Activation of 2-propyn-1-ol derivatives by indenylruthenium(II) and -osmium(II) complexes: X-ray crystal structures of the allenylidene complexes [M(=C=C=CPh2)(η5-C9H7)(PPh 3)2][PF6]·CH2Cl2 (M = Ru, Os) and EHMO calculations

Article abstract of DOI:10.1021/om9509397

The allenylidene complexes [M(=C=C=CR₂)(η⁵-C₉H₇)L ₂][PF₆] (M = Ru, L = PPh₃, L₂ = 1,2-bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)methane (dppm), R₂ = 2 Ph (1a-c), C₁₂H₈ (2,2′-biphenyldiyl) (2a-c); M = Os, L = PPh₃, R₂ = 2Ph (3), C₁₂H₈ (4)) have been prepared by reaction of the complexes [MCl(η⁵-C₉H₇)L₂] with HC≡CC(OH)R₂ and NaPF₆ in refluxing methanol. The crystal structures of [M(=C=C=CPh₂)(η⁵-C₉H₇)(PPh ₃)₂][PF₆]·CH₂Cl₂ (M = Ru (1a), Os (3)) were determined by X-ray diffraction methods. In the structures the M=C=C=C chains are nearly linear (M-C(1)-C(2) = 168.5-(5)° (1a) and 169.3(4)° (3); C(1)-C(2)-C(3) = 168.2(7)° (1a) and 168.0(5)° (3)) with M=C(1) distances of 1.878(5) A?(1a) and 1.895(4) A? (3). The indenyl ligand is η⁵-bonded to the metal with the benzo ring orientated cis with respect to the allenylidene group. Extended Hu?ckel molecular orbital calculations have been used to rationalize the preferred cis orientation. The reaction of [RuCl(η⁵-C₉H₇)L₂] (L = PPh₃, L₂ = dppe, dppm) with HC≡CCMe(OH)Ph and NaPF₆ in refluxing methanol leads to the formation of the allenylidene complexes [Ru-{=C=C=C(Me)Ph}(η⁵-C₉H₇)L ₂][PF₆] (6a-c) along with the vinylvinylidene isomers [Ru-{=C=C(H)C(Ph)=CH₂}(η⁵-C₉H ₇)L₂][PF₆] (L = PPh₃ (5a), L₂ = dppe (5b), dppm (5c)). Only complex 6a could be isolated by chromatography (SiO₂) from these mixtures along with complex 7a obtained from the deprotonation of the vinylvinylidene complex 5a. The treatment of these reaction mixtures with potassium carbonate yields the neutral σ-enynyl derivatives [Ru{C≡CC(Ph)=CH₂}(η⁵-C₉H ₇)L₂] (7a-c). The monosubstituted allenylidene complex [Ru{=C=C=C(H)Ph}(η⁵-C₉H₇)(PPh ₃)₂][PF₆] (9) has been prepared by the reaction of [RuCl(η⁵-C₉H₇)(PPh₃) ₂] with HC=CCH(OH)Ph and NaPF₆ in methanol. Under similar reaction conditions [RuCl(η⁵-C₉H₇)L₂] reacts with HC=CCH(OH)R and NaPF₆ to afford the alkenylmethoxycarbene derivatives [Ru{=C(OMe)C(H)=CH(R)}(η⁵-C₉H₇)L ₂][PF₆] (L₂ = dppe, R = Ph (11b); L₂ = dppm, R = Ph (11c), H (13)). [RuCl(η⁵-C₉H₇)(PPh₃) ₂] also reacts with HC=CC(OH)H₂ to give the hydroxyvinylidene complex [Ru{=C=CH(CH₂OH)}(η⁵-C₉H ₇)-(PPh₃)₂][PF₆] (12), which is stable toward the dehydration process.

Full text of DOI:10.1021/om9509397

Organometallics 1996, 15, 2137-2147
2137
Activa tion of 2-P r op yn -1-ol Der iva tives by
In d en ylr u th en iu m (II) a n d -osm iu m (II) Com p lexes: X-r a y
Cr ysta l Str u ctu r es of th e Allen ylid en e Com p lexes
[M(dCdCdCP h 2)(η5-C9H7)(P P h 3)2][P F 6]‚CH2Cl2 (M ) Ru ,
Os) a n d EHMO Ca lcu la tion s
Victorio Cadierno,† M. Pilar Gamasa,† J ose´ Gimeno,*,†
Mercedes Gonza´lez-Cueva,† Elena Lastra,† J avier Borge,‡
Santiago Garc´ıa-Granda,‡ and Enrique Pe´rez-Carren˜o‡
Departamento de Quı´mica Orga´nica e Inorga´nica and Departamento de Quı´mica Fı´sica y
Analı´tica, Instituto de Quı´mica Organometa´lica “Enrique Moles” (Unidad Asociada al CSIC),
Facultad de Qu´ımica, Universidad de Oviedo, 33071 Oviedo, Spain
Received December 6, 1995X
The allenylidene complexes [M(dCdCdCR2)(η5-C9H7)L2][PF6] (M ) Ru, L ) PPh3, L2 )
1,2-bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)methane (dppm), R2 ) 2
Ph (1a -c), C12H8 (2,2′-biphenyldiyl) (2a -c); M ) Os, L ) PPh3, R2 ) 2Ph (3), C12H8 (4))
have been prepared by reaction of the complexes [MCl(η5-C9H7)L2] with HCtCC(OH)R2 and
NaPF6 in refluxing methanol. The crystal structures of [M(dCdCdCPh2)(η5-
C9H7)(PPh3)2][PF6]‚CH2Cl2 (M ) Ru (1a ), Os (3)) were determined by X-ray diffraction
methods. In the structures the MdCdCdC chains are nearly linear (M-C(1)-C(2) ) 168.5-
(5)° (1a ) and 169.3(4)° (3); C(1)-C(2)-C(3) ) 168.2(7)° (1a ) and 168.0(5)° (3)) with MdC(1)
distances of 1.878(5) Å (1a ) and 1.895(4) Å (3). The indenyl ligand is η5-bonded to the metal
with the benzo ring orientated “cis” with respect to the allenylidene group. Extended Hu¨ckel
molecular orbital calculations have been used to rationalize the preferred “cis” orientation.
The reaction of [RuCl(η5-C9H7)L2] (L ) PPh3, L2 ) dppe, dppm) with HCtCCMe(OH)Ph
and NaPF6 in refluxing methanol leads to the formation of the allenylidene complexes [Ru-
{dCdCdC(Me)Ph}(η5-C9H7)L2][PF6] (6a -c) along with the vinylvinylidene isomers [Ru-
{dCdC(H)C(Ph)dCH2}(η5-C9H7)L2][PF6] (L ) PPh3 (5a ), L2 ) dppe (5b), dppm (5c)). Only
complex 6a could be isolated by chromatography (SiO2) from these mixtures along with
complex 7a obtained from the deprotonation of the vinylvinylidene complex 5a . The
treatment of these reaction mixtures with potassium carbonate yields the neutral σ-enynyl
derivatives [Ru{CtCC(Ph)dCH2}(η5-C9H7)L2] (7a -c). The monosubstituted allenylidene
complex [Ru{dCdCdC(H)Ph}(η5-C9H7)(PPh3)2][PF6] (9) has been prepared by the reaction
of [RuCl(η5-C9H7)(PPh3)2] with HCtCCH(OH)Ph and NaPF6 in methanol. Under similar
reaction conditions [RuCl(η5-C9H7)L2] reacts with HCtCCH(OH)R and NaPF6 to afford the
alkenylmethoxycarbene derivatives [Ru{dC(OMe)C(H)dCH(R)}(η5-C9H7)L2][PF6] (L2 ) dppe,
R ) Ph (11b); L2 ) dppm, R ) Ph (11c), H (13)). [RuCl(η5-C9H7)(PPh3)2] also reacts with
HCtCC(OH)H2 to give the hydroxyvinylidene complex [Ru{dCdCH(CH2OH)}(η5-C9H7)-
(PPh3)2][PF6] (12), which is stable toward the dehydration process.
In tr od u ction
in the study of the activation of alkynes by indenylru-
thenium complexes, and we recently reported that the
reactions of these derivatives with terminal alkynes and
alkynols allow the preparation of alkynyl, vinylidene,
Fischer-type carbene, vinylvinylidene, and enynyl
complexes.2k,4 Furthermore, we have also reported
initial studies on the reactivity of the mono- and
disubstituted allenylidene complexes [Ru{dCdCdC(R)-
Ph}(η5-C9H7)(PPh3)2]+ (R ) Ph, H), showing that the
allenylidene moiety is an excellent building block for the
preparation of polyunsaturated chains including yne-
propynyl,5 polyenynyl, alkynyl-carbene, and vinylidene-
carbene species.6
Although the chemistry of transition-metal alle-
nylidene complexes [M]dCdCdCR2 is comparatively
much less developed than that of the vinylidene deriva-
tives,1 during the last few years the interest in studying
these highly unsaturated carbene species has notably
increased.2 This is probably due to the fact that the
carbon chain contains a high degree of unsaturation
with the presence of three carbon atoms potentially
activated. Since its reactivity still remains largely
unexplored,3 the potential utility in chemical transfor-
mations has not been yet exploited. We are interested
We now report the synthesis and characterization of
the disubstituted, very stable allenylidene complexes
[M(dCdCdCRR′)(η5-C9H7)L2][PF6] (M ) Ru, Os) ob-
tained by the activation of disubstituted propargyl
alcohols HCtCC(OH)R2 with half-sandwich indenyl
† Departamento de Qu´ımica Orga´nica e Inorga´nica.
‡ Departamento de Qu´ımica F´ısica y Anal´ıtica.
X Abstract published in Advance ACS Abstracts, March 15, 1996.
(1) (a) Bruce, M. I.; Swincer, A. G. Adv. Organomet. Chem. 1983,
22, 59. (b) Bruce, M. I. Chem. Rev. 1991, 91, 197. (c) Antonova, A. B.;
J ohansson, A. A. Russ. Chem. Rev. (Engl. Trans.) 1989, 58, 693.
0276-7333/96/2315-2137$12.00/0 © 1996 American Chemical Society

2138 Organometallics, Vol. 15, No. 8, 1996
Cadierno et al.
Sch em e 1
Sch em e 2
Resu lts a n d Discu ssion
Syn th esis of Disu bstitu ted Allen ylid en er u th e-
n iu m a n d -Osm iu m Com p lexes. The reaction of
[RuCl(η5-C9H7)L2] (L ) PPh3, L2 ) dppe, dppm) with
disubstituted propargyl alcohols HCtCC(OH)R2 (R )
Ph, R2 ) C12H8 (2,2′-biphenyldiyl)) in refluxing metha-
nol and in the presence of a slight excess of NaPF6 gives
the allenylideneruthenium complexes 1a -c and 2a -c
in good yields (72-83%) (Scheme 2). Under similar
reaction conditions [OsCl(η5-C9H7)(PPh3)2]7 reacts with
an excess of the alcohols to yield complexes 3 (R ) Ph,
55% yield) and 4 (R2 ) C12H8 (2,2′-biphenyldiyl), 39%
yield), which are, to the best of our knowledge, the first
examples of allenylideneosmium derivatives.
complexes [MCl(η5-C9H7)L2] (L ) PPh3, M ) Ru, Os; L2
) dppm, dppe, M ) Ru). It is also shown that the
stabilization of the allenylidene moiety by the metal
substrate depends on the nature of the propargyl
alcohols and on the ancillary ligands. Thus, while the
reaction of the monosubstituted propargyl alcohol
HCtCCH(OH)Ph with [RuCl(η5-C9H7)(PPh3)2] in MeOH
leads to the formation of [Ru{dCdCdC(H)Ph}(η5-C9H7)-
(PPh3)2]+, Fischer type vinylcarbene complexes [Ru{dC-
(OMe)C(H)dCH(R)}(η5-C9H7)L2]+ are obtained when
metal substrates containing chelating phosphines, [RuCl-
(η5-C9H7)L2] (L ) dppm, dppe), are used for the activa-
tion of either HCtCCH(OH)Ph or HCtCC(OH)H2. We
also show that with the presence of a deprotonatable
group as a substituent of the propargyl alcohol, i.e.
HCtCCMe(OH)Ph, a competitive process takes place
which leads to the formation of the allenylidene complex
B, along with the vinylvinylidene isomer C (Scheme 1).
These reactions show the synthetic limitations of the
well-established methodology for the preparation of
allenylideneruthenium(II) complexes which was first
reported by Selegue in 1982.2j
All the allenylidene complexes are air stable in the
solid state and soluble in chlorinated solvents and
tetrahydrofuran. They have been characterized by
microanalysis, conductance measurements, mass spec-
tra (FAB), infrared and NMR (1H, 31P{1H}, 13C{1H})
spectroscopy (details are given in the Experimental
Section and Tables 1 and 2), and X-ray diffraction
(complexes 1a and 3). The formation of the allenylidene
chain is confirmed by the appearance in the IR spectra
(KBr) of a strong ν(CdCdC) absorption (asymmetric
stretching vibration) in the range 1908-1952 cm-1 31P-
.
{1H} NMR spectra show a single signal, which is
consistent with the chemical equivalence of both phos-
phorus atoms. 1H NMR spectra exhibit resonances for
aromatic, indenyl, and methylene ((CH2)2P2 or PCH2P)
groups, in accordance with the proposed structures
(Table 1).
The 13C{1H} NMR spectra of the ruthenium com-
plexes (Table 2) show the typical low-field resonance (δ
(2) For leading references see the following. Ti: (a) Binger, P.;
Mu¨ller, P.; Wenz, R.; Mynott, R. Angew. Chem., Int. Ed. Engl. 1990,
29, 1037. Cr and W: (b) Fischer, E. O.; Kalder, H. J .; Frank, A.; Ko¨hler,
F. H.; Huttner, G. Angew. Chem., Int. Ed. Engl. 1976, 15, 623. (c)
Berke, H.; Ha¨rter, P.; Huttner, G.; von Seyerl, J . J . Organomet. Chem.
1981, 219, 317. (d) Berke, H.; Ha¨rter, P.; Huttner, G.; Zsolnai, L.
Chem. Ber. 1982, 115, 695. (e) Fischer, H.; Roth, G.; Reindl, D.; Toll,
C. J . Organomet. Chem. 1993, 454, 133. (f) Fischer, H.; Reindl, D.;
Roth, G. Z. Naturforsch. 1994, 49B, 1207. (g) Aumann, R.; J asper,
B.; Fro¨hlich, R. Organometallics 1995, 14, 3173. Mn: (h) Berke, H.
Angew. Chem., Int. Ed. Engl. 1976, 15, 624. (i) Berke, H.; Huttner,
G.; von Seyerl, J . Z. Naturforsch. 1981, 86B, 1277. Ru: (j) Selegue, J .
P. Organometallics 1982, 1, 217. (k) Cadierno, V.; Gamasa, M. P.;
Gimeno, J .; Lastra, E.; Borge, J .; Garc´ıa-Granda, S. Organometallics
1994, 13, 745 and references therein. (l) Touchard, D.; Pirio, N.;
Dixneuf, P. H. Organometallics 1995, 14, 4920 and references therein.
(m) Werner, H.; Stark, A.; Steinert, P.; Gru¨nwald, C.; Wolf, J . Chem.
Ber. 1995, 128, 49. (n) Braun, T.; Steinert, P.; Werner, H. J .
Organomet. Chem. 1995, 488, 169. Rh: (o) Werner, H.; Rappert, T.;
Wiedemann, R.; Wolf, J .; Mahr, N. Organometallics 1994, 13, 2721.
(p) Schwab, P.; Werner, H. J . Chem. Soc., Dalton Trans. 1994, 3415.
(q) Windmu¨ller, B.; Wolf, J .; Werner, H. J . Organomet. Chem. 1995,
502, 147.
2
290-302 t ppm; J CP ) 16-20 Hz), expected for CR of
the metal carbene moiety. Câ and Cγ resonances appear
as singlets in the ranges δ 202-212 and 148-157 ppm,
respectively. These values can be compared to those
shown by other isoelectronic allenylideneruthenium
complexes.2j-n In the spectra of the osmium derivatives
the CR resonances are observed as a broad signal which
appears at a lower field (δ 337.0 (3) and 340.5 ppm (4))
compared to that of the corresponding ruthenium
complexes. However, Câ and Cγ carbon resonances have
chemical shifts similar to those of the ruthenium
complexes.
In contrast to the aforementioned reactions [RuCl-
(η5-C9H7)L2] species (L ) PPh3, L2 ) dppe, dppm) react
with HCtCCMe(OH)Ph in a different way, since a
mixture of vinylvinylidene complexes 5a -c and disub-
stituted allenylidene complexes 6a-c is obtained (Scheme
3).
(3) An allenylideneruthenium(II) complex has been proposed as an
active species in the catalyzed tandem cyclization-reconstitutive
addition of propargyl alcohols with allyl alcohols: Trost, B. M.; Flygare,
J . A. J . Am. Chem. Soc. 1992, 114, 5476.
(4) Gamasa, M. P.; Gimeno, J .; Mart´ın-Vaca, B. M.; Borge, J .; Garc´ıa-
Granda, S.; Pe´rez-Carren˜o, E. Organometallics 1994, 13, 4045.
(5) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J . Orga-
nomet. Chem. 1994, 474, C27.
(6) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-
Granda, S. J . Chem. Soc., Chem. Commun. 1994, 2495.
The outcome of this reaction shows the two possible
pathways in the activation of 1-alkyn-3-ols by ruthe-
(7) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva, M.; Lastra, E.
J . Chem. Soc., Dalton Trans., in press.

Activation of 2-Propyn-1-ol Derivatives
Organometallics, Vol. 15, No. 8, 1996 2139
Ta ble 1. 31P {1H} a n d 1H NMR Da ta for th e Allen ylid en e Com p lexesa
1H
η5-C9H7
e
complex
31P{1H} H-1,3 H-2 J HH H-4,7, H-5,6
others
[Ru(dCdCdCPh2)(η5-C9H7)(PPh3)2][PF6]b (1a )
[Ru(dCdCdCC12H8)(η5-C9H7)(PPh3)2]PF6]c (2a )
[Ru(dCdCdCPh2)(η5-C9H7)(dppe)][PF6]b (1b)
47.92 s 5.48 d 5.00 t 2.5 6.61 m, d
49.37 s 5.52 d 5.15 t 2.4 6.52 m, d
81.73 s 5.72 d 5.25 t 2.7 d, d
7.00-7.73 m (PPh3 and Ph)
6.97-7.59 m (PPh3 and Ph)
2.65 m, 2.74 m (P(CH2)2P); 6.87-7.56 m
(PPh2 and Ph)
[Ru(dCdCdCC12H8)(η5-C9H7)(dppe)][PF6]b (2b)
[Ru(dCdCdCPh2)(η5-C9H7)(dppm)][PF6]b (1c)
[Ru(dCdCdCC12H18)(η5-C9H7)(dppm)][PF6]c (2c)
81.55 s 5.81 d 5.25 t 2.1 d, d
8.18 s 6.12 d 5.61 t 2.8 d, d
8.23 s 6.11 d 5.59 t 2.8 6.78 m, d
2.94 m, 2.98 m (P(CH2)2P); 6.88-7.50 m
(PPh2 and Ph)
4.45 m, 5.34 m (PCHaHbP); 6.99-7.62 m
(PPh2 and Ph)
4.67 m, 5.34 m (PCHaHbP); 6.94-7.52 m
(PPh2 and Ph)
6.72-7.79 m (PPh3 and Ph)
6.99-7.97 m (PPh3 and Ph)
1.96 s (CH3); 7.03-7.93 m (PPh3 and Ph)
6.87-7.72 m (PPh3 and Ph); 9.09 s
(dCdCdCH)
[Os(dCdCdCPh2)(η5-C9H7)(PPh3)2][PF6]b (3)
[Os(dCdCdCC12H8)(η5-C9H7)(PPh3)2][PF6]b (4)
-1.33 s 5.73 d 5.19 t 1.9 d, d
-0.77 s 5.75 d 5.70 t 2.5 6.51 m, d
[Ru{dCdCdC(Me)Ph}(η5-C9H7)(PPh3)2][PF6]c (6a ) 49.34 s 5.41 d 5.07 t 2.6 6.51 m, d
[Ru{dCdCdC(H)Ph}(η5-C9H7)(PPh3)2][PF6]b (9)
47.90 s 5.41 d 5.46 t 1.6 6.36 m, d
a
b
δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; t, triplet; m, multiplet. Spectra recorded in CDCl3. c Spectra recorded
in CD2Cl2. Overlapped by the PPh3, PPh2, or Ph protons. e Legend for indenyl skeleton:
d
Sch em e 3
in dichloromethane, the orange enynyl complexes 7a -c
were obtained (62-82% yield) (Scheme 3). The forma-
tion of these species results from the deprotonation both
of the acidic vinylidene proton on 5 and of one proton
of the methyl group in 6. Complexes 7a -c were
analytically and spectroscopically characterized. IR
spectra (KBr) show the characteristic ν(CtC) absorp-
tions between 2060 and 2068 cm-1, and the 31P{1H}
NMR spectra consisted of a single resonance at δ 52.93
1
(7a ), 88.09 (7b), and 19.50 (7c) ppm. In the H NMR
spectra the olefinic dCH2 resonances appear in the
range of 4.71-5.39 ppm as doublets (J HH ≈ 2 Hz). 13C-
{1H} NMR spectra display characteristic triplet reso-
nances at δ 113.85-116.21 ppm (2J CP ) 22.5-24.4 Hz)
for the RusCt carbon nucleus. The dCH2 and Câ
nuclei resonate as two singlets in the ranges δ 110.49-
111.52 and 111.62-112.84 ppm, respectively.
Indenyl carbon resonances (Table 2) have been also
assigned, and they are in accordance with the proposed
η5 coordination.9 As has been proven previously, the
parameter ∆δ(C-3a,7a) ) δ(C-3a,7a(η-indenyl complex))
- δ(C-3a,7a(sodium indenyl)) can be used as an indica-
tion of the indenyl distortion.10 The calculated values
for the allenylidene complexes, which are in the range
ca. -16 to -21 ppm, are indicative of a moderate
distortion of the indenyl ring, and they are consistent
with the X-ray diffraction studies for complexes 1a and
3.
Different views of the molecular geometries of 1a and
3 are shown in Figure 1. The structure of 3 is the first
described for an indenylosmium complex. Selected bond
distances and angles are listed in Table 4. The struc-
tures are isotypic, and the molecules consist of
[M(dCdCdCPh2)(η5-C9H7)(PPh3)2]+ cations (M ) Ru,
Os), hexafluorophosphate anions, and one CH2Cl2 mol-
ecule of crystallization. The indenyl ligand exhibits the
usual allylene η5 coordination type in the pseudoocta-
nium complexes (Scheme 1). We and others have
reported2k,8 that the spontaneous dehydration following
the initial formation of the hydroxyvinylidene complex
(A) leads either to an allenylidene or vinylvinylidene
complex. It is apparent that in the activation of
HCtCCMe(OH)Ph, which contains a deprotonatable
methyl group, both dehydration pathways are competi-
tive.
The use of chromatography methods (SiO2) for the
separation of the vinylvinylidene and allenylidene com-
plexes failed due to the deprotonation of the acidic
vinylidene complexes and the extensive decomposition
processes. Only the allenylidene complex 6a (55%) and
the enynyl complex 7a (10%) (resulting from the depro-
tonation of the initially formed 5a ) could be separated.
The disubstituted allenylidene complex 6a displays
spectroscopic properties similar to those of allenylidene
complexes 1a -c and 2a -c (Tables 1 and 2). It is
noteworthy that the 31P{1H} NMR spectrum shows a
singlet signal. This is consistent either with a rapid
rotation of the allenylidene group through the RudC
bond at room temperature or with a locked “vertical”
position in accordance with the calculated low-energy
barrier and the crystallographic studies (see below).
When the reaction mixtures containing the complexes
5a -c and 6a -c were treated with an excess of K2CO3
(9) (a) Zhou, Z.; J ablonski, C.; Bridson, J . J . Organomet. Chem. 1993,
461, 215 and references therein. (b) Ceccon, A.; Elsevier, C. J .;
Ernsting, J . M.; Gambaro, A.; Santi, S.; Venzo, A. Inorg. Chim. Acta
1993, 204, 15.
(8) Selegue, J . P.; Young, B. A.; Logan, S. L. Organometallics 1991,
10, 1972.
(10) (a) Baker, R. T.; Tulip, T. H. Organometallics 1986, 5, 839. (b)
Kohler, F. G. Chem. Ber. 1974, 107, 570.

2140 Organometallics, Vol. 15, No. 8, 1996
Cadierno et al.
F igu r e 1. (a) Perspective view of the structure of the cationic complex [Ru(dCdCdCPh2)(η5-C9H7)(PPh3)2]+ (1a ). (b) Top
view of the structure of the cationic complex [Os(dCdCdCPh2)(η5-C9H7)(PPh3)2]+ (3). For clarity, aryl groups of the
triphenylphosphine ligands are omitted (C* ) centroid of the indenyl ring).
Ta ble 2. 13C{1H} NMR Da ta for th e Allen ylid en e Com p lexesa
η5-C9H7
complex C-1,3 C-2 C-3a,7a ∆δ(C-3a,7a)b C-4,5,6,7 RudCR 2J CP
Câ
Cγ
others
1a
2a
1b
87.20 97.45 112.40
87.20 97.82 112.81
81.33 97.09 111.29
-18.30
-17.89
-19.41
124.11, c 290.90 t 18.6 208.44 156.59 126.54-144.21 (m, PPh3 and Ph)
121.71, c 291.39 t 18.1 211.17 150.02 123.94-145.39 (m, PPh3 and Ph)
124.60, c 292.84 t 19.2 203.54 157.32 28.99 (m, P(CH2)2P); 126.48-143.32
(m, PPh2 and Ph)
2b
1c
2c
82.88 97.68 111.73
80.16 95.47 111.72
81.55 96.34 111.31
-18.97
-18.98
-19.39
121.76, c 293.99 t 18.4 207.59 149.86 29.69 (m, P(CH2)2P); 123.57-145.19
(m, PPh2 and Ph)
125.03, c 290.26 t 16.8 202.25 155.54 48.85 (t, J CP ) 26.9, PCH2P); 127.94-143.24
(m, PPh2 and Ph)
121.66, c 290.77 t 16.3 205.24 148.05 49.27 (t, J CP ) 27.06, PCH2P); 123.69-144.94
(m, PPh2 and Ph)
3
4
6a
83.88 94.24 110.12
83.36 94.28 110.83
86.13 96.85 111.90
-20.58
-19.87
-18.80
c, c
c, c
336.41 m
340.55 m
218.76 149.12 124.19-136.20 (m, PPh3 and Ph)
281.58 147.13 120.55-139.29 (m, PPh3 and Ph)
123.70, c 292.88 t 19.1 202.47 156.93 30.97 (s, CH3); 126.12-142.09
(m, PPh3 and Ph)
9
87.03 97.14 111.88
-18.82
123.66, c 301.39 t 18.7 212.16 142.70 128.76-146.12 (m, PPh3 and Ph)
a
b
Spectra recorded in CD2Cl2; δ in ppm and J in Hz. Abbreviations: s, singlet; t, triplet; m, multiplet. ∆δ(C-3a,7a) ) δ(C-3a,7a(η-
indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c Overlapped by PPh3, PPh2, or Ph carbons.
hedral three-legged piano-stool geometry. The interli-
gand angles P(1)-M-P(2), C(1)-M-P(1), and C(1)-M-
P(2) and those between the centroid C* and the legs
show values, for both complexes, typical of a pseudooc-
tahedron. The diphenylallenylidene ligand is bound to
the metals in a nearly linear fashion with M-C(1)
(1.878(5) Å, M ) Ru; 1.895(4) Å, M ) Os), C(1)-C(2)
(1.260(7) Å, M ) Ru; 1.265(6) Å, M ) Os), C(2)-C(3)
(1.353(7) Å, M ) Ru; 1.349(7) Å, M ) Os) bond lengths.
The observed distances in the allenylidene chain are not
as expected for double carbon-carbon bonds, indicating
a contribution of the canonical form [M]sCtCsC+Ph2.
These bonding parameters can be compared with those
shown by other ruthenium(II) allenylidene complexes,
i.e. [Ru(dCdCdCPh2)(η5-C5H5)(PMe3)2]+,2j [RudCdCdC-
(C13H20)}(η5-C9H7)(PPh3)2]+,2k [Ru{dCdCdC(OMe)-
(dppm)2]+.12 The dihedral angle DA between the pseudo
mirror plane of the metallic moiety (containing the
metal atom, the C(1) atom, and the centroid of the five-
carbon ring of the indenyl ligand) and the mean alle-
nylidene plane C(1), C(2), C(3), C(81), C(91) is 15.5(3)°
(M ) Ru) and 16.8(2)° (M ) Os), showing a deviation
from the coplanarity as expected by theoretical studies.13
The most conspicuous feature of the structures is the
cis orientation of the benzo ring of the indenyl ligand
with respect to the allenylidene group, in contrast to
the trans structure observed for analogous vinylidene
complexes.4 However, as is also observed in the vi-
nylidene chain of the latter complexes, the C(1), C(2),
and C(3) atoms are not contained in the mirror plane
of the molecule (Figure 1) showing conformational
angles (CA), defined as the dihedral angle between the
CHdCPh2}Cl(NP3)]+ (NP3
)
N(CH2CH2PPh2)3),11
(12) Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. J . Chem. Soc.,
Chem. Commun. 1991, 980.
(13) (a) The vertical conformation of the allenylidene group in the
model complex [Ru(dCdCdCH2)(η5-C9H7)(PH3)2]+ is 4.8 kcal/mol more
stable than the horizontal one: Pe´rez-Carren˜o, E.; Garc´ıa-Granda, S.
Unpublished results. (b) Schilling, B. E. R.; Hoffmann, R.; Lichten-
berger, D. L. J . Am. Chem. Soc. 1979, 101, 585.
[RuCl2(dCdCdCPh2){κ(P)-iPr2PCH2CO2Me]{κ2(P,O)-
iPr2PCH2CO2Me}],2m and [RuCl{dCdCdC(C14H10)}-
(11) Wolinska, A.; Touchard, D.; Dixneuf, P. H.; Romero, A. J .
Organomet. Chem. 1991, 420, 217.
(14) Borge, J .; Garc´ıa-Granda, S. Unpublished results.

Activation of 2-Propyn-1-ol Derivatives
Organometallics, Vol. 15, No. 8, 1996 2141
Ta ble 3. Cr ysta llogr a p h ic Da ta for Com p lexes
1a a n d 3
1a
3
formula
a, Å
b, Å
C61H49Cl2F6P3Ru
13.339(3)
19.67(2)
20.82(1)
99.88(4)
1160.88
5382(5)
C61H49Cl2F6P3Os
13.308(4)
19.382(8)
20.73(1)
100.47(7)
1250.08
c, Å
â, deg
mol wt
V, Å3
5259(4)
1.58
D
calcd, g cm-3
1.43
F(000)
2368
2496
wavelength, Å
temp, K
0.710 73
293
0.710 73
200
radiation
Mo KR
Mo KR
monochromator
space group
graphite cryst
P21/c
graphite cryst
P21/c
cryst syst
monoclinic
0.30, 0.26, 0.23
0.54
monoclinic
0.46, 0.46, 0.20
2.68
cryst size, mm
µ, mm-1
range of abs
0.46-1.00
0.62-1.00
diffraction geom
θ range, deg
ω-2θ
ω-2θ
1.43-24.97
1.45-24.99
index ranges for data collecn
no. of rflns measd
no. of indep rflns
no. of variables
agreement between equiv rflnsa
final R factors R(I > 2σ(I))
0 e h e 15, 0 e k e 23, -24 e l e +24
0 e h e +15, 0 e k e +23, -24 e l e +24
10 038
9443
655
0.054
R1 ) 0.0548
wR2 ) 0.1445
R1 ) 0.1228
wR2 ) 0.1720
9841
9239
659
0.034
R1 ) 0.033
wR2 ) 0.097
R1 ) 0.045
wR2 ) 0.098
final R factors R (all data)
Rint ) ∑(I - I )/∑I.
a
planes C**(centroid of the benzo ring of the indenyl
ligand)C*, Ru or Os and C*, Ru or Os and C(1) (Table
4), of 9.6(3) and 9.4(2)° for 1a and 3, respectively. The
preferred cis conformation observed in these structures
and in the analogous indenyl complex [Ru{dCdCdC-
(C13H20)}(η5-C9H7)(PPh3)2]+ can be rationalized on the
basis of theoretical calculations (see below). Steric
requirements do not seem to have an influence in
determining the conformational preferences cis (alle-
nylidene complexes) and trans (vinylidene complexes),4
since intramolecular distances H-H for both types of
derivatives are similar (the shortest values are in the
range of 2.17-2.25 Å).
Although the indenyl group is η5-bonded to the metal
atoms, the structures show slight distortions of the five-
carbon ring from the planarity with hinge angles (HA)
of 6.2(4) and 5.3(3)° and fold angles (FA) of 8.1(3) and
7.9(3)° for 1a and 3, respectively (Table 4). The char-
acteristic slippage of the indenyl ring is also observed
with slip-fold (∆) values of 0.121(5) (1a ) and 0.095(4)
(3), which are significantly lower than those shown by
the analogous vinylidene derivatives (Table 5). This
feature may be related to the stronger π-acceptor
properties of the allenylidene group (see discussion
below).
tion of unsaturated alkoxycarbene derivatives16 of type
I. However, the allenylidene complex 1a reacts with
stronger nucleophiles such as methoxide or acetylide
anions, which are added regioselectively to the Cγ atom
to give the functionalized alkynyl derivatives II.5,17
Providing that the oxidation potentials (measured by
cyclic voltammetry) for the ruthenium complexes [RuCl-
(η5-C9H7)L2] are E1/2 ) 0.45 (L ) PPh3), 0.39 (L2
)
dppm), and 0.43 (L2 ) dppe)18 vs 0.92 V for [Ru(C6Me6)-
Cl2(PPh3)], the difference in the behavior can be ex-
plained on the basis of the greater electron-releasing
ability of the indenyl derivatives, which generates
weaker electrophilic sites in the allenylidene chain with
respect to the arene derivatives. An effective steric
protection of CR by the benzo ring of the indenyl ligand
which is over the allenylidene chain (see Figure 1)
cannot be discarded either. The inertness of Cγ toward
the nucleophilic attack of methanol is most probably
based on a steric hindrance due to the presence of the
bulky phenyl or 1,1′-biphenyldiyl substituents as well
as the phenyl groups of the phosphines. As discussed
below with regard to the reactions with the secondary
propargyl alcohol HCtCCH(OH)Ph and the propargyl
It is worth mentioning that all allenylidene complexes
are unreactive toward refluxing methanol and other
alcohols in spite of theoretical calculations15 establishing
that both CR and Cγ atoms of the allenylidene chain are
electrophilic sites. In fact, this behavior is accomplished
in the reactions of analogous complexes such as [Ru-
(arene)Cl2(PR3)] with alkynols which lead to the forma-
(16) Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.; Rickard,
C. E. F.; Roper, W. R. Organometallics 1992, 11, 809.
(17) (a) Phosphines are also added regioselectively to give alky-
nylphosphonio derivatives.6 (b) Intramolecular migrations of phos-
phines to CR have been observed, depending on the nature of the added
phosphine (unpublished results).
(15) EHMO calculations on [Ru(dCdCdCH2)(η5C9H7)(PH3)2]+ show
that the LUMO is centered CR (25%) and Cγ (38%): Pe´rez-Carren˜o, E.
Doctoral Thesis, University of Oviedo, 1996.
(18) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Mart´ın-
Vaca, B. M.; Monti, D.; Bassetti, M. Organometallics 1996, 15, 302.

2142 Organometallics, Vol. 15, No. 8, 1996
Cadierno et al.
Ta ble 4. Selected Bon d Dista n ces a n d Slip P a r a m eter ∆a (Å) a n d Bon d An gles a n d Dih ed r a l An gles F A,b
HA,c DA,d a n d CAe (d eg) for [Ru (dCdCdCP h 2)(η5-C9H7)(P P h 3)2][P F 6]‚CH2Cl2 (1a ) a n d
[Os(dCdCdCP h 2)(η5-C9H7)(P P h 3)2][P F 6]‚CH2Cl2 (3)
1a
3
1a
3
Distances
M-C*
1.951(5)
2.321(2)
2.358(2)
1.878(5)
2.364(5)
2.251(5)
2.264(5)
2.230(5)
2.359(5)
1.842(5)
1.837(5)
1.822(5)
1.844(5)
1.829(5)
1.835(5)
1.950(5)
2.312(2)
2.350(2)
1.895(4)
2.344(5)
2.242(4)
2.272(4)
2.265(5)
2.353(4)
1.826(4)
1.829(5)
1.838(4)
1.828(4)
1.846(4)
1.842(4)
C(1)-C(2)
1.260(7)
1.353(7)
1.469(9)
1.475(8)
1.403(8)
1.418(7)
1.455(7)
1.404(8)
1.399(7)
1.433(8)
1.417(7)
1.365(8)
1.391(9)
1.344(8)
0.121(5)
1.265(6)
1.349(7)
1.482(8)
1.465(7)
1.426(6)
1.428(6)
1.433(6)
1.424(6)
1.397(7)
1.436(6)
1.429(7)
1.357(7)
1.424(7)
1.353(7)
0.095(4)
M-P(1)
C(2)-C(3)
M-P(2)
M-C(1)
C(3)-C(81)
C(3)-C(91)
C(70)-C(78)
C(70)-C(74)
C(70)-C(71)
C(71)-C(72)
C(72)-C(73)
C(73)-C(74)
C(74)-C(75)
C(75)-C(76)
C(76)-C(77)
C(77)-C(78)
∆
M-C(70)
M-C(71)
M-C(72)
M-C(73)
M-C(74)
P(1)-C(11)
P(1)-C(21)
P(1)-C(31)
P(2)-C(41)
P(2)-C(51)
P(2)-C(61)
Angles
C*-M-C(1)
124.1(2)
121.6(2)
120.6(2)
88.7(2)
123.1(2)
122.2(1)
120.6(2)
89.5(1)
C(78)-C(70)-C(74)
C(78)-C(70)-C(71)
C(74)-C(70)-C(71)
C(72)-C(71)-C(70)
C(71)-C(72)-C(73)
C(72)-C(73)-C(74)
C(75)-C(74)-C(70)
C(75)-C(74)-C(73)
C(73)-C(74)-C(70)
C(76)-C(75)-C(74)
C(77)-C(78)-C(70)
C(78)-C(77)-C(76)
119.5(5)
133.3(5)
106.8(5)
108.7(5)
107.3(5)
109.8(5)
119.4(5)
133.6(5)
107.0(4)
118.1(5)
119.3(6)
121.4(6)
119.6(4)
133.2(4)
107.0(4)
108.6(4)
107.7(4)
108.9(4)
120.1(4)
132.4(4)
107.5(4)
118.2(5)
118.5(5)
122.0(5)
C*-M-P(1)
C*-M-P(2)
C(1)-M-P(1)
C(1)-M-P(2)
P(1)-M-P(2)
97.4(2)
98.4(1)
96.95(5)
168.5(5)
168.2(7)
118.2(6)
122.4(6)
119.4(5)
121.9(6)
95.73(5)
169.3(4)
168.0(5)
116.8(5)
122.8(5)
120.4(4)
121.5(5)
M-C(1)-C(2)
C(1)-C(2)-C(3)
C(2)-C(3)-C(81)
C(2)-C(3)-C(91)
C(81)-C(3)-C(91)
C(75)-C(76)-C(77)
FA
DA
8.1(3)
15.5(3)
7.9(3)
16.8(2)
HA
CA
6.2(4)
9.6(3)
5.3(3)
9.4(2)
a
b
∆ ) d(M-C(74),C(70)) - d(M-C(71),C(73)). FA (fold angle) ) angle between normals to least-squares planes defined by C(71),
C(72), C(73) and C(70), C(74), C(75), C(76), C(77), C(78). c HA (hinge angle) ) angle between normals to least-squares planes defined by
d
C(71), C(72), C(73) and C(71), C(74), C(70), C(73). DA (dihedral angle) ) angle between normals to least-squares planes defined by C*,
M, C(1) and C(1), C(2), C(3), C(81), C(91). e CA (conformational angle) ) angle between normals to least-squares planes defined by C**,
C*, M and C*, M, C(1). C* ) centroid of C(70), C(71), C(72), C(73), C(74). C** ) centroid of C(70), C(74), C(75), C(76), C(77), C(78). M
) Ru, Os.
Ta ble 5. Slip P a r a m eter ∆ a n d Dih ed r a l An gles F A, HA, a n d CA for In d en yl Com p lexesa
M-C* (Å)
∆ (Å)
FA (deg)
HA (deg)
CA (deg)
ref
[{Ru}(dCdCMe2)]+
1.97(9)
0.197(7)
0.175(6)
0.1974(1)
0.0820(4)
0.095(4)
0.1211(4)
13.1(6)
11.9(5)
12.2(4)
5.1(5)
7.9(3)
8.1(3)
8.1(6)
6.6(5)
7.5(4)
5.3(5)
5.3(3)
6.2(4)
157.8(4)
164.6(3)
160.0(3)
12.2(6)
9.4(2)
4
[{Ru}(dCdC(H)Ph)]+
[{Ru}(dCdC(Me)(C6H9))]+
[{Ru}(dCdCdC(C13H20))]+
[{Os}(dCdCdCPh2)]+
[{Ru}(dCdCdCPh2)]+
1.964(6)
1.970(9)
1.942(5)
1.950(5)
1.951(5)
14
14
2k
b
9.6(3)
b
a
∆ ) d[M - C(74),C(70)] - d[M - C(71),C(73)]; F A ) C(71), C(72), C(73)/C(70), C(74), C(75), C(76), C(77), C(78); HA ) C(71), C(72),
C(73)/C(71), C(74), C(70), C(73); CA ) C**, C*, M/C*, M, C(1); {M} ) M(η5-C9H7)(PPh3)2 (M ) Ru, Os). This work.
b
Sch em e 4
alcohol itself, the ability of the allenylidene chain to
undergo nucleophilic additions is mainly dependent on
the overall protection of the electrophilic carbon atoms
by the type of ancillary phosphine ligands in the
ruthenium complex.
Syn th esis of th e Mon osu bstitu ted Allen ylid en e
Com p lex [R u {dCdCdC(H)P h }(η5-C9H 7)(P P h 3)2]+
a n d Meth oxya lk en ylca r ben e Com p lexes by Acti-
va tion of 1-P h en yl-2-p r op yn -1-ol. The outcome of
the reactions of the secondary propargyl alcohol 1-phen-
yl-2-propyn-1-ol with ruthenium indenyl complexes
[RuCl(η5-C9H7)L2] (L ) PPh3; L2 ) dppm, dppe) depends
on the precursor complex (Scheme 4).
and Experimental Section). The most remarkable fea-
tures of the NMR spectra are (i; 1H NMR) the low-field
singlet signal at δ 9.09 ppm of the allenic proton
dCdCdCH and (ii; 13C NMR) the typical signal of the
carbenic CR, which appears as a triplet at δ 301.39 ppm
(2J CP ) 18.7 Hz), and the expected resonances of the Câ
and Cγ atoms at δ 212.16 and 142.70 ppm, respectively
(in accordance with their sp and sp2 character). When
Thus, [RuCl(η5-C9H7)(PPh3)2] reacts with HCtCCH-
(OH)Ph in methanol and in the presence of NaPF6 to
give, after 48 h of stirring at room temperature, complex
9, isolated as a red stable solid (63% yield). The
spectroscopic properties of 9 are similar to those of the
allenylidene complexes 1a and 2a (see Tables 1 and 2

Activation of 2-Propyn-1-ol Derivatives
Organometallics, Vol. 15, No. 8, 1996 2143
the reaction is monitored by 31P{1H} NMR spectroscopy,
the spectra show the formation of an intermediate
species. After 24 h of stirring, the spectrum displays
two doublet signals (AB system) at δ 39.47 and 39.87
ppm (2J PP ) 23.1 Hz), identified as the methoxyvi-
nylidene complex 8. The nonequivalence of the phos-
phorus nuclei is due to the presence of a chiral group
on the molecule, as has been also reported for the
analogous chiral methoxyvinylidene complex [Ru-
{dCdCHCH(Me)OMe}(η5-C5Me5)(PMe2Ph)2][PF6].19 The
Sch em e 5
1
characterization is confirmed by H and 13C{1H} NMR
spectroscopy (see Experimental Section). All attempts
to isolate the complex 8 failed since, during the workup
of the solution, MeOH is readily eliminated to give the
allenylidene complex 9. This reaction is reversible to
give back the methoxyvinylidene complex 8, which is
also readily formed by addition of methanol to the
allenylidene complex 9.
similarly found for the allenylidene derivatives and
other alkoxycarbene complexes.4
The formation of 11b,c can be understood as the
result of the nucleophilic addition of methanol to the
electrophilic CR atom of the initially formed monosub-
stituted allenylidene complex [Ru]+dCdCdC(H)Ph. As
we have shown before, the bis(triphenylphosphine)-
ruthenium complex 9 is able to protect the CR atom of
the allenylidene chain from the nucleophilic additions
and only the attack on the Cγ atom is observed.5,6 This
behavior contrasts with the formation of the carbene
complexes 11b,c, showing that small steric differences
between the ancillary ligands in the metal auxiliary are
able to control the nucleophilic attacks and therefore
the stabilization of the allenylidene group. All attempts
to isolate the allenylidene intermediate species using
CH2Cl2 as solvent under different reaction conditions
were unsuccessful.
The nature of the complex 8 is also assessed by
studying its reactivity. Thus, the treatment of a metha-
nol solution with potassium carbonate leads to the
formation of the neutral methoxyalkynyl complex 10,
isolated as a stable solid (66%). Complex 10 is probably
formed through the deprotonation of the acidic vi-
nylidene proton of the methoxyvinylidene complex 8.
The alkynyl group is identified by the expected ν(CtC)
absorption band at 2076 cm-1 in the IR spectrum and
by 13C{1H} NMR spectroscopy (see Experimental Sec-
tion). Similarly to the precursor complex 8 the phos-
phorus NMR spectrum also shows two doublet reso-
nances of the diastereotopic phosphorus nuclei (at δ
2
52.15 and 52.60 ppm; J PP ) 10.1 Hz), consistent with
the presence in the molecule of the chiral group.
In order to study the influence of the ancillary ligands
in the ability of the indenylruthenium complexes to
stabilize the allenylidene chain, the activation of
HCtCCH(OH)Ph by [RuCl(η5-C9H7)L2] (L2 ) dppe,
dppm) was also investigated. Surprisingly, under simi-
lar reaction conditions alkenylcarbene complexes 11b
(70%) and 11c (77%) were isolated as air-stable solids.
Rea ction of [Ru Cl(η5-C9H7)L2] (L ) P P h 3, L2
)
d p p m ) w ith 2-P r op yn -1-ol. [RuCl(η5-C9H7)(PPh3)2]
reacts with HCtCCH2(OH)/NaPF6 in methanol to give
the yellow hydroxyvinylidene complex 12 (67%). The
complex is stable toward dehydration, and the formation
of
the
unsubstituted
allenylidene
group
[Ru]+dCdCdCH2 is inhibited (Scheme 5). Isolation of
similar stable hydroxyvinylidene complexes obtained
from [RuCl(η5-C5Me5)(PMe2Ph)2] have been also re-
ported.19 The 31P{1H} NMR spectrum shows a singlet
at δ 38.44 ppm, consistent with the chemical equiva-
lence of the phosphorus atoms. The hydroxy proton
resonance occurs as a broad signal at δ 1.63 ppm in the
1H NMR spectra, while the vinylidene proton signal
appears as a triplet at δ 4.67 ppm (J HH ) 7.5 Hz), due
to the coupling with the vicinal CH2 protons. The CH2
protons resonate as a doublet at δ 3.90 ppm (J HH ) 7.5
Hz). The 13C{1H} NMR spectrum shows the RudC
resonance as a triplet at δ 344.31 ppm (2J CP ) 16.9 Hz)
and the expected signals for CH2 and Câ at δ 53.77 and
113.58 ppm, respectively.
1
Analytical and spectroscopic data (infrared and H, 31P-
{1H}, and 13C{1H} NMR) are in accordance with the
proposed formulations (see Experimental Section for
1
details). 31P{1H}, 13C{1H}, and H NMR spectra (aro-
matic, indenyl, and (CH2)2P2 or PCH2P groups) exhibit
resonances which can be compared to those observed
for analogous (carbene)ruthenium indenyl complexes
[Ru{dC(OMe)Me}(η5-C9H7)L2][PF6] (L2 ) dppe, dppm).4
Significantly, 31P{1H} NMR spectra show single reso-
nances at δ 91.96 (11b) and 14.18 (11c) ppm. 1H NMR
spectra, exhibit, besides the methoxy resonances (δ 2.76
(11b) and 2.79 (11c) ppm), doublet signals at δ 5.37 and
6.53 (11c) and δ 5.96 (11b) ppm (J HH ) ca. 16 Hz)
assigned to the CH olefinic protons (the other expected
signal is presumably masked by the aromatic reso-
nances). The high values of the coupling constants are
typical of an E configuration of the CHdCH bond. The
presence of the carbene group is confirmed by the low-
field triplet signals in the 13C{1H} NMR spectra at δ
298.31 (11b) and 298.75 (11c) ppm (2J CP ) 12.9 Hz (11b)
and 11.7 Hz (11c)). The ∆δ(C-3a,7a) values -18.59
(11b) and -19.72 (11c) are also consistent with a
moderate distortion of the η5-indenyl ligand, as was
In contrast, the reaction of [RuCl(η5-C9H7)(dppm)]
with HCtCC(OH)H2 in refluxing methanol afforded the
yellow alkenyl carbene complex 13 (80%). Its spectro-
scopic properties are similar to those of the analogous
alkenylcarbene complex 11c (see Experimental Section).
In particular, the 13C{1H} NMR spectrum shows the
typical resonances expected for the unsaturated carbene
group (δ(RudC) 300.59 (2J CP ) 11.7 Hz); δ(dCH2)
113.69; δ(HCd) 144.60 ppm). The formation of the
carbene complex 13 from [RuCl(η5-C9H7)(dppm)], as has
been also noted before the activation of the secondary
propargyl alcohol, is a clear indication of the influence
(19) Le Lagadec, R.; Roman, E.; Toupet, L.; Mu¨ller, U.; Dixneuf, P.
H. Organometallics 1994, 13, 5030.

2144 Organometallics, Vol. 15, No. 8, 1996
Cadierno et al.
F igu r e 3. Plot of the total orbital energies (kcal/mol) of
[Ru(dCdCdCH2)(η5-C9H7)(PH3)]+ vs the conformational
angle (CA) for ∆ values 0.05, 0.10, and 0.20 Å. A value of
0 kcal/mol is taken for the most stable conformation: CA
) 180°.
F igu r e 2. Orbital interaction diagram for [Ru-
(dCdCdCH2)(η5-C9H7)(PH3)2]+ from the fragments [Ru-
(dCdCdCH2)(PH3)2]2+ and [C9H7]- with the indenyl ligand
in a cis conformation.
bonding interaction between the metal fragment and the
indenyl ring has π character, mainly involving the
unoccupied orbitals 3a′ and 2a′′ and the two orbitals of
the indenyl anion π′′ and π′. The main bonding interac-
tion can be visualized as electron transfer from the filled
π orbitals of the indenyl ring to the empty 3a′ and 2a′′
orbitals of the metal fragment.
In order to investigate the conformational cis prefer-
ence of the indenyl ring found in the allenylidene
complexes, we have studied the orbital interactions for
cis (CA ) 0°) and trans (CA ) 180°) orientations. The
total orbital energies have been calculated for the
different conformation angle in the range 0-180° (Fig-
ure 3). It is found, however, that the trans orientation
is 1.9 kcal/mol more stable than the cis, with a rotation
barrier of 5.9 kcal/mol.
It is interesting to note that the orientation preference
of the indenyl group appears to be related to the
distortion parameters (Table 5), since ∆ and FA values
in the vinylidene complexes with a trans orientation
(average 0.19 Å and 12.4°, respectively) are significantly
larger than those found in the allenylidene complexes
with a cis orientation (average 0.10 Å and 7.0°, respec-
tively). In order to study the effect of the distortion
parameters of the indenyl ligand on its orientation, we
have also calculated the total orbital energies in our
model for virtual ∆ values of 0.05 and 0.20 Å (Figure
3). As is shown, a trans orientation (CA ) 180°) would
be clearly preferred for ∆ ) 0.20 Å (ca. 4.6 kcal/mol more
stabilized with respect to the cis orientation), whereas
there is no preference for ∆ ) 0.05 Å, since similar
energy values are found for both cis and trans orienta-
tions. This trend allows the prediction of the trans
conformation adopted by the vinylidene complexes for
which the largest indenyl distortion parameters are
found. However, for the experimental ∆ distortion
parameters found for the allenylidene complexes (in the
range of 0.082 and 0.121 Å) the difference in the total
energies is so small that no preferred orientation can
be predicted in these cases on the basis only of this
argument. This dilemma can be resolved using the
overlap analysis,20 achieving a complete agreement
between the calculated and experimental results. Thus,
of PPh3 in protecting the allenylidene CR atom vs the
small-bite chelating dppm ligand to undergo nucleo-
philic additions.
EHMO Ca lcu la tion s. Extended Hu¨ckel molecular
orbital calculations have been carried out on
[M(dCdCdCH2)(PH3)2(C9H7)]+ (M ) Ru, Os). In our
optimized geometry for the ground state, we use the
overall values of the relevant structural parameters
(including the indenyl distortion parameters ∆, FA, DA,
and HA) as determined by the X-ray diffraction studies
of the complexes [Ru(dCdCdCPh2)(PPh3)2(C9H7)]+,
[Os(dCdCdCPh2)(PPh3)2(C9H7)]+ (see above), and [Ru-
{dCdCdC(C13H20)}(PPh3)2(C9H7)]+.2k For the purpose
of the electronic structure description, we consider the
model complex to have a mirror plane. The projection
of the metal atom onto the indenyl plane is slightly away
(∆ ) 0.10) from η5 toward η3 coordination.
The calculations were performed using fragment
analyses in order to obtain an approximate MO com-
position. Figure 2 shows the orbital interaction diagram
between the indenyl ligand and the [Ru(dCdCdCH2)-
(PH3)2] fragment in the cis orientation, as determined
by the X-ray diffraction study. The five important
frontier orbitals of the metal fragment are ordered,
according to increasing energies, 1a′′, 1a′, 2a′, 2a′′, and
2
2
3a′. The orbital 3a′ is a hybrid between dxz (32%), dx -y
(24%), and px (22%). The 2a′′ orbital is an antibonding
combination of the metal orbitals dyz (54%) and py (10%),
with a π-type orbital (py) of the allenylidene ligand. The
2
filled orbitals 2a′, 1a′, and 1a′′ are hybrid orbitals of dz ,
2
2
dx -y and dxy, with minor contributions of dxz and dyz.
On the left of Figure 2 the principal π orbitals of the
indenyl ring are shown. The superscripts refer to the
mirror plane symmetry. The LUMO is essentially
localized in the allenylidene ligand, while the HOMO
has a large contribution of the metal fragment orbital
2
2a′ (mainly dz ). The next occupied molecular orbital is
a bonding combination of π′ with 3a′ and an antibonding
one with 1a′. The two following orbitals are a bonding
combination between π′′ and both 2a′′ and 1a′′, respec-
tively. The lowest molecular orbital shown is a bonding
interaction of π′ and 1a′. The diagram shows that the
(20) Rogers, R. D.; Atwood, J . L.; Albright, T. A.; Lee, W. A.; Rausch,
M. D. Organometallics 1984, 3, 263.

Activation of 2-Propyn-1-ol Derivatives
Organometallics, Vol. 15, No. 8, 1996 2145
) 669, [M+ - PPh3 - C9H7] ) 553. 2a : 83; 1932, 838. Anal.
Calcd for RuC60H45P3F6; C, 67.10; H, 4.22. Found: C, 66.92;
H, 4.17. 125; [M+] ) 929, [M+ - C15H8] ) 741, [M+ - PPh3] )
667, [M+ - PPh3 - C9H7] ) 551, [M+ - C15H8 - PPh3 - C9H7]
) 479. 1b: 75; 1943, 837. Anal. Calcd for RuC50H41P3F6: C,
63.20; H, 4.35. Found: C, 62.32; H, 4.45. 109; [M+] ) 805,
[M+ - C15H10] ) 615. 2b: 74; 1936, 837. Anal. Calcd for
RuC50H39P3F6; C, 63.36; H, 4.15. Found: C, 62.34; H, 4.12.
138; [M+] ) 803, [M+ - C15H8] ) 615. 1c: 76; 1935, 838. Anal.
Calcd for RuC49H39P3F6: C, 62.81; H, 4.20. Found: C, 63.01;
the calculated values of the overlap populations for the
cis conformations, which are π′′|2a′′ ) 0.2415 and
π′|3a′ ) 0.2012, indicate that the cis conformation is
preferred with respect to the trans (0.2346 and 0.2069,
respectively) mainly due to the significantly larger
overlap value of the asymmetric orbitals. We have
previously reported similar EHMO calculations for the
vinylidene complex [Ru(dCdCMe2)(η5-C9H7)(PPh3)2]+
and have found a minimum energy value and a most
favored overlapping for the trans orientation, in ac-
cordance with the conformation adopted also in the solid
state.4
It is now apparent that the nature of the unsaturated
carbene seems to determine both the preferred confor-
mation and the distortion of the indenyl ligand. We
believe that these distortions may arise from the
stronger π-acceptor electronic capacity of the alle-
nylidene group, as has been found by EHMO calcula-
tions.21 Due to this fact, the allenylidene group is able
to accept more electronic density through back-donation,
favoring the η5 indenyl coordination and consequently
a lesser distortion, as is observed in the crystal structure
determinations.
H, 4.35. 101; [M+] ) 791, [M+ - C15H10 - C9H7] ) 485, [M+
dppm] 407. 2c: 72; 1952, 839. Anal. Calcd for
-
)
RuC49H37P3F6: C, 63.02; H, 3.99. Found: C, 62.33; H, 3.68.
118; [M+] ) 789, [M+ - C15H8] ) 601.
Syn t h esis of [Os(dCdCdCR2)(η5-C9H7)(P P h 3)2][P F 6]
(R2 ) 2 P h (3), C12H8 (4)). Gen er a l P r oced u r e. A solution
of [OsCl(η5-C9H7)(PPh3)2] (1 mmol), NaPF6 (336 mg, 2 mmol),
and the corresponding propargylic alcohol (5 mmol) was heated
under reflux in 50 mL of MeOH (time of reaction is indicated
below). The color progressively changed from red to purple.
After the mixture was cooled, the solvent was removed under
vacuum, the solid residue was extracted with CH2Cl2, and the
extract was filtered. Concentration of the resulting solution
to ca. 5 mL followed by the addition of 50 mL of diethyl ether
precipitated a purple solid, which was washed with diethyl
ether and dried in vacuo. Reaction time, yield (%), IR data
(KBr, ν(CdCdC), ν(PF6-), cm-1), and analytical data are as
follows. 3: 3.5 h; 55; 1908, 839. Anal. Calcd for
OsC60H47P3F6: C, 61.85; H, 4.07. Found: C, 62.12; H, 4.34.
4: 1 h; 39; 1922, 840. Anal. Calcd for OsC60H45P3F6: C, 61.96;
H, 3.90. Found: C, 63.19; H, 3.99.
Syn th esis of [Ru {dCdCdC(Me)P h }(η5-C9H7)(P P h 3)2]-
[P F 6] (6a ). A solution of [RuCl(η5-C9H7)(PPh3)2] (776 mg, 1
mmol), HCtCCMe(OH)Ph (292 mg, 2 mmol), and NaPF6 (336
mg, 2 mmol) in 50 mL of MeOH was heated under reflux for
30 min. The color progressively changed from red to purple.
The solvent was removed under vacuum, and the solid residue
was extracted with CH2Cl2 and the extract was filtered. The
resulting solution was concentrated to ca. 5 mL and trans-
ferred to a silica gel chromatography column. Elution with
dichloromethane gave a purple band, which was collected and
evaporated to give 6a . Yield (%), IR data (KBr; ν(CdCdC),
ν(PF6-), cm-1), analytical data, conductivity (acetone, 20 °C,
Ω-1 cm2 mol-1), and mass spectral data (FAB, m/e) are as
follows: 55; 1934, 839. Anal. Calcd for RuC55H45P3F6: C,
65.15; H, 4.47. Found: C, 64.86; H, 4.03. 117; [M+] ) 869,
[M+ - C10H8] ) 741, [M+ - PPh3] ) 607, [M+ - C10H8 - PPh3]
) 479.
Syn th esis of [Ru {CtCC(P h )dCH2}(η5-C9H7)L2] (L )
P P h 3 (7a ); L2 ) d p p e (7b), d p p m (7c)). Gen er a l P r oce-
d u r e. A solution of [RuCl(η5-C9H7)L2] (1 mmol), HCtCCMe-
(OH)Ph (292 mg, 2 mmol), and NaPF6 (336 mg, 2 mmol) was
heated under reflux in 50 mL of MeOH for 30 min. The color
progressively changed from red to purple. After the mixture
was cooled, the solvent was removed under vacuum, the solid
residue was extracted with CH2Cl2, and the extract was
filtered. Concentration of the resulting solution to ca. 5 mL
followed by the addition of 50 mL of diethyl ether precipitated
a purple solid, which was washed with diethyl ether and then
dissolved in 20 mL of CH2Cl2. The solution was treated with
K2CO3 (1.382 g, 10 mmol) and the mixture stirred at room
temperature for 3 h. The color progressively changed from
purple to orange. The solvent was removed under vacuum,
and the solid residue was extracted with diethyl ether and
filtered. Evaporation of the diethyl ether gave 7a -c as an
orange solid. Yield (%), IR data (KBr; ν(CtC), cm-1), analyti-
cal data, and NMR spectroscopic data are as follows. 7a : 76;
2060. Anal. Calcd for RuC55H44P2: C, 76.11; H, 5.11.
Found: C, 76.01; H, 5.17. 31P{1H} (C6D6) δ 52.93 (s) ppm; 1H
Exp er im en ta l Section
The reactions were carried out under dry nitrogen using
Schlenk techniques. All solvents were dried by standard
methods and distilled under nitrogen before use. The com-
plexes [RuCl(η5-C9H7)L2] (L ) PPh3,22 L2 ) dppe,22 dppm18) and
[OsCl(η5-C9H7)(PPh3)2]7 were prepared by literature methods.
NaPF6 (Aldrich Chemical Co.) and the propargylic alcohols
HCtCC(OH)Ph2, HCtCCH(OH)Ph, HCtCC(OH)C12H8 (Lan-
caster Chemical Co.), HCtCCMe(OH)Ph (Aldrich Chemical
Co.), and HCtCC(OH)H2 (Fluka AG Chemical Co.) were used
as received.
Infrared spectra were recorded on a Perkin-Elmer 1720-XFT
spectrometer. Mass spectra (FAB) were recorded using a VG-
Autospec spectrometer, operating in the possitive mode; 3-ni-
trobenzyl alcohol (NBA) was used as the matrix. The conduc-
tivities were measured at room temperature, in ca. 10-3 mol
dm-3 acetone solutions, with a J enway PCM3 conductimeter.
The C and H analyses were carried out with a Perkin-Elmer
240-B microanalyzer. NMR spectra were recorded on a Bruker
AC300 instrument at 300 MHz (1H), 121.5 MHz (31P), or 75.4
MHz (13C) using SiMe4 or 85% H3PO4 as standard. 1H, 13C-
{1H}, and 31P{1H} NMR spectroscopic data for the allenylidene
complexes are collected in Tables 1 and 2.
Syn th esis of [Ru (dCdCdCR2)(η5-C9H7)L2][P F 6] (L )
P P h 3, R2 ) 2 P h (1a ), C12H8 (2a ); L2 ) d p p e, R2 ) 2 P h
(1b), C12H8 (2b); L2 ) d p p m , R2 ) 2 P h (1c), C12H8 (2c)).
Gen er a l P r oced u r e. A solution of [RuCl(η5-C9H7)L2] (1
mmol), the corresponding propargylic alcohol (2 mmol), and
NaPF6 (336 mg, 2 mmol) was heated under reflux in 50 mL of
MeOH for 30 min. The color progressively changed from red
to violet. After the mixture was cooled, the solvent was
removed under vacuum, the solid residue was extracted with
CH2Cl2, and the extract was filtered. Concentration of the
resulting solution to ca. 5 mL followed by the addition of 50
mL of diethyl ether precipitated a violet solid, which was
washed with diethyl ether and dried in vacuo. Yield (%), IR
data (KBr; ν(CdCdC), ν(PF6-), cm-1), analytical data, con-
ductivity (acetone, 20 °C, Ω-1 cm2 mol-1), and mass spectral
data (FAB, m/e) are as follows. 1a : 72; 1933, 837. Anal.
Calcd for RuC60H47P3F6: C, 66.98; H, 4.39. Found: C, 66.44;
H, 4.96. 132; [M+] ) 931, [M+ - C15H10] ) 741, [M+ - PPh3]
(C6D6) δ 4.41 (d, 2H, J HH ) 2.6 Hz, H-1,3), 5.17 (d, 1H, J HH
2.2 Hz, dCH), 5.21 (t, 1H, J HH ) 2.6 Hz, H-2), 5.38 (d, 1H,
J HH ) 2.2 Hz, dCH), 6.15 and 6.42 (m, 2H each, H-4,7 and
)
(21) Pe´rez-Carren˜o, E.; Garc´ıa-Granda, S. Unpublished results.
(22) Oro, L. A.; Ciriano, M. A.; Campo, M.; Foces-Foces, C.; Cano,
F. H. J . Organomet. Chem. 1985, 289, 117.

2146 Organometallics, Vol. 15, No. 8, 1996
Cadierno et al.
2
H-5,6), 6.58-7.82 (m, 35H, Ph) ppm; 13C{1H} (C6D6) δ 73.44
(s, C-1,3), 93.58 (s, C-2), 108.10 (s, C-3a,7a), 110.49 (s, dCH2),
112.84 (s, tCâ), 113.85 (t, J CP ) 22.5 Hz, RusCR), 121.91,
124.72 (s, C-4,7 and C-5,6), 126.15-140.67 (m, Ph, dC) ppm;
∆δ(C-3a,7a) ) -22.60. 7b : 82; 2063. Anal. Calcd for
RuC45H38P2: C, 72.86; H, 5.16. Found: C, 72.57; H, 5.24. 31P-
{1H} (C6D6) δ 88.09 (s) ppm; 1H (C6D6) δ 1.85 (m, 2H,
or C-3), 74.78 (d, J CP ) 5.3 Hz, C-1 or C-3), 76.31 (s, CH),
2
95.28 (s, C-2), 104.35 (vt, J CP ) 23.9 Hz, RusCR), 109.29,
109.59, and 110.10 (s, tCâ, C-3a,7a), 123.26, 123.45, 125.90,
and 126.08 (s, C-4,5,6,7), 127.07-143.95 (m, Ph) ppm.
2
Syn th esis of [Ru {dC(OMe)C(H)dCH(P h )}(η5-C9H7)L2]-
[P F 6] (L2 ) d p p e (11b), d p p m (11c)). Gen er a l P r oced u r e.
A solution of [RuCl(η5-C9H7)L2] (1 mmol), HCtCCH(OH)Ph
(264 mg, 2 mmol), and NaPF6 (336 mg, 2 mmol) in 50 mL of
MeOH was stirred at a temperature and for a time that are
indicated below. The color progressively changed from red to
brown. The solvent was removed under vacuum, the solid
residue was extracted with CH2Cl2, and the extract was
filtered. Concentration of the resulting solution to ca. 5 mL
followed by the addition of 50 mL of diethyl ether precipitated
a brown solid, which was washed with diethyl ether and dried
in vacuo. Temperature (°C), reaction time, yield (%), IR data
(KBr; ν(PF6-), cm-1), analytical data, conductivity (acetone, 20
°C, Ω-1 cm2 mol-1), and NMR spectroscopic data are as follows.
11b: 25; 12 h; 70; 837. Anal. Calcd for RuC45H41P3F6O: C,
59.67; H, 4.56. Found: C, 59.25; H, 4.46. 128; 31P{1H} (CD2-
Cl2) δ 91.96 (s) ppm; 1H (CD2Cl2) δ 2.57 (m, 2H, P(CHaHb)2P),
2.76 (s, 3H, OCH3), 2.84 (m, 2H, P(CHaHb)2P), 5.14 (t, 1H, J HH
) 2.7 Hz, H-2), 5.37 (d, 1H, J HH ) 16.7 Hz, dCH), 5.46 (d, 2H,
J HH ) 2.7 Hz, H-1,3), 6.53 (d, 1H, J HH ) 16.7 Hz, dCH),
6.57 and 6.88 (m, 2H, each, H-4,7 and H-5,6), 7.10-7.49 (m,
25H, Ph) ppm; 13C{1H} (CD2Cl2) δ 28.23 (m, P(CH2)2P), 62.77
(s, OCH3), 78.21 (s, C-1,3), 100.18 (s, C-2), 112.11 (s, C-3a,7a),
124.54 (s, Ind6), 127.24-137.92 (m, Ph, CHdCH, Ind6), 298.31
P(CHaHb)2P), 2.40 (m, 2H, P(CHaHb)2P), 4.89 (d, 1H, J HH
)
2.0 Hz, dCH), 5.02 (d, 2H, J HH ) 2.1 Hz, H-1,3), 5.12 (t, 1H,
J HH ) 2.1 Hz, H-2), 5.39 (d, 1H, J HH ) 2.0 Hz, dCH), 6.90 (m,
2H, Ind6), 6.99-7.60 (m, 27H, Ph, Ind6) ppm; 13C{1H} (C6D6)
δ 28.24 (m, P(CH2)2P), 70.22 (s, C-1,3), 92.52 (s, C-2), 108.23
2
(s, C-3a,7a), 111.43 (s, dCH2), 111.62 (s, tCâ), 116.21 (t, J CP
) 24.4 Hz, Ru-CR), 124.06, 124.47 (s, C-4,7 and C-5,6),
126.77-142.01 (m, Ph, dC) ppm; ∆δ(C-3a,7a) ) -22.47. 7c:
62; 2068. Anal. Calcd for RuC44H36P2: C, 72.61; H, 4.98.
Found: C, 72.41; H, 4.90. 31P{1H} (C6D6) δ 19.50 (s) ppm; 1H
(C6D6) δ 4.17 (m, 2H, PCH2P), 4.71 (d, 1H, J HH ) 2.4 Hz, dCH),
5.15 (t, 1H, J HH ) 2.7 Hz, H-2), 5.29 (d, 2H, J HH ) 2.7 Hz,
H-1,3), 5.31 (d, 1H, J HH ) 2.4 Hz, dCH), 6.93-7.55 (m, 29H,
2
Ph, Ind6) ppm; 13C{1H} (C6D6) δ 49.95 (t, J CP ) 23.3 Hz,
PCH2P), 68.08 (s, C-1,3), 89.34 (s, C-2), 107.56 (s, C-3a,7a),
2
111.52 (s, dCH2), 112.22 (s, tCâ), 116.64 (t, J CP ) 22.9 Hz,
Ru-CR), 123.55, 125.14 (s, C-4,7 and C-5,6), 126.67-141.69
(m, Ph, dC) ppm; ∆δ(C-3a,7a) ) -23.14.
Syn t h esis of [R u {dCdCdC(H )P h }(η5-C9H 7)(P P h 3)2]-
[P F 6] (9). A solution of [RuCl(η5-C9H7)(PPh3)2] (776 mg, 1
mmol), HCtCCH(OH)Ph (132 mg, 1 mmol), and NaPF6 (168
mg, 1 mmol) in 50 mL of MeOH was stirred for 24 h at room
temperature. The solvent was removed under vacuum, the
solid residue was extracted with CH2Cl2, and the extract was
filtered. The resulting solution was stirred for an additional
20 h at room temperature. Concentration to ca. 5 mL followed
by the addition of 50 mL of diethyl ether precipitated a red
solid, which was washed with diethyl ether and dried in vacuo.
Yield (%), IR data (KBr; ν(CdCdC), ν(PF6-), cm-1), analytical
data, conductivity (acetone, 20 °C, Ω-1 cm2 mol-1), and mass
spectral data (FAB, m/e) are as follows: 63; 1936, 838. Anal.
Calcd for RuC54H43P3F6: C, 64.86; H, 4.33. Found: C, 63.98;
H, 4.33. 102; [M+] ) 855, [M+ - C9H6] ) 741, [M+ - PPh3] )
593, [M+ - C9H6 - PPh3] ) 479.
2
(t, J CP ) 12.9 Hz, RudCR) ppm; ∆δ(C-3a,7a) ) -18.59. 11c:
65; 2.5 h; 77; 838. Anal. Calcd for RuC44H39P3F6O: C, 59.26;
H, 4.40. Found: C, 58.75; H, 4.39. 127; 31P{1H} (CD2Cl2) δ
14.18 (s) ppm; 1H (CD2Cl2) δ 2.79 (s, 3H, OCH3), 5.02 (m, 2H,
PCH2P), 5.45 (t, 1H, J HH ) 2.8 Hz, H-2), 5.72 (d, 1H, J HH
)
2.8 Hz, H-1,3), 5.96 (d, 1H, J HH ) 16.6 Hz, dCH), 6.69-6.87
(m, 5H, dCH, H-4,7 and H-5,6), 7.22-7.49 (m, 25H, Ph) ppm;
13C{1H} (CD2Cl2) δ 49.45 (t, J CP ) 25.1 Hz, PCH2P), 61.99 (s,
OCH3), 76.77 (s, C-1,3), 98.63 (s, C-2), 110.98 (s, C-3a,7a),
124.12 (s, Ind6), 127.04-135.13 (m, Ph, dCH, Ind6), 136.78 (s,
2
dCH), 298.75 (t, J CP ) 11.7 Hz, RudCR) ppm; ∆δ(C-3a,7a) )
-19.72.
Syn th esis of [Ru {dCdCH(CH2OH)}(η5-C9H7)(P P h 3)2]-
[P F 6] (12). A suspension of [RuCl(η5-C9H7)(PPh3)2] (776 mg,
1 mmol), HCtCC(OH)H2 (265 µL, 5 mmol), and NaPF6 (504
mg, 3 mmol) was heated under reflux in 50 mL of MeOH for
20 min. The color progressively changed from red to yellow.
After the mixture was cooled, the solvent was removed under
vacuum, the solid residue was extracted with CH2Cl2, and the
extract was filtered. Concentration of the resulting solution
to ca. 5 mL followed by the addition of 50 mL of diethyl ether
precipitated a yellow solid, which was washed with diethyl
ether and dried in vacuo. Yield (%), IR data (KBr; ν(PF6-),
cm-1), analytical data, conductivity (acetone, 20 °C, Ω-1 cm2
mol-1), and NMR spectroscopic data are as follows: 67; 839.
Anal. Calcd for RuC48H41P3F6O: C, 61.21; H, 4.38. Found:
Ch ar acter ization of [Ru {dCdCH(CHP h OMe)}(η5-C9H7)-
(P P h 3)2][P F 6] (8). To a solution of 30 mg (0.03 mmol) of [Ru-
{dCdCdC(H)Ph}(η5-C9H7)(PPh3)2][PF6] in 1 mL of deuterated
chloroform (in a NMR tube) was added 100 µL of MeOH (2.5
mmol) to quantitatively give complex 8. NMR spectroscopic
2
data are as follows: 31P{1H} (CDCl3) δ 39.47 (d, J PP ) 23.1
2
1
Hz), 39.87 (d, J PP ) 23.1 Hz) ppm; H (CDCl3) δ 2.98 (d, 3H,
J HH ) 3.3 Hz, OCH3), 4.46 (m, 1H, CH), 4.63 (d, 1H, J HH ) 7.0
Hz, dCH), 5.27, 5.46, and 5.64 (sb, 1H each, H-1,2,3), 5.90 (m,
2H, Ind6), 6.75-7.39 (m, 37H, Ph, Ind6) ppm; 13C{1H} (CDCl3)
2
δ 56.18 (s, OCH3), 76.89 (s, CH), 84.91 (d, J CP ) 4.1 Hz, C-1
2
or C-3), 85.39 (d, J CP ) 3.6 Hz, C-1 or C-3), 99.67 (s, C-2),
115.73, 116.49 (s, C-3a,7a), 117.93 (s, dCH), 123.73, 124.10
2
1
(s, Ind6), 127.91-142.33 (m, Ph, Ind6), 343.85 (vt, J CP ) 16.1
C, 60.79; H, 4.58. 111; 31P{1H} (CDCl3) δ 38.44 (s) ppm; H
Hz, RudCR) ppm; ∆δ(C-3a,7a) ) -14.59 (average).
(CDCl3) δ 1.63 (s, 1H, OH), 3.90 (d, 2H, J HH ) 7.5 Hz, CH2),
4.67 (t, 1H, J HH ) 7.5 Hz, dCH), 5.48 (d, 2H, J HH ) 2.2 Hz,
H-1,3), 5.67 (m, 2H, Ind6), 6.28 (t, 1H, J HH ) 2.2 Hz, H-2),
6.76-7.71 (m, 32H, Ph, Ind6) ppm; 13C{1H} (CDCl3) δ 53.77
(s, CH2), 82.16 (s, C-1,3), 99.80 (s, C-2), 113.58 (dCH), 116.07
(s, C-3a,7a), 123.03 (s, Ind6), 128.39-133.88 (m, Ph, Ind6),
344.31 (t, 2J CP ) 16.9 Hz, RudCR) ppm; ∆δ(C-3a,7a) ) -14.63.
Syn th esis of [Ru {dC(OMe)C(H)dCH2}(η5-C9H7)(dppm )]-
[P F 6] (13). A solution of [RuCl(η5-C9H7)(dppm)] (636 mg, 1
mmol), HCtCC(OH)H2 (106 µL, 2 mmol), and NaPF6 (336 mg,
2 mmol) was heated under reflux in 50 mL of MeOH for 45
min. The color progressively changed from red to yellow.
After the mixture was cooled, the solvent wsa removed under
vacuum, the solid residue was extracted with CH2Cl2, and the
extract was filtered. Concentration of the resulting solution
to ca. 5 mL followed by the addition of 50 mL of diethyl ether
precipitated a yellow solid, which was washed with diethyl
Syn t h esis of [R u {CtCCH (OMe)P h }(η5-C9H 7)(P P h 3)2]
(10). A solution of [Ru{dCdCdC(H)Ph}(η5-C9H7)(PPh3)2][PF6]
(999 mg, 1 mmol) in 100 mL of MeOH was treated with K2-
CO3 (1.382 g, 10 mmol) and the mixture stirred at room
temperature for 30 min. The color progressively changed from
red to orange. The solvent was removed under vacuum, the
solid residue was extracted with diethyl ether, and the extract
was filtered. Evaporation of the diethyl ether gave 10 as an
orange solid. Yield (%), IR data (KBr; ν(CtC), cm-1), analyti-
cal data, and NMR spectroscopic data are as follows: 66; 2076.
Anal. Calcd for RuC55H46P2O: C, 74.56; H, 5.23. Found: C,
74.89; H, 5.43. 31P{1H} (C6D6) δ 52.15 (d, 2J PP ) 10.1 Hz), 52.60
2
(d, J PP ) 10.1 Hz) ppm; 1H (C6D6) δ 3.60 (s, 3H, OCH3), 4.65,
4.69, and 5.48 (sb, 1H each, H-1,2,3), 5.57 (s, 1H, CH), 6.40
and 6.68 (m, 2H each, H-4,5,6,7), 6.86-7.84 (m, 35H, Ph) ppm;
2
13C{1H} (C6D6) δ 55.12 (s, OCH3), 74.65 (d, J CP ) 6.2 Hz, C-1

Activation of 2-Propyn-1-ol Derivatives
Organometallics, Vol. 15, No. 8, 1996 2147
2
ether and dried in vacuo. Yield (%), IR data (KBr; ν(PF6-),
cm-1), analytical data, conductivity (acetone, 20 °C, Ω-1 cm2
mol-1), and NMR spectroscopic data are as follows: 80; 835.
Anal. Calcd for RuC38H35P3F6O: C, 55.95; H, 4.32. Found:
Com p lex 3. The function minimized was [w(Fo - Fc2)2/
∑w(Fo2)2]1/2; w ) 1/[σ2(Fo2) + (0.0671P)2], where P ) (Max(Fo2,0)
+ 2Fc )/3, with σ2(Fo2) from counting statistics. The maximum
2
shift to esd ratio in the last full-matrix least-squares cycle was
0.020. The CH2Cl2 solvent molecule, which was affected with
strong structural disorder, was refined as a rigid group with
its hydrogen atoms geometrically placed and refined with fixed
(1.2 times the thermal parameter of the bonded carbon atom)
thermal parameters. The final difference Fourier map showed
no peaks higher than 1.52 e Å-3 (near the disordered CH2Cl2)
1
C, 55.66; H, 4.19. 113; 31P{1H} (CDCl3) δ 14.18 (s) ppm; H
(CDCl3) δ 2.74 (s, 3H, OCH3), 4.69 (d, 1H, J HH ) 17.8 Hz,
dCH2); 5.07 (m, 2H, PCH2P), 5.23 (d, 1H, J HH ) 12.5 Hz,
dCH2), 5.47 (t, 1H, J HH ) 2.4 Hz, H-2), 5.71 (d, 2H, J HH ) 2.4
Hz, H-1,3), 6.15 (dd, 1H, J HH ) 17.8 Hz, J HH ) 12.5 Hz, dCH),
6.10-7.41 (m, 24H, Ph, Ind6) ppm; 13C{1H} (CDCl3) δ 49.67
2
(d, J CP ) 25.3 Hz, PCH2P), 61.76 (s, OCH3), 77.21 (s, C-1,3),
nor deeper than -1.24 e Å-3
.
99.04 (s, C-2), 110.59 (s, C-3a,7a), 113.69 (s, dCH2), 123.79,
127.01 (s, C-4,7 and C-5,6), 129.22-134.56 (m, Ph), 144.60 (s,
Atomic scattering factors were taken from ref 30. Geo-
metrical calculations were made with PARST.31 The crystal-
lographic plots were made with EUCLID.32 All calculations
were performed at the University of Oviedo on the Scientific
Computer Center and X-ray group VAX computers.
2
dCH), 300.59 (t, J CP ) 11.7 Hz, RudCR) ppm; ∆δ(C-3a,7a) )
-20.11.
X-r a y Diffr a ction Stu d ies. Data collection, crystal, and
refinement parameters are collected in Table 3. The unit cell
parameters were obtained from the least-squares fit of 25
reflections (with θ between 10 and 20° (1a ) and 15 and 20°
(3)). Data were collected with the ω-2θ scan technique and
a variable scan rate, with a maximum scan time of 60 s per
reflection. The intensity of the primary beam was checked
throughout the data collection by monitoring three standard
reflections every 60 min. On all reflections, profile analysis23,24
was performed. Lorentz and polarization corrections were
applied, and the data were reduced to |Fo| values. The
structure was solved by DIRDIF25(Patterson methods and
phase expansion). Isotropic least-squares refinement using
SHELX7626,27 converged to R ) 0.121 (1a ) and 0.088 (3). At
this stage an empirical absorption correction was applied using
DIFABS.28 Hydrogen atoms were geometrically placed. Dur-
ing the final stages of the refinement, the positional param-
eters and the anisotropic thermal parameters of the non-H
atoms were refined. The geometrically placed hydrogen atoms
were isotropically refined with a common thermal parameter,
riding on their parent atoms. Finally, a full-matrix least-
squares refinement on F2 was made using SHELXL93.29
Com p lex 1a . The function minimized was [∑w(Fo2 - Fc2)2/
∑w(Fo2)2]1/2; w ) 1/[σ2(Fo2) + (0.1106P)2], where P ) (Max(Fo2,0)
+ 2Fc2)/3 and σ2(Fo2) is taken from from counting statistics.
The maximum shift to esd ratio in the last full-matrix least-
squares cycle was 0.001. The CH2Cl2 solvent molecule was
affected with strong structural disorder. The Cl atoms were
isotropically refined, and one of them (Cl(2)) was found in two
disordered positions (occupation factors 0.57(1) and 0.43(1)).
Its hydrogen atoms were geometrically placed, but two differ-
ent positions were refined, one for each Cl(2) position. The
final difference Fourier map showed no peaks higher than 0.81
Molecu la r Or bita l Ca lcu la tion s. Calculations were car-
ried out at the extended Hu¨ckel level33 on compound 1a , using
as a model [Ru(dCdCdCH2)(η5-C9H7)(PH3)2]+, by the weighted
H
ij formula.34 Standard atomic parameters were taken for H,
C, N, O, and P. The exponents (ú) and the valence shell
ionization potentials (Hii, in eV) for ruthenium were respec-
tively 2.078 and -8.60 for 5s and 2.043 and -5.10 for 5p. A
linear combination of two Slater-type orbitals (ú1 ) 5.378, c1
) 0.5340; ú2 ) 2.303, c2 ) 0.6365) was used to represent the
atomic d orbitals. The Hii value for 4d was set equal to -12.20
eV.
In our structural model the hydrogen atoms replace the
phenyl groups in the phosphine ligands. We optimized the
PH3 and indenyl groups with bond distances C-H ) 1.080 Å,
P-H ) 1.437 Å, and C-C ) 1.421 Å in the five-membered
ring and C-C ) 1.405 Å in the six-membered ring, keeping
the idealized angles.
The calculations were carried out on a MicroVAX 3400
computer at the Scientific Computer Center at the University
of Oviedo, with a locally modified version of the program ICON.
Ack n ow led gm en t. This work was supported by the
Direccio´n General de Investigacio´n Cient´ıfica y Te´cnica
(Project PB93-0325) and the EU (Human Capital Mobil-
ity programme, Project ERBCHRXCT 940501). We
thank the Ministerio de Educacio´n y Ciencia of Spain
(MEC) and Fundacio´n para la Investigacio´n Cient´ıfica
y Te´cnica de Asturias (FICYT) for fellowships to M.G.-
C. and V.C., respectively.
Su p p or tin g In for m a tion Ava ila ble: Crystal structure
data for 1a and 3, including tables of atomic parameters,
anisotropic thermal parameters, bond distances, and bond
angles and plots showing all carbon atoms of the PPh3 ligands
(46 pages). Ordering information is given on any current
masthead page.
e Å-3 nor deeper than -1.01 e Å-3
.
(23) Grant, D. F.; Gabe, E. J . J . Appl. Crystallogr. 1978, 11, 114.
(24) Lehman, M. S.; Larsen, F. K. Acta Crystallogr., Sect. A 1974,
30, 580.
(25) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garc´ıa-Granda, S.; Gould, R. O.; Smits, J . M. M.; Smykalla, C. The
DIRDIF Program System; Technical Report; Crystallographic Labora-
tory, University of Nijmegen: Nijmegen, The Netherlands, 1992.
(26) Sheldrick, G. M. SHELX76: Program for Crystal Structure
Determination; University of Cambridge: Cambridge, U.K., 1976.
(27) van der Maelen Uria, J . F. Ph.D. Thesis, University of Oviedo,
1991.
(28) Walker, N.; Stuart, D. Acta Crystallogr., Sect. A 1983, 39, 158.
(29) Sheldrick, G. M. SHELXL93. In Crystallographic Computing
6; Flack, P., Parkanyi, P., Simon, K., Ed.; IUCr/Oxford University
Press: Oxford, U.K., 1993.
OM9509397
(30) International Tables for X-Ray Crystallography; Kynoch
Press: Birmingham, U.K., 1974; Vol. IV.
(31) Nardelli, M. Comput. Chem. 1983, 7, 95.
(32) Spek, A. L. The EUCLID Package. In Computational Crystal-
lography; Sayre, D., Ed.; Clarendon Press; Oxford, U.K., 1982; p 528.
(33) Hoffmann, R. J . Chem. Phys. 1963, 39, 1397.
(34) Ammeter, J . H.; Bu¨rgi, H.-B.; Thibeault, J .; Hoffmann, R. J .
Am. Chem. Soc. 1978, 100, 3686.