol, cm-1): ν(CtC) 2168 (m); ν(CO) 1934 (vs); ν(CdCdC)
1927 (s); ν(Ph) 1594 (m). 1H NMR (300 MHz, 293 K, C6D6): δ
7.70-6.80 (15H, Ph), 4.95 (s, 5H, Cp), 1.97 (m, 3H, PCHCH3),
0.94 (dd, 9H, J (HH) ) 6.8, J (PH) ) 13.5, PCHCH3), 0.86 (dd,
9H, J (HH) ) 7.0, J (PH) ) 12.8, PCHCH3). 31P{1H} NMR
(121.4 MHz, 293 K, C6D6): δ 70.2 (s). 13C{1H} NMR (75.4
MHz, 293 K, C6D6): δ 209.7 (d, J (PC) ) 1.5, dCd), 207.0 (d,
J (PC) ) 19.6, CO), 140.1, 139.9 (both s, Cipso), 131.6-125.9
(Ph), 98.3 (s, )CPh2), 94.7, 91.3 (s, CtC), 86.4 (s, Cp), 74.3 (d,
J (PC) ) 11.9, Ru-C)), 27.7 (d, J (PC) ) 22.4, PCHCH3), 20.0,
19.5 (both s, PCHCH3). The orange n-hexane solution was
concentrated to ca. 3 mL, and 3 precipitated as a white solid,
which was washed with cold n-hexane. Yield: 56 mg (18%).
Anal. Calcd for C38H41OPRu: C, 70.67; H, 6.40. Found: C,
70.18; H, 6.38. IR (Nujol, cm-1): ν(CtC) 2109, 2096 (both m);
ν(CO) 1931 (vs); ν(Ph) 1598 (m). 1H NMR (300 MHz, 293 K,
C6D6): δ 8.20-6.90 (15H, Ph), 4.80 (s, 5H, Cp), 2.03 (m, 3H,
PCHCH3), 1.10 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.4, PCHCH3),
0.84 (dd, 9H, J (HH) ) 6.9, J (PH) ) 12.7, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, C6D6): δ 74.8 (s). 13C{1H} NMR (75.4
MHz, 293 K, C6D6): δ 206.4 (d, J (PC) ) 19.0, CO), 147.7, 147.4
(both s, Cipso), 131.9-124.8 (Ph), 106.8 (s, Câ), 95.1, 83.1 (both
s, PhCtC), 90.9 (d, J (PC) ) 22.2, CR), 85.6 (s, Cp), 48.2 (s,
Cγ), 27.3 (d, J (PC) ) 23.7, PCHCH3), 20.3, 19.5 (both s,
PCHCH3).
Complex 10 was isolated as an orange solid in 97%
yield. The presence of a vinylidene ligand in this
complex is mainly supported by the 1H and 13C{1H}
NMR spectra. The 1H NMR spectrum contains the
characteristic dCH- resonance, which appears at 5.75
ppm as a doublet with a P-H coupling constant of 1.4
Hz, whereas the 13C{1H} NMR spectrum shows a
doublet at 356.0 ppm with a P-C coupling constant of
11.3 Hz for the R-carbon atom of the vinylidene group.
Con clu d in g Rem a r k s
Previously, we have reported that the allenylidene
complex 1 reacts with water, alcohols, thiols, and
benzophenone imine to afford R,â-unsaturated hydroxy-
carbene, alkoxycarbene, (alkylthio)carbene, and 2-azaal-
lenyl 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 the allenylidene ligand of
1. This study has revealed that although phenylacety-
lene, acetone, and methane do not react with 1, the
products resulting from the formal addition of H-C
bonds of these molecules to the CR-Câ or Câ-Cγ bonds
of the allenylidene ligand of 1 can be easily obtained.
P r ep a r a t ion of [R u (η5-C5H 5){C(CtCP h )CH dCP h 2}-
(CO)(P iP r 3)]BF 4 (4). A solution of 2 (119 mg, 0.18 mmol) in
5 mL of dichloromethane was treated with tetrafluoroboric acid

5834 Organometallics, Vol. 16, No. 26, 1997
Esteruelas et al.
(26 µL, 0.18 mmol, 54% in diethyl ether). Immediately, the
color turned from yellow to dark brown, and the solution was
concentrated almost to dryness. By slow addition of diethyl
ether, 4 was obtained as a dark brown solid. Yield: 120 mg
(89%). Anal. Calcd for C38H42BF4OPRu: C, 62.21; H, 5.77.
Found: C, 62.32; H, 5.45. IR (Nujol, cm-1): ν(CtC) 2123 (m);
ν(CO) 1950 (vs); ν(Ph) 1590 (w); ν(CdC) 1502 (m); ν(BF4) 1053
(vs, br). 1H NMR (300 MHz, 293 K, (CD3)2CO): δ 8.31 (br s,
1H, HC)), 7.54-6.96 (15H, Ph), 5.71 (s, 5H, Cp), 2.55 (m, 3H,
PCHCH3), 1.36, 1.24 (both dd, 18H, J (HH) ) 7.4, J (PH) ) 14.8,
PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, (CD3)2CO): δ
68.2 (s). 13C{1H} NMR (75.4 MHz, 293 K, (CD3)2CO): δ 283.0
(br, RudC), 202.7 (d, J (PC) ) 16.2, CO), 148.7 (br s, 1H, HC)),
141.3, 138.9 (both s, Cipso), 131.8, 131.7, 131.4, 131.3, 130.4,
130.2, 129.2, 128.8, 128.7 (all s, Ph), 122.5 (s, )CPh2), 106.9
(br s, CtCPh), 93.3 (br, Cp), 77.3 (s, CtCPh), 29.8 (br d, J (PC)
) 23.9, PCHCH3), 19.8, 19.6 (both s, PCHCH3).
P r ep a r a tion of Ru (η5-C5H5){CtCC(P h )2CH2C(O)CH3}-
(CO)(P iP r 3) (5). 1 (350 mg, 0.55 mmol) was added in small
amounts to a stirred suspension of potassium hydroxide (69
mg, 85%, 1.05 mmol) in 10 mL of acetone at 303 K, and the
mixture was stirred for 10 min. The solvent was removed in
vacuo from the yellow solution, 12 mL of toluene was added,
and the mixture was filtered to eliminate NaBF4 and excess
of potassium hydroxide. The solvent was removed in vacuo,
and the residue was extracted with 6 fractions of 10 mL of
n-hexane each at 203 K. The yellow n-hexane solution was
concentrated to ca. 2 mL, and 5 precipitated as a white solid.
The solid was washed with cold n-hexane. Yield: 85 mg (25%).
Anal. Calcd for C33H41O2PRu: C, 65.87; H, 6.87. Found: C,
65.26; H, 7.04. IR (Nujol, cm-1): ν(CtC) 2108 (m); ν(CO) 1931
(vs); ν(C)O) 1702 (s); ν(Ph) 1595 (m). 1H NMR (300 MHz, 293
K, C6D6): δ 7.72-7.70 (10H, Ph), 4.87 (s, 5H, Cp), 3.36 (s, 2H,
CH2), 2.01 (s, 3H, CH3), 1.92 (m, 3H, PCHCH3), 1.04 (dd, 9H,
J (HH) ) 7.1, J (PH) ) 14.5, PCHCH3), 0.81 (dd, 9H, J (HH) )
7.1, J (PH) ) 12.9, PCHCH3). 31P{1H} NMR (121.4 MHz, 293
K, C6D6): δ 75.1 (s). 13C{1H} NMR (75.4 MHz, 293 K, C6D6):
δ 206.5 (d, J (PC) ) 18.1, CO), 205.7 (s, CdO), 148.7, 148.5
(both s, Cipso), 128.0-125.9 (Ph), 110.2 (s, Câ), 90.9 (d, J (PC)
) 21.1, CR), 85.6 (d, J (PC) ) 0.9, Cp), 57.3, 49.5 (both s, CH2
+ Cγ), 31.4 (s, CH3), 27.2 (d, J (PC) ) 23.9, PCHCH3), 20.2,
19.4 (both s, PCHCH3).
P r ep a r a tion of Ru (η5-C5H5){CtCC(P h )2CD2C(O)CD3}-
(CO)(P iP r 3) (5-d 5). To a stirred solution of diisopropylamine
(55 µL, 0.40 mmol) in 10 mL of tetrahydrofuran at 195 K was
added butyllithium (247 µL, 0.40 mmol, 1.6 M in n-hexane).
The mixture was stirred for 1.5 h and then was treated with
acetone-d6 (29 µL, 0.40 mmol) and stirred for 30 min. The
temperature was slowly increased to 243 K, and then 1 (250
mg, 0.40 mmol) was added. The mixture was stirred for 1 h
while the temperature slowly increased to room temperature,
and the color changed from dark red to yellow. The solvent
was evaporated, 40 mL of n-hexane was added, and the
mixture was filtered to eliminate LiBF4. The solution was
concentrated to ca. 2 mL, and 5-d 5 precipitated as a white
solid. Yield: 58 mg (24%). 1H NMR (300 MHz, 293 K, C6D6):
δ 7.72-7.70 (10H, Ph), 4.87 (s, 5H, Cp), 1.92 (m, 3H, PCHCH3),
1.04 (dd, 9H, J (HH) ) 7.1, J (PH) ) 14.5, PCHCH3), 0.81 (dd,
9H, J (HH) ) 7.1, J (PH) ) 12.9, PCHCH3). 2D{1H} NMR
(46.07 MHz, 293 K, C6H6): δ 3.29 (br s, CD2), 1.93 (s, CD3).
31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ 75.1 (s).
3H, PCHCH3), 2.20 (s, 3H, CH3), 1.27 (dd, 9H, J (HH) ) 7.4,
J (PH) ) 16.4, PCHCH3), 1.18 (dd, 9H, J (HH) ) 7.4, J (PH) )
14.8, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ
68.7 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus
DEPT): δ 308.1 (Cquat, d, J (PC) ) 9.6, RudC), 201.5 (Cquat, d,
J (PC) ) 15.6, CO), 149.9 (Cquat, s, CH3-C)), 143.6, 143.2 (Cquat
,
both s, Cipso), 129.0, 128.9, 127.4, 127.3, 127.1, 126.8 (-, all s,
Ph), 113.8 (-, s, )CH), 90.4 (-, s, Cp), 66.4 (+, s, CH2), 43.8
(Cquat, s, CPh2), 29.3 (-, d, J (PC) ) 24.9, PCHCH3), 19.7, 19.5
(-, both s, PCHCH3), 17.8 (-, s, CH3). MS (FAB+): m/z )
603 (M+).
Rea ction of 5 w ith Deu ter a ted Tr iflu or oa cetic Acid :
P r ep a r a tion of [Ru (η5-C5H5){CCD2C(P h )2CHdC(CH3)O}-
(CO)(P iP r 3)]BF 4 (6-d 2). A solution of 5 (11.5 mg, 0.019 mmol)
in 0.5 mL of CDCl3 in an NMR tube was treated with
deuterated trifluoroacetic acid (3.0 µL, 0.038 mmol). The NMR
tube was sealed under argon, and measurements were made
immediately. 1H NMR (300 MHz, 293 K, CDCl3): δ 7.41-
7.02 (10H, Ph), 5.68 (br s, 1H, CdCH), 5.00 (s, 5H, Cp), 2.35
(m, 3H, PCHCH3), 2.20 (s, 3H, CH3), 1.27 (dd, 9H, J (HH) )
7.4, J (PH) ) 16.4, PCHCH3), 1.18 (dd, 9H, J (HH) ) 7.4, J (PH)
) 14.8, PCHCH3). 2D{1H} NMR (46.07 MHz, 293 K, CH2Cl2):
δ 3.97, 3.55 (both br, CD2).31P{1H} NMR (121.4 MHz, 293 K,
CDCl3): δ 68.7 (s).
Rea ction of 5-d 5 w ith Tetr a flu or obor ic Acid : P r ep a r a -
t ion of [R u (η5-C5H 5){CCH 2C(P h )2CDdC(CD3)O}(CO)-
(P iP r 3)]BF 4 (6-d 4). A solution of 5-d 5 (10.4 mg, 0.017 mmol)
in 0.5 mL of CDCl3 in an NMR tube was treated with
tetrafluoroboric acid (4.6 µL, 0.034 mmol). The NMR tube was
sealed under argon, and measurements were made immedi-
ately. 1H NMR (300 MHz, 293 K, CDCl3): δ 7.41-7.02 (10H,
Ph), 5.09 (s, 5H, Cp), 4.34, 3.49 (both d, 2H, J gem ) 16.0, CH2),
2.35 (m, 3H, PCHCH3), 1.27 (dd, 9H, J (HH) ) 7.4, J (PH) )
16.4, PCHCH3), 1.18 (dd, 9H, J (HH) ) 7.4, J (PH) ) 14.8,
PCHCH3). 2D{1H} NMR (46.07 MHz, 293 K, CH2Cl2): δ 5.90
(br, CdCD), 2.30 (s, CD3).31P{1H} NMR (121.4 MHz, 293 K,
CDCl3): δ 68.7 (s).
P r epar ation of Ru (η5-C5H5){CtCC(P h )2CH[C(O)CH3]2}-
(CO)(P iP r 3) (7). A solution of 1 (250 mg, 0.40 mmol) was
treated with sodium acetylacetonate (49 mg, 0.40 mmol) in
10 mL of tetrahydrofuran, and the mixture was stirred for 2
min. The color turned from dark red to pale yellow and the
solvent was removed in vacuo. Toluene (12 mL) was added,
and the mixture was filtered to eliminate NaBF4. The solvent
was removed in vacuo, and the residue was washed with
n-pentane to afford 7 as a white solid. Yield: 200 mg (79%).
Anal. Calcd for C35H43O3PRu: C, 65.30; H, 6.73. Found: C,
65.02; H, 6.54. IR (Nujol, cm-1): ν(CtC) 2105 (m); ν(CO) 1938
(vs); ν(C)O) 1710, 1699 (both s); ν(Ph) 1595 (w). 1H NMR (300
MHz, 293 K, C6D6): δ 7.99-6.89 (10H, Ph), 4.93 (s, 5H, Cp),
4.90 (s, 1H, CH), 2.11, 2.07 (both s, 6H, 2CH3), 1.92 (m, 3H,
PCHCH3), 1.11 (dd, 9H, J (HH) ) 7.1, J (PH) ) 14.5, PCHCH3),
0.90 (dd, 9H, J (HH) ) 7.1, J (PH) ) 13.0, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, C6D6): δ 75.5 (s). 13C{1H} NMR (75.4
MHz, 293 K, C6D6): δ 206.3 (d, J (PC) ) 18.0, CO), 205.7, 205.4
(both s, CdO), 147.5, 147.4 (both s, Cipso), 128.0-126.4 (Ph),
108.0 (s, Câ), 94.8 (d, J (PC) ) 19.5, CR), 85.6 (s, Cp), 77.3 (s,
CH), 52.9 (s, Cγ), 31.4, 31.3 (both s, CH3), 27.5 (d, J (PC) )
23.4, PCHCH3), 20.3 (s, PCHCH3), 19.5 (d, J (PC) ) 1.4,
PCHCH3).
P r ep a r a t ion of R u (η5-C5H 5){C(CH 3)dCdCP h 2}(CO)-
(P iP r 3) (8) a n d Ru (η5-C5H5){CtCC(P h 2)CH3}(CO)(P iP r 3)
(9). A solution of 1 (300 mg, 0.48 mmol) in 5 mL of tetrahy-
drofuran at 195 K was treated with methyllithium (300 µL,
0.48 mmol, 1.6 M in diethyl ether), and immediately the color
turned from dark red to yellow. The temperature was
increased to room temperature, and the solvent was evapo-
rated. Toluene (12 mL) was added, and the mixture was
filtered to eliminate LiBF4. The solvent was removed in vacuo,
and the residue was extracted with n-hexane to afford 9 as a
P r epar ation of [Ru (η5-C5H5){CCH2C(P h )2CHdC(CH3)O}-
(CO)(P iP r 3)]BF 4 (6). A solution of 5 (80 mg, 0.13 mmol) in 5
mL of diethyl ether was treated with tetrafluoroboric acid (38
µL, 0.26 mmol, 54% in diethyl ether). Immediately, 6 precipi-
tated as a pink solid. Yield: 79 mg (86%). Anal. Calcd for
C
33H42BF4O2PRu: C, 57.48; H, 6.14. Found: C, 56.94; H, 5.84.
IR (Nujol, cm-1): ν(CO) 1985 (vs); ν(CdC-O) 1701 (m); ν(Ph)
1599 (m); ν(BF4) 1045 (vs, br). 1H NMR (300 MHz, 293 K,
CDCl3): δ 7.41-7.02 (10H, Ph), 5.67 (br s, 1H, CdCH), 5.09
(s, 5H, Cp), 4.35, 3.52 (both d, 2H, J gem ) 16.0, CH2), 2.35 (m,
white solid. Yield: 170 mg (64%). Anal. Calcd for C31H39
-

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 16, No. 26, 1997 5835
Ta ble 2. Cr ysta l Da ta a n d Da ta Collection a n d
Refin em en t for [Ru (η5-C5H5){C(CtCP h )-
CHdCP h 2}(CO)(P iP r 3)]BF 4 (4)
OPRu: C, 66.52; H, 7.02. Found: C, 66.67; H, 6.82. IR (Nujol,
cm-1): ν(CtC) 2114 (m); ν(CO) 1930 (vs); ν(Ph) 1597 (m). 1H
NMR (300 MHz, 293 K, C6D6): δ 7.60-6.80 (10H, Ph), 4.86
(s, 5H, Cp), 2.11 (s, 3H, CH3), 1.90 (m, 3H, PCHCH3), 1.88
(dd, 9H, J (HH) ) 7.2, J (PH) ) 14.4, PCHCH3), 0.86 (dd, 9H,
J (HH) ) 7.2, J (PH) ) 13.2, PCHCH3). 31P{1H} NMR (121.4
MHz, 293 K, C6D6): δ 75.0 (s). 13C{1H} NMR (75.4 MHz, 293
K, C6D6): δ 206.6 (d, J (PC) ) 18.9, CO), 150.7, 150.5 (both s,
Crystal Data
formula
mol wt
C38H42BF4OPRu
733.57
color and habit
cryst size, mm
symmetry
space group
a, Å
b, Å
c, Å
yellow, prismatic block
0.32 × 0.22 × 0.27
monoclinic
P21/n
C
ipso), 128.2-125.6 (Ph), 113.2 (s, Câ), 85.6 (d, J (PC) ) 1.3, Cp),
85.6 (d, J (PC) ) 21.8, CR), 47.3 (s, Cγ), 32.4 (s, CH3), 27.2 (d,
J (PC) ) 23.5, PCHCH3), 20.2 (s, PCHCH3), 19.4 (d, J (PC) )
1.6, PCHCH3). The solvent from the yellow n-hexane solution
was evaporated, and the residue was washed with methanol
to afford 8 as a yellow solid. Yield: 49 mg (18%). Anal. Calcd
for C31H39OPRu: C, 66.52; H, 7.02. Found: C, 66.40; H, 7.14.
IR (Nujol, cm-1): ν(CO) 1914 (vs); ν(CdCdC) 1889 (s); ν(Ph)
1596 (m). 1H NMR (300 MHz, 293 K, C6D6): δ 7.70-7.10 (10H,
Ph), 4.93 (s, 5H, Cp), 2.49 (s, CH3), 1.89 (m, 3H, PCHCH3),
0.97 (dd, 9H, J (HH) ) 7.4, J (PH) ) 14.2, PCHCH3), 0.73 (dd,
9H, J (HH) ) 7.1, J (PH) ) 12.8, PCHCH3). 31P{1H} NMR
(121.4 MHz, 293 K, C6D6): δ 72.6 (s). 13C{1H} NMR (75.4
MHz, 293 K, C6D6): δ 208.3 (d, J (PC) ) 20.7, CO), 200.0 (d,
J (PC) ) 2.3, dCd), 141.9, 141.8 (both s, Cipso), 129.3-125.0
(Ph), 97.7 (s, )CPh2), 88.3 (d, J (PC) ) 10.1, Ru-C)), 85.9 (d,
J (PC) ) 0.9, Cp), 32.9 (s, CH3), 27.1 (d, J (PC) ) 22.0,
PCHCH3), 20.1, 19.08 (both s, PCHCH3).
P r ep a r a tion of [Ru (η5-C5H5){CdCHC(P h )2CH3}(CO)-
(P iP r 3)]BF 4 (10). A solution of 9 (68.5 mg, 0.12 mmol) in 5
mL of diethyl ether was treated with tetrafluoroboric acid (17
µL, 0.12 mmol, 54% in diethyl ether). Immediately, 10
precipitated as an orange solid. Yield: 77 mg (97%). Anal.
Calcd for C31H40BF4OPRu: C, 57.50; H, 6.23. Found: C, 57.16;
H, 6.31. IR (Nujol, cm-1): ν(CO) 2010 (vs); ν(CdC) 1673 (m);
ν(Ph) 1599 (w); ν(BF4) 1049 (vs, br). 1H NMR (300 MHz, 293
K, (CD3)2CO): δ 7.37-7.17 (10H, Ph), 5.75 (d, 1H, J (PH) )
1.4, HC)), 5.50 (s, 5H, Cp), 2.39 (m, 3H, PCHCH3), 1.92 (s,
3H, CH3), 1.28 (dd, 9H, J (HH) ) 7.1, J (PH) ) 10.5, PCHCH3),
1.23 (dd, 9H, J (HH) ) 7.1, J (PH) ) 9.8, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, (CD3)2CO): δ 79.1 (s). 13C{1H} NMR
(75.4 MHz, 293 K, (CD3)2CO): δ 356.0 (d, J (PC) ) 11.3, CR),
198.1 (d, J (PC) ) 15.1, CO), 147.5, 146.6 (both s, Cipso), 128.6,
128.4, 127.4, 127.1, 127.0, 126.9 (all s, Ph + Câ), 92.5 (s, Cp),
47.9 (s, Cγ), 31.0 (s, CH3), 28.9 (d, J (PC) ) 25.6, PCHCH3),
20.0, 19.6 (both s, PCHCH3).
X-r a y Str u ctu r e An a lysis of Com p lex [Ru (η5-C5H5)-
{C(CtCP h )CHdCP h 2}(CO)(P iP r 3)]BF 4 (4). Crystals suit-
able for the X-ray diffraction study were obtained by slow
diffusion of diethyl ether into a concentrated solution of 4 in
CH2Cl2. A summary of the crystal data and refinement
parameters is reported in Table 2. The yellow, prismatic
crystal, of approximate dimensions 0.32 × 0.22 × 0.27 mm,
was glued on a glass fiber and mounted on a Siemens-STOE
AED-2 diffractometer. A group of 57 reflections in the range
20° e 2θ e 35° was carefully centered at 298 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
semiempirical method.25 The structure was solved by Patter-
son (Ru atom, SHELXTL-PLUS26) and conventional Fourier
techniques and refined by full-matrix least-squares on F2
(SHELXL9327). An isopropyl group of a phosphine ligand
(C(36)-C(38)) was observed to be disordered. The disordered
group was modeled by including two different isopropyl groups
with a complementary occupancy factor refined to a final value
9.687(1)
18.539(3)
19.785(2)
99.88(1)
3500.4(8)
4
â, deg
V, Å3
Z
Dcalcd, g cm-3
1.392
Data Collection and Refinement
diffractometer
four-circle Siemens-STOE AED
λ(Mo KR), Å; technique
monochromator
µ, mm-1
0.710 73; bisecting geometry
graphite oriented
0.54
ω/2θ
3° e 2θ e 50°
298
scan type
2θ range, deg
temp, K
no. of data collect
no. of unique data
no. of params refined
6337
6149 (Rint ) 0.0498)
456
0.0530
0.1472
1.066
R1 (F2 > 2σ(F2))
a
b
wR2 (all data (Fo g 0))
Sc (all data)
a
b
2
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/
∑[w(Fo2)2]}1/2
.
c Goof ) S ) {∑[w(Fo - Fc2)2]/(n - p)}1/2, where n
2
is the number of reflections and p is the number of refined
parameters.
of 0.67(3) for the a-labeled atoms and 0.33(3) for the b-labeled
ones. Both, a- and b-labeled groups were refined with a
common restrained C(36)-C(37) and C(36)-C(38) distance
(1.54(1) Å). The BF4-anion was also observed to be disordered.
It was modeled on the basis of two different moieties sharing
the central boron atom with complementary occupancy factors
refined to a final values of 0.59(3) and 0.41(3). Both groups
were refined with a common restrained B-F distance (1.33-
(1) Å). Anisotropic parameters were used in the last cycles of
refinement for all non-hydrogen atoms, except those of the
isopropyl group involved in the disorder. The hydrogen atoms
were calculated and refined riding on carbon atoms with a
common isotropic thermal parameter. Atomic scattering fac-
tors, corrected for anomalous dispersion for Ru and P, were
implemented by the program. The refinement converged to
R1 ) 0.0530 (F2 > 2σ(F2)) and wR2 ) 0.1472 (all data Fo g 0),
with weighting parameters x ) 0.0799 and y ) 4.85.
Ack n ow led gm en t. We thank the DGICYT (Project
No. PB-95-0806, Programa de Promocio´n General del
Conocimiento) for financial support. E.O. thanks the
DGA (Diputacio´n General de Arago´n) for a grant.
Ap p en d ix: The extended Hu¨ckel calculations have
been carried out on model complex [Ru(η5-C5H5)-
(CdCdCH2)(CO)(PH3)]+ using standard geometrical
parameters. The calculations have been performed
using the program CACAO28 with the supplied atomic
Hii parameters.
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, and bond distances
and angles (12 pages). Ordering information is given on any
current masthead page.
(25) North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr.
1968, A24, 351.
(26) Sheldrick, G. SHELXTL-PLUS; Siemens Analitical X-Ray
Instruments Inc.: Madison, WI, 1990.
(27) Sheldrick, G. SHELXL-93. Program for Crystal Structure
Refinement; Institu¨t fu¨r Anorganische Chemie der Universita¨t: Go¨t-
tingen, Germany, 1993.
OM9708539
(28) Mealli, C.; Proserpio, D. M. J . Chem. Educ. 1990, 67, 39.